JP2018193476A - Manufacturing method of terminal vinyl group-containing propylene polymer - Google Patents

Abstract

To provide a method for manufacturing a terminal vinyl group-containing propylene polymer low in molecular weight, high in terminal vinyl rate and good in particulate shape at high activity.SOLUTION: Propylene is single polymerized, or propylene and a comonomer selected from a group consisting of ethylene and α-olefin are copolymerized by using a catalyst for olefin polymerization containing following Component (A), Component (B) and Component (C). Component (A): a metallocene compound represented by the general formula (1). Component (B): a compound forming an ion pair by reacting with the Component (A) or an ion exchangeable layering silicate. Component (C): an organic aluminum compound. The resulting terminal vinyl group-containing propylene polymer has following properties (I) and (II). Property (I) number average molecular weight measured by GPC is smaller than 50,000. Property (II) terminal vinyl rate is 0.7 or more.SELECTED DRAWING: None

Description

  The present invention relates to a method for producing a terminal vinyl group-containing propylene polymer, and more particularly to a method for producing a terminal vinyl group-containing propylene polymer having a low molecular weight, high stereoregularity, and good particle properties.

Polypropylene is widely used as a daily life component, industrial component, etc. because of its high chemical stability, excellent mechanical properties, and low cost. Furthermore, attempts have been made to increase the functionality of polypropylene having an unsaturated bond by utilizing the reactivity resulting from the unsaturated bond. A terminal vinyl group-containing propylene polymer (terminal vinyl group-containing polypropylene polymer) is expected to be used as a macromer and as a raw material for functionalization.
The terminal vinyl group-containing propylene-based polymer is considered to cause a polymer growth termination reaction by causing β-methyl elimination instead of normal β-hydrogen elimination in the polymerization reaction of propylene (see Non-Patent Document 1). ). However, under the polymerization conditions (catalyst components, etc.) that cause β-methyl elimination disclosed in Non-Patent Document 1, only an atactic propylene polymer having no stereoregularity can be obtained. Was sacrificed.
As a method for obtaining a propylene polymer having a terminal vinyl group having stereoregularity, a method using a chiral stereorigid transition metal compound represented by dimethylsilylene bis (2-methyl-4-phenylindenyl) zirconium dichloride (patent) (Refer to claim 10 of Non-patent Document 2) and rac-dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4-phenyl-indenyl}] hafnium. A method using a metallocene compound having a bridged indene ring having a heterocyclic ring constituting a 5-membered ring at the 2-position of the indene ring and having an aryl group at the 4-position (see claim 1 of Patent Document 2) has been proposed. .

By the way, it is considered that a compound obtained by functionalizing a terminal vinyl group-containing propylene polymer is suitable for applications such as paints and primers. In such applications, the terminal vinyl group-containing propylene polymer and the compound obtained by functionalizing the terminal vinyl group-containing propylene polymer are soluble in a solvent and have high affinity with other base materials. Is preferred. In order to improve solubility in solvents and affinity with other substrates, terminal vinyl group-containing propylene polymers and compounds functionalized with terminal vinyl group-containing propylene polymers must have a low molecular weight. Is desirable.
In the method of Patent Document 1, the number average molecular weight (Mn) is 2,000 Dalton to 50,000 Dalton, and the total number of vinyl groups per 1,000 carbon atoms is 7000 ÷ Mn or more. It is said that a terminal vinyl group-containing propylene-based polymer having the following is obtained. However, this method requires slurry polymerization at a relatively high temperature and low pressure in order to obtain a terminal vinyl structure with high selectivity. Under such polymerization conditions, the produced propylene polymer does not have a sufficiently high stereoregularity.
In the method of Patent Document 2, a terminal vinyl group-containing propylene polymer having high stereoregularity is obtained. However, in the method of Patent Document 2, for example, as can be seen from the fact that the number average molecular weight of all Examples exceeds 50,000, Patent Document 2 efficiently produces a terminal vinyl group-containing propylene polymer having a low molecular weight. It cannot be said that the method to do is described.

JP-T-2001-525461 JP 2009-299046 A

J. et al. Am. Chem. Soc. 114, 1992, 1025-1032 Resconi Macromol. Rapid Commun. 2000, 21, 1103-1107

When the present inventors examined the manufacturing method of the terminal vinyl group containing propylene polymer by patent document 2, it was the method of patent document 2, and the terminal vinyl group containing propylene polymer with low molecular weight and high stereoregularity was carried out. In order to manufacture, it has been found that there are problems to be solved.
For example, in bulk polymerization, the chain transfer reaction must be relatively increased by polymerization at a high temperature, and there is a problem that the shape and properties of the polymer particles are deteriorated.
In addition, in the slurry polymerization, propylene is used at a low pressure to polymerize relatively to suppress the growth reaction, and there is a problem that the polymerization activity is halved.
Accordingly, an object of the present invention is to provide a method for producing a terminal vinyl group-containing propylene polymer having a low molecular weight, a high terminal vinyl ratio, and good particle properties with high activity.

The method for producing a terminal vinyl group-containing propylene polymer of the present invention comprises propylene homopolymerization or propylene using an olefin polymerization catalyst containing the following component (A), component (B) and component (C). And a comonomer selected from the group consisting of ethylene and α-olefin, to produce a propylene-based polymer having the following characteristics (I) and (II).
Characteristic (I) Number average molecular weight measured by GPC is less than 50,000 Characteristic (II) Terminal vinyl ratio is 0.7 or more Component (A): Metallocene compound represented by the following general formula (1)

[R ¹¹ and R ¹² are each independently a heterocyclic group constituting a 5-membered ring having at least one hydrocarbon group having 3 or more carbon atoms which may have a hetero atom as a substituent (provided that the 5-membered The hetero atom of the heterocyclic group constituting the ring is not directly bonded to the alkadienyl group.
R ¹³ and R ¹⁴ are each independently an aryl group having a substituent only at the 4-position, and the substituent contains at least one atom selected from the group consisting of a hetero atom and a halogen atom. Or a hydrocarbon group having 3 to 6 carbon atoms.
X ¹¹ and Y ¹¹ are independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms. Represents an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, an amino group, or a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms.
Q ¹¹ has a divalent hydrocarbon group having 1 to 20 carbon atoms, a silylene group that may have a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms. Represents an optionally germinylene group.
However, the substituent of the heterocyclic group constituting the 5-membered ring is not the same as the substituent of the aryl group, and the substituent having the largest total number of carbon atoms and heteroatoms among the substituents of the heterocyclic group. The total number of groups is larger than the total number of carbon atoms and heteroatoms that the substituents of the aryl group have. ]
Component (B): Compound that reacts with component (A) to form an ion pair or ion-exchangeable layered silicate component (C): Organoaluminum compound

In the method for producing a terminal vinyl group-containing propylene polymer of the present invention, in the metallocene compound represented by the general formula (1), R ¹¹ and R ¹² are independently the following general formula (2-1): , (2-2) or (2-3).

[R ²¹ and R ²² are each independently a hydrogen atom or a hydrocarbon group having 3 or more carbon atoms which may have a hetero atom, and at least one of R ²¹ and R ²² has a hetero atom. Represents a hydrocarbon group having 3 or more carbon atoms. However, the hetero atom of the hydrocarbon group is not directly bonded to the heterocyclic group constituting the 5-membered ring. R ²¹ and R ²² are not bonded to form a ring. ]

In the method for producing a terminal vinyl group-containing propylene polymer of the present invention, in the metallocene compound represented by the general formula (1), R ¹¹ and R ¹² independently have a substituent only at the 5-position. A heterocyclic group constituting a member ring, wherein the substituent is a hydrocarbon group having 3 or more carbon atoms which may have a hetero atom (provided that the hetero atom of the heterocyclic group constituting the 5-member ring) Are not directly bonded to the alkadienyl group).

The method for producing a terminal vinyl group-containing propylene-based polymer according to the present invention includes the metallocene compound represented by the general formula (1), wherein the heterocyclic group represented by R ¹¹ and R ¹² is tertiary carbonized as a substituent. It is preferable that the aryl group having a hydrogen group and represented by R ¹³ and R ¹⁴ has a secondary hydrocarbon group as a substituent.

In the method for producing a terminal vinyl group-containing propylene polymer of the present invention, the propylene polymer preferably further has the following property (III).
Characteristic (III) The amount of coarse powder is 1 mass% or less In the method for producing a terminal vinyl group-containing propylene polymer of the present invention, the propylene polymer preferably further has the following characteristic (IV).
Characteristic (IV) Melting point (Tm) is less than 153 ° C. In the method for producing a terminal vinyl group-containing propylene polymer of the present invention, the amount of hydrogen used during polymerization exceeds 0 as a feed mass ratio of propylene. It is preferably × 10 ⁻⁴ or less.

  According to the present invention, it is possible to provide a method for producing a terminal vinyl group-containing propylene polymer having a low molecular weight, a high terminal vinyl ratio, and good particle properties with high activity.

It is a figure explaining the baseline and section of a chromatogram in GPC.

The method for producing a terminal vinyl group-containing propylene polymer of the present invention comprises propylene homopolymerization or propylene using an olefin polymerization catalyst containing the following component (A), component (B) and component (C). And a comonomer selected from the group consisting of ethylene and α-olefin, to produce a propylene-based polymer having the following characteristics (I) and (II).
Characteristic (I) Number average molecular weight measured by GPC is less than 50,000 Characteristic (II) Terminal vinyl ratio is 0.7 or more Component (A): Metallocene compound represented by the following general formula (1)

[R ¹¹ and R ¹² are each independently a heterocyclic group constituting a 5-membered ring having at least one hydrocarbon group having 3 or more carbon atoms which may have a hetero atom as a substituent (provided that the 5-membered The hetero atom of the heterocyclic group constituting the ring is not directly bonded to the alkadienyl group.
R ¹³ and R ¹⁴ are each independently an aryl group having a substituent only at the 4-position, and the substituent contains at least one atom selected from the group consisting of a hetero atom and a halogen atom. Or a hydrocarbon group having 3 to 6 carbon atoms.
X ¹¹ and Y ¹¹ are independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms. Represents an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, an amino group, or a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms.
Q ¹¹ has a divalent hydrocarbon group having 1 to 20 carbon atoms, a silylene group that may have a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms. Represents an optionally germinylene group.
However, the substituent of the heterocyclic group constituting the 5-membered ring is not the same as the substituent of the aryl group, and the substituent having the largest total number of carbon atoms and heteroatoms among the substituents of the heterocyclic group. The total number of groups is larger than the total number of carbon atoms and heteroatoms that the substituents of the aryl group have. ]
Component (B): Compound that reacts with component (A) to form an ion pair or ion-exchangeable layered silicate component (C): Organoaluminum compound

The present invention is described in detail below.
1. Olefin polymerization catalyst (1) Component (A)
Component (A) is a metallocene compound represented by the general formula (1).
In the general formula (1), R ¹¹ and R ¹² are each independently a heterocyclic group constituting a 5-membered ring having a hydrocarbon group having 3 or more carbon atoms which may have a hetero atom as a substituent. However, the hetero atom of the heterocyclic group constituting the 5-membered ring is not directly bonded to the alkadienyl group.
In R ¹¹ and R ¹² , the direction of propylene to be inserted is regularly controlled by introducing a substituent having an appropriate size onto the heterocyclic group. Further, this substituent makes it easy for the methyl group at the β-position of the growing polymer chain to be directed to the vacant coordination field on the transition metal, so that the β-methyl elimination reaction is likely to proceed, and a polypropylene having a terminal vinyl group introduced with high selectivity. Can be obtained.

R ¹¹ and R ¹² are preferably the same as each other.
Also, R ¹¹ and R ^12, the carbon adjacent to the heterocyclic groups heteroatoms that constitute the five-membered ring, is preferably connected to an alkadienyl group in the general formula (1).
The hydrocarbon group may have 3 or more carbon atoms, preferably 7 or less, more preferably 6 or less, still more preferably 5 or less, and particularly preferably 4.
In addition, examples of the hetero atom include silicon, oxygen, sulfur, nitrogen, boron, and phosphorus, which may be present in the carbon chain and interposed between carbon-carbon bonds.
R ¹¹ and R ¹² are each independently a heterocyclic group constituting a 5-membered ring having a substituent only at the 5-position, and the substituent may have a heteroatom having 3 carbon atoms. The above hydrocarbon group is preferable (however, the hetero atom of the heterocyclic group constituting the 5-membered ring is not directly bonded to the alkadienyl group).
The hydrocarbon group having 3 or more carbon atoms as a substituent of the heterocyclic group may be any of alkyl, cycloalkyl, and aromatic hydrocarbon groups, but is preferably a tertiary hydrocarbon group.

As a preferable structure of R ¹¹ and R ^12, a structure of a hetero 5-membered ring represented by any of the following general formulas (2-1), (2-2), or (2-3) can be given.

[R ²¹ and R ²² are each independently a hydrocarbon group having 3 or more carbon atoms which may have a hydrogen atom or a hetero atom, and at least one of R ²¹ and R ²² may have a hetero atom. It represents a good hydrocarbon group having 3 or more carbon atoms. However, the hetero atom of the hydrocarbon group is not directly bonded to the heterocyclic group constituting the 5-membered ring. R ²¹ and R ²² are not bonded to form a ring. ]

As preferable examples of R ²¹ and R ²² , R ²¹ is i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, n-hexyl, cyclopropyl, cyclopentyl, cyclohexyl, phenyl. Group, furyl group, particularly preferably t-butyl, and R ²² is preferably a hydrogen atom.

In the general formula (1), R ¹³ and R ¹⁴ are each independently an aryl group having a substituent only at the 4-position, and the substituent is at least one selected from the group consisting of a hetero atom and a halogen atom. It is a C3-C6 hydrocarbon group which may contain these atoms.
R ¹³ and R ¹⁴ are preferably the same as each other.
The aryl group is preferably a phenyl group.
Examples of heteroatoms include silicon, oxygen, sulfur, nitrogen, boron, and phosphorus.
When the hydrocarbon group contains a hetero atom, the hetero atom may be present in the carbon chain and interposed between carbon-carbon bonds.
The halogen atom may be any of a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
The hydrocarbon group may have 3 to 6 carbon atoms, preferably 5 or less, more preferably 4 or less, and still more preferably 3.
The hydrocarbon group having 3 to 6 carbon atoms as the substituent for the aryl group may be any of alkyl, cycloalkyl, and aromatic hydrocarbon groups, but is preferably a secondary hydrocarbon group.

A preferred structure of R ¹³ and R ¹⁴ includes a structure having a substituent at the 4-position on the phenyl group represented by the following general formula (3).
^4-R 31 -Ph- ··· formula (3)
[R ³¹ is a hydrocarbon group having 3 to 6 carbon atoms which may contain at least one atom selected from the group consisting of a hetero atom and a halogen atom. However, R ³¹ is different from R ²¹ and R ²² . ]
Preferred examples of R ³¹ are i-propyl, n-butyl, i-butyl, s-butyl, trimethylsilyl, n-pentyl, n-hexyl, cyclopropyl, cyclopentyl, cyclohexyl, phenyl group, furyl group, especially I-propyl is preferred.

In the present invention, the substituent of the heterocyclic group constituting the 5-membered ring and the substituent of the aryl group are not the same, and among the substituents of the heterocyclic group, the total number of carbon atoms and heteroatoms is The total number of the largest substituents is larger than the total number of carbon atoms and heteroatoms that the substituents of the aryl group have.
That is, when there are a plurality of non-identical substituents on the heterocyclic group (R ¹¹ and R ¹² ) (for example, when the substituents having different structures are present at the 4-position and 5-position on the heterocyclic group) The total number of carbon atoms and heteroatoms of the substituent having the largest total number of carbon atoms and heteroatoms of the substituent, and the total number of carbon atoms and heteroatoms of the substituent on the aryl group When compared, the total number of the substituent having the largest total number of carbon atoms and heteroatoms on the heterocyclic group is the total number of carbon atoms and heteroatoms of the substituent on the aryl group. Bigger than.
In addition, when only one substituent exists on the heterocyclic group, the substituent is the substituent having the maximum total number. Moreover, the substituent of the heterocyclic group and the substituent of the aryl group may not have a hetero atom, and when there is no hetero atom, the number of hetero atoms is zero. Furthermore, the substituent of the aryl group may not have a carbon atom, and when it does not have a carbon atom, the number of carbon atoms is zero.
As a preferred specific example, the substituents on the heterocyclic groups R ¹¹ and R ¹² are t-butyl groups (4 carbon atoms and 0 heteroatoms and the total number is 4), and R ¹³ is an aryl group. And the 4-position substituent on R ¹⁴ is an i-propyl group (3 carbon atoms and 0 heteroatoms with a total number of 3).

The present invention provides a method for producing a highly active terminal vinyl group-containing propylene polymer having a low molecular weight, a high terminal vinyl ratio, and good particle properties.
The reason why high activity is obtained is not necessarily clear, but by introducing a substituent having 3 or more carbon atoms onto R ¹³ and R ¹⁴ that are aryl groups, the electron density of the transition metal changes, thereby propylene. It is considered that the rate of reaction for insertion into the substrate increases and the growth rate increases.
In addition, as another function of increasing the activity, the substituent on the aryl group can cause the polymer chain to grow due to its bulkiness. Turn to avoid. As a result, the orientation of the next propylene inserted is controlled by both the growing polymer chain oriented to avoid this 6-membered ring moiety and also by the heterocyclic groups R ¹¹ and R ¹² , and the position and stereoregulation. Propylene insertion is performed.
At this time, the heterocyclic groups R ¹¹ and R ¹² simultaneously improve the efficiency of the terminal vinyl group by increasing the β-position methyl group elimination reaction by simultaneously controlling the orientation of the β-position methyl group of the growing polymer chain. Both steric and regioregularity is controlled by a combination of substituents on aryl groups R ¹³ and R ¹⁴ and substituents on heterocyclic groups R ¹¹ and R ^12. Yes.
Eventually, both the growth reaction rate and the β-methyl elimination reaction rate are controlled by the combined effect of each substituent, thereby creating a polymer chain of a specific length, that is, a polymer of a specific molecular weight. It is done.
Therefore, in the present invention, the growth reaction can be achieved by combining the substituents on the heterocyclic groups R ¹¹ and R ¹² and the substituents on the aryl groups R ¹³ and R ¹⁴ with specific substituents. By balancing the termination reaction by β-methyl elimination, a terminal vinyl group-containing propylene polymer having a specific molecular weight (number average molecular weight of less than 50,000) can be obtained with high regularity and high activity.

X ¹¹ and Y ¹¹ are each independently a ligand that forms a σ bond with Hf, and together with the component (B) and the component (C), generates an active metallocene having olefin polymerization ability.
Therefore, as long as this object is achieved, X ¹¹ and Y ¹¹ are not limited in the type of ligand.
X ¹¹ and Y ¹¹ are independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms. , An oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, an amino group, or a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms. From the viewpoint of the stability of the metallocene compound, a halogen atom, a carbon number of 1 to 20 Are preferred, with chlorine, bromine, methyl, ethyl, isopropyl and phenyl being particularly preferred.

Q ¹¹ has a divalent hydrocarbon group having 1 to 20 carbon atoms and a hydrocarbon group having 1 to 20 carbon atoms, which may contain a divalent halogen, bonding two five-membered rings. It represents a silylene group or a germylene group which may be present.
When two hydrocarbon groups are present on the above-mentioned silylene group or germylene group, they may be bonded to each other to form a ring structure.
Specific examples of Q ¹¹ include alkylene groups such as methylene, methylmethylene, dimethylmethylene, 1,2-ethylene;
Arylalkylene groups such as diphenylmethylene;
A silylene group;
Alkylsilylene groups such as methylsilylene, dimethylsilylene, diethylsilylene, di (n-propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene;
(Alkyl) (aryl) silylene groups such as methyl (phenyl) silylene;
Arylsilylene groups such as diphenylsilylene;
Alkyl oligosilylene groups such as tetramethyldisilylene;
Germylene group;
An alkylgermylene group obtained by replacing silicon of a silylene group having a divalent hydrocarbon group having 1 to 20 carbon atoms with germanium;
(Alkyl) (aryl) germylene group;
Examples thereof include an arylgermylene group.
In these, the silylene group which has a C1-C20 hydrocarbon group, or the germylene group which has a C1-C20 hydrocarbon group is preferable, and an alkylsilylene group and an alkylgermylene group are especially preferable.

As preferable compounds among the compounds represented by the general formula (1), the following compounds can be exemplified.
(1) Dichloro [1,1′-dimethylsilylenebis {2- (5-tert-butyl-2-furyl) -4- (4-isopropyl-phenyl) -indenyl}] hafnium (2) Dichloro [1,1 '-Dimethylsilylenebis {2- (5-phenyl-2-furyl) -4- (4-isopropyl-phenyl) -indenyl}] hafnium (3) dichloro [1,1'-dimethylsilylenebis {2- (5 -T-butyl-4-methyl-2-furyl) -4- (4-isopropyl-phenyl) -indenyl}] hafnium

(2) Component (B)
Component (B) is a compound or ion-exchange layered silicate that reacts with component (A) to form an ion pair.
A component (B) may be individual and may use 2 or more types. Ion exchange layered silicate is preferable.

(2-1) Compound that forms an ion pair with component (A) Examples of the compound that reacts with component (A) to form an ion pair include an aluminum oxy compound and a boron compound. Specific examples include compounds represented by the following general formulas (I) to (III).

In the above general formulas (I) and (II), R ^a represents a hydrogen atom or a hydrocarbon group, preferably a hydrocarbon group having 1 to 10 carbon atoms, particularly preferably a hydrocarbon group having 1 to 6 carbon atoms. . Moreover, several ^Ra may be same or different, respectively. P represents an integer of 0 to 40, preferably 2 to 30.
The compounds represented by the general formulas (I) and (II) are compounds that are also referred to as aluminoxanes. 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.
In the general formula (III), R ^b represents a hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms. The compound represented by the general formula (III) is 10: 1 to 1 type of trialkylaluminum or two or more types of trialkylaluminum and an alkylboronic acid represented by the general formula R ^b B (OH) ₂ . It can be obtained by a 1: 1 (molar ratio) reaction.
As the boron compound, a complex of a cation such as a carbonium cation or an ammonium cation with an organic boron compound such as triphenylboron, tris (3,5-difluorophenyl) boron, or tris (pentafluorophenyl) boron, or Various organoboron compounds such as tris (pentafluorophenyl) boron can be mentioned.

(2-2) Ion-exchangeable layered silicate Ion-exchangeable layered silicate (hereinafter sometimes abbreviated as silicate) is a structure in which layers composed of ionic bonds and the like are stacked in parallel with each other by a binding force. This refers to a silicate compound having a crystal structure, having interlayer ions between layers, and capable of exchanging interlayer ions contained therein.
Most silicates are naturally produced mainly as the main component of clay minerals. Generally, it is dispersed / swelled in water and purified by the difference in sedimentation speed, etc., but it is not necessary that the impurities are completely removed, and impurities other than the ion-exchange layered silicate (quartz) , Cristobalite, etc.). Depending on the type, amount, particle size, crystallinity, and dispersion state of these impurities, it may be preferable to pure silicate, and such a complex is also included in the ion-exchange layered silicate of component (B). .
Further, the silicate used in the present invention is not limited to a natural product, and may be an artificial synthetic product.

Specific examples of the ion-exchange layered silicate include, for example, layered silicates having a 1: 1 type structure or a 2: 1 type structure described in Haruo Shiramizu “Clay Mineralogy” Asakura Shoten (1988) and the like. Can be mentioned.
The 1: 1 type structure indicates a structure based on a stack in which a single-layer tetrahedral sheet and a single-layer octahedral sheet are combined as described in the above-mentioned “clay mineralogy”.
The 2: 1 type structure refers to a structure based on a stack in which two layers of tetrahedral sheets sandwich one layer of octahedral sheets.
Specific examples of the ion-exchange layered silicate having a 1: 1 type structure include kaolin silicates such as dickite, nacrite, kaolinite, metahalloysite, and halloysite, and serpentine group silicates such as chrysotile, lizardite, and antigolite. Examples include salts.
Specific examples of ion-exchange layered silicate having a 2: 1 type structure include smectite silicates such as montmorillonite, beidellite, nontronite, saponite, hectorite, stevensite, vermiculite silicates such as vermiculite, mica , Mica group silicates such as illite, sericite, sea chlorite, attapulgite, sepiolite, palygorskite, bentonite, pyrophyllite, talc, chlorite group and the like. These may form a mixed layer.
Among these, the main component is preferably an ion-exchange layered silicate having a 2: 1 type structure. More preferably, the main component is a smectite group silicate, and still more preferably, the main component is montmorillonite.
The type of interlayer cation (cation contained between the layers of the ion-exchange layered silicate) is not particularly limited, but as a main component, alkali metal of the first group of the periodic table such as lithium and sodium, calcium, magnesium, etc. Alkaline earth metals of Group 2 of the periodic table, or transition metals such as iron, cobalt, copper, nickel, zinc, ruthenium, rhodium, palladium, silver, iridium, platinum, and gold are relatively easily available. It is preferable in a certain point.

(2-3) Treatment of ion-exchangeable layered silicate The ion-exchangeable layered silicate may be used in a dry state or in a slurry state in a liquid.
In addition, the shape of the ion-exchange layered silicate is not particularly limited, and may be a naturally produced shape, a shape when artificially synthesized, or a shape by operations such as pulverization, granulation, and classification. You may use the processed ion exchange layered silicate.
Of these, the granulated ion-exchange layered silicate is particularly preferable because it gives good polymer particle properties when the ion-exchange layered silicate is used as a catalyst component.
Regarding the treatment method of the ion-exchange layered silicate, reference can be made to the description in paragraphs 0042 to 0071 of JP-A-2009-299046.

The component (B) preferably used in the present invention is a chemically treated ion exchange layered silicate having an Al / Si atomic ratio of 0.01 to 0.25, preferably 0.03 to 0.24. And more preferably in the range of 0.05 to 0.23. The Al / Si atomic ratio is considered to be an index of the acid treatment strength of the clay portion.
Aluminum and silicon in the ion-exchange layered silicate are measured by a method of preparing a calibration curve by a chemical analysis method by JIS method and quantifying with a fluorescent X-ray.

(3) Component (C)
Component (C) used in the present invention is an organoaluminum compound, and preferably an organoaluminum compound represented by the following general formula (4) is used.
_{(AlR n X 3-n)} m ··· formula (4)
[In said general formula (4), R represents a C1-C20 alkyl group, X represents a halogen, hydrogen, an alkoxy group, or an amino group, n is 1-3, m is 1-2. Each represents an integer. ]
The organoaluminum compounds can be used alone or in combination.
Specific examples of the organoaluminum compound include trimethylaluminum, triethylaluminum, trinormalpropylaluminum, trinormalbutylaluminum, triisobutylaluminum, trinormalhexylaluminum, trinormaloctylaluminum, trinormaldecylaluminum, diethylaluminum chloride, diethylaluminum. Examples thereof include sesquichloride, diethylaluminum hydride, diethylaluminum ethoxide, diethylaluminum dimethylamide, diisobutylaluminum hydride, and diisobutylaluminum chloride. Of these, trialkylaluminum and alkylaluminum hydride with m = 1 and n = 3 are preferable. More preferably, R is a trialkylaluminum having 1 to 8 carbon atoms.

(4) Preparation of catalyst The catalyst for olefin polymerization preferably used in the present invention comprises the above component (A), component (B) and component (C). These can be obtained by contacting them inside or outside the polymerization vessel. The olefin polymerization catalyst may be subjected to prepolymerization in the presence of olefin.
The usage-amount of a component (A), a component (B), and a component (C) is arbitrary.
For example, the usage-amount of the component (A) with respect to a component (B) becomes like this. Preferably it is 0.1 micromol-1000 micromol with respect to 1 g of components (B), More preferably, it is the range of 0.5 micromol-500 micromol.
Moreover, the usage-amount of the component (C) with respect to a component (A) is the molar ratio of the aluminum of the component (C) with respect to the transition metal of a component (A), Preferably it is 0.01-5 * 10 < ⁶ >, More preferably, it is 0. .1 to 1 × 10 ⁴ range.
The order in which the component (A), the component (B), and the component (C) are contacted is arbitrary, and after contacting two of these components, the remaining one component may be contacted, The components may be contacted simultaneously. In these contacts, a solvent may be used for sufficient contact. Examples of the solvent include aliphatic saturated hydrocarbons, aromatic hydrocarbons, aliphatic unsaturated hydrocarbons, halides thereof, and prepolymerized monomers. Specific examples of the aliphatic saturated hydrocarbon and the aromatic hydrocarbon include hexane, heptane, toluene and the like. Moreover, as a prepolymerization monomer, propylene can be used as a solvent.

(5) Prepolymerization It is preferable that the olefin polymerization catalyst is subjected to prepolymerization consisting of a small amount of polymerization by contacting an olefin. Preliminary polymerization can improve the catalyst activity, and can suppress the production cost.
Although the olefin to be used is not particularly limited, ethylene, propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, 3-methyl-1-butene, vinylcycloalkane, styrene, and the like can be used. A propylene is preferable, and propylene is preferable.
The olefin feed method may be any method such as a feed method for maintaining the olefin at a constant speed or constant pressure in the prepolymerization tank, a combination thereof, or a stepwise change.
The prepolymerization temperature and the prepolymerization time are not particularly limited, but are preferably in the range of −20 ° C. to 100 ° C. and 5 minutes to 24 hours, respectively.
The mass ratio of the prepolymerized polymer to the component (B) is preferably 0.01 to 100, and more preferably 0.1 to 50.
Moreover, a component (C) can also be added at the time of prepolymerization.
A method of coexisting a polymer such as polyethylene or polypropylene and a solid of an inorganic oxide such as silica or titania at the time of contacting or after the contact of the above components is also possible.
The catalyst may be dried after the prepolymerization. The drying method is not particularly limited, but examples include drying under reduced pressure, heat drying, and drying by circulating a drying gas. These methods may be used alone or in combination of two or more methods. It may be used. In the drying step, the catalyst may be stirred, vibrated, fluidized, or allowed to stand.

2. Monomer The monomer to be used is propylene alone or a combination of propylene and a comonomer selected from the group consisting of ethylene and α-olefin.
As the α-olefin, for example, an α-olefin having 4 to 10 carbon atoms can be used. More specifically, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, 3-methyl-1-butene, vinylcyclohexane, styrene and the like can be exemplified. The ethylene and / or α-olefin copolymerized with propylene may be one kind or a combination of two or more kinds. Preferably, it is 1 type or 2 types chosen from ethylene and 1-butene.
The copolymerization ratio of propylene and a comonomer selected from the group consisting of ethylene and α-olefin is not particularly limited, but is usually 0.1 to 7 mol%.

3. Polymerization Method In the present invention, any mode can be adopted as long as the olefin polymerization catalyst and the monomer come into contact efficiently. Specifically, a slurry method using an inert solvent, a bulk polymerization method using propylene as a solvent without substantially using an inert solvent, or a gas phase polymerization method for maintaining each monomer in a gaseous state without using a liquid solvent. Etc. can be adopted.
As the polymerization method, a method of performing continuous polymerization, batch polymerization, or prepolymerization is also applied.
Further, the number of polymerization stages may be one, and a mode such as two stages of bulk polymerization, gas phase polymerization after bulk polymerization, and two stages of gas phase polymerization is also possible, and it is possible to produce with more polymerization stages. .
Among these, it is preferable to perform one-stage bulk polymerization using propylene as a solvent.

The polymerization temperature is preferably 0 to 90 ° C, more preferably 60 to 85 ° C, and further preferably 70 to 80 ° C.
The polymerization pressure is preferably 0 to 5 MPaG, more preferably 0 to 4 MPaG.

In the case of the production method disclosed in Patent Document 2 (Japanese Patent Application Laid-Open No. 2009-299046) described above, terminal vinyl having a low molecular weight is obtained by relatively increasing the β-methyl elimination reaction rate by performing bulk polymerization at a higher temperature. A group-containing polypropylene can be obtained, but on the other hand, local heat generation cannot be removed, and the grown particles collapse to generate fine powder. In addition, the growing particles are fused together to form aggregates and lumps, which exceeds the critical temperature of propylene as a solvent. As a result, there has been a problem that the shape and properties of the polymer particles are deteriorated.
In response to such a problem, the present invention has a structure of a bisindenyl hafnium complex, a 5-membered heterocycle having a specific substituent at the 2-position of the indene ring as a ligand, and the indene ring By using a catalyst system containing a metallocene compound substituted with an aryl group having a specific substituent at the 4-position, polymerizing in a temperature range suitable for bulk polymerization, the shape and properties of the polymer are good at a specific molecular weight or less. Terminal vinyl group-containing polypropylene can be obtained.
Furthermore, hydrogen can be used supplementarily during the polymerization process in order to improve the activity.
The reason why the activity is improved is considered to be a dormant active site, for example, a π-allyl-transition metal complex as a side reaction or just after 2,1 insertion of propylene. It is thought to be activated.
Many transition metal complex catalysts have a high rate of chain transfer to hydrogen and function as an effective chain transfer agent to produce a saturated end, making it difficult to produce a terminal vinyl structure.
However, in the production method of the present invention, surprisingly, even when hydrogen is added, the effect as a chain transfer agent is poor, and the vinyl end ratio is still kept high due to the reactivation.
Therefore, in the production method of the present invention, by using hydrogen as an auxiliary during the polymerization step, the activity is improved and the vinyl end ratio is kept high.

The amount of hydrogen used in the polymerization, hydrogen as the feed mass ratio of propylene, 0 to 2.0 × ^{10 -4,} preferably 2.0 × ^{10 -4} or less than 0, more preferably 2.0 × It is in the range of 10 ^{−5 to} 1.5 × 10 ⁻⁴ , more preferably 3.0 × 10 ^{−5 to} 1.0 × 10 ⁻⁴ .
When performing bulk polymerization, the concentration of the gas phase part is on average 0 to 10000 ppm, preferably 100 to 8000 ppm, more preferably 200 to 1000 ppm. Can be obtained.

4). Terminal vinyl group-containing propylene polymer The terminal vinyl group-containing propylene polymer produced according to the present invention is a propylene homopolymer or a copolymer of propylene and a comonomer selected from the group consisting of ethylene and α-olefin. is there.
According to the present invention, by using the propylene polymerization catalyst described above and producing a terminal vinyl group-containing propylene polymer having a small molecular weight, the terminal vinyl has a high terminal vinyl ratio and also has a good polymer shape and properties. A group-containing propylene polymer can be produced with high activity.
Hereinafter, the terminal vinyl group-containing propylene polymer produced according to the present invention will be described.

(1) Number average molecular weight The terminal vinyl group-containing propylene polymer produced by the present invention has the following property (I).
Characteristic (I): Number average molecular weight measured by GPC is less than 50,000 The terminal vinyl group-containing propylene polymer of the present invention has a number average molecular weight (Mn) of less than 50,000, preferably 40,000 or less. Yes, more preferably 30,000 or less. Within the above range, the polymerization activity can be increased. Further, since the amount of the terminal vinyl group per unit mass is increased, the resulting propylene polymer also has a secondary effect that a sufficient amount of functional groups can be introduced by modification.
On the other hand, the number average molecular weight (Mn) is preferably 50,000 or more, more preferably 10,000 or more, and further preferably 15,000 or more. In the above range, the particle properties are good.
In the present invention, as a polymerization catalyst component, a 5-membered heterocyclic ring having a structure of a bisindenyl hafnium complex and having a specific substituent at the 2-position of the indene ring, which is a ligand, and 4 of the indene ring A metallocene compound substituted with an aryl group having a specific substituent at the position is used. Since the metallocene compound with this specific structure has a fast β-methyl elimination reaction rate, it is a terminal vinyl having a low molecular weight at a relatively low temperature. A group-containing propylene polymer can be easily obtained. The elimination reaction rate can also be controlled by changing the polymerization temperature, propylene concentration, and pressure. For example, in the complexes shown in the examples, the number average molecular weight (Mn) can be decreased as the polymerization temperature increases.

Here, the value of the number average molecular weight (Mn) is obtained by gel permeation chromatography (GPC), and the details of the measuring method and measuring instrument are as follows.
Equipment: GPC manufactured by Waters (ALC / GPC, 150C)
Detector: MIRAN, 1A, IR detector manufactured by FOXBORO (measurement wavelength: 3.42 μm)
Column: AD806M / S (3 pieces) manufactured by Showa Denko KK
Mobile phase solvent: o-dichlorobenzene (ODCB)
Measurement temperature: 140 ° C
Flow rate: 1.0 mL / min Injection rate: 0.2 mL

The sample was prepared by preparing a 1 mg / mL solution using the sample and ODCB (containing 0.5 mg / mL dibutylhydroxytoluene (BHT)), and taking about 1 hour at 140 ° C. To do.
The baseline and section of the obtained chromatogram are performed as shown in FIG.
Further, the conversion from the retention capacity obtained by GPC measurement to the molecular weight is performed using a standard curve prepared in advance by standard polystyrene. The standard polystyrenes used are all the following brands manufactured by Tosoh Corporation.
Brand: F380, F288, F128, F80, F40, F20, F10, F4, F1, A5000, A2500, A1000
Inject 0.2 mL of a solution dissolved in ODCB (containing 0.5 mg / mL BHT) so that each is 0.5 mg / mL to create a calibration curve. The calibration curve uses a cubic equation obtained by approximation by the least square method.
The following numerical value is used for the viscosity formula: [η] = K × Mα used for conversion to molecular weight.
PS: K = 1.38 × 10 ⁻⁴ , α = 0.7
PP: K = 1.03 × 10 ⁻⁴ , α = 0.78

(2) Terminal Vinyl Ratio The terminal vinyl group-containing propylene polymer produced according to the present invention has the following characteristic (II).
Characteristic (II) The terminal vinyl ratio is 0.7 or more In the present invention, the terminal vinyl ratio means the ratio of the chain having a vinyl group at the terminal out of all the polymer chains of the terminal vinyl group-containing propylene polymer, Calculated by the following formula.
(Terminal vinyl ratio) = {[Vi] / ((total number of terminals) −LCB number)} × 2
(Where [Vi] is the number of terminal vinyl groups per 1000 monomer units calculated by ¹ H-NMR. The total number of terminals is the total number of terminals per 1000 monomer units calculated by ¹³ C-NMR. (The LCB number is the number of methine carbons at the base of a branched chain having 7 or more carbon atoms per 1000 monomer units calculated by ¹³ C-NMR.)
The terminal vinyl group-containing polypropylene of the present invention has a terminal vinyl ratio of 0.7 or more, preferably 0.75 or more. More preferably, it is 0.8 or more, and ideally 1.0 (all polymer chains have a vinyl group at the terminal). By increasing the terminal vinyl ratio and within the above range, the stereoregularity can be enhanced at the same time.

(2-1) Relationship between reaction mechanism and terminal structure In the present invention, when obtaining a propylene polymer having a terminal vinyl ratio of 0.7 or more, the relationship between the reaction mechanism and the terminal structure obtained is as follows. .
In the polymerization of propylene, β-hydrogen elimination generally occurs, and a vinylidene structure (propyl-vinylidene structure) terminal represented by the following structural formula (1-b) is generated.
In addition, when hydrogen is used, chain transfer to hydrogen usually takes place preferentially and the end of the i-butyl structure represented by the following structural formula (1-c) is generated.
However, when a complex having a special structure is used as a polymerization catalyst, a special chain transfer reaction generally called β-methyl elimination occurs, and a vinyl structure (1-propenyl structure) represented by the following structural formula (1-a) (Reference: Macromol. Rapid Commun. 2000, 21, 1103-1107).
In addition, in the polymerization of propylene, the following terminal structure is generated due to the reaction mechanism. After propylene insertion and β-hydrogen elimination, a terminal of i-butenyl structure represented by the following structural formula (1-d) is generated through a π-allyl intermediate that can be extracted from the γ-position.
In addition, propylene may cause irregular 2,1 insertion. After such an irregular bond occurs, it undergoes chain transfer to hydrogen, β hydrogen elimination, or π allyl intermediate. When hydrogen is desorbed, an n-butyl structure represented by the following structural formula (1-e), a 1-butenyl structure represented by the following structural formula (1-f), and a terminal vinylene structure represented by the following structural formula (1-g) ( The end of (2-butenyl structure) is formed. Here, the 1-butenyl structure (structural formula (1-f)) is included in the terminal vinyl group of the present invention.
Further, when ethylene or 1-butene is used as a comonomer in the present invention, the following terminals are generated due to the mechanism.
After the insertion of ethylene, chain transfer to hydrogen produces an end of the n-propyl structure represented by the following structural formula (1-h).
When β-hydrogen elimination occurs after ethylene insertion, a terminal of 1-propenyl structure represented by the following structural formula (1-a) is generated.
After 1-butene insertion, chain transfer to hydrogen produces the end of the i-pentyl structure represented by the following structural formula (1-i).
When β-hydrogen elimination occurs after 1-butene insertion, the end of the butyl-vinylidene structure represented by the following structural formula (1-j) is generated.

  The starting end is always a saturated hydrocarbon end, and no unsaturated bond appears at both ends. This means that when the terminal vinyl group-containing polypropylene of the present invention is modified, only one terminal is modified. On the other hand, for example, a polymer having terminal unsaturated bonds obtained by thermally decomposing polypropylene may have vinylidene (Vd) groups at both ends, and when the unsaturated bond is modified from this, Both ends may be modified, and the form is different from the terminal vinyl group-containing polypropylene of the present invention.

Therefore, in order to increase the terminal vinyl ratio, the reaction generating the structural formulas (1-b) to (1-e) and (1-g) to (1-j) is suppressed, and the structural formula (1-a) , Polymerization conditions that promote the reaction that yields (1-f) are preferred.
Among the polymerization conditions, regarding the catalyst, as described above, a 5-membered heterocyclic ring having a structure of a bisindenyl hafnium complex and having a specific substituent at the 2-position of the indene ring, which is a ligand, and the same indene By using an olefin polymerization catalyst containing a metallocene compound substituted with an aryl group having a specific substituent at the 4-position of the ring, the chain transfer reaction that generates the structural formula (1-a) can be promoted.
In addition, when an olefin polymerization catalyst containing such a metallocene compound is used, even when hydrogen is used, surprisingly, although the activity increases, a β-methyl elimination reaction occurs preferentially, and vinyl Structure (1-propenyl structure): Structural formula (1-a) is mainly generated. This selectivity can also be controlled by changing the polymerization temperature. For example, in the olefin polymerization catalyst including the metallocene compound shown in the examples, the terminal vinyl ratio can be increased as the polymerization temperature increases.

(2-2) Method for Specifying Terminal Vinyl Ratio A terminal vinyl ratio can be specified by performing ¹ H-NMR and ¹³ C-NMR by the method described below.
[Sample preparation and measurement conditions]
A 200 mg sample is an NMR sample having an inner diameter of 10 mmφ together with 2.4 ml of o-dichlorobenzene / deuterated benzene bromide (C ₆ D ₅ Br) = 4/1 (volume ratio) and hexamethyldisiloxane which is a reference substance of chemical shift It put into the pipe | tube and melt | dissolved uniformly with the block heater of 150 degreeC.
The NMR measurement was performed using an AV400 type NMR apparatus of Bruker BioSpin Co., Ltd. equipped with a 10 mmφ cryoprobe.
¹ H-NMR was used for quantification of the unsaturated terminal. The measurement conditions for ¹ H-NMR were as follows: the sample temperature was 120 ° C., the pulse angle was 4.5 °, the pulse interval was 2 seconds, and the number of integrations was 512 times. The chemical shift was set such that the proton signal of hexamethyldisiloxane was set to 0.09 ppm, and the chemical shift of the signal by other protons was based on this.
¹³ C-NMR was used for quantification of the saturated terminal. The measurement conditions of ¹³ C-NMR were a sample temperature of 120 ° C., a pulse angle of 90 °, a pulse interval of 15 seconds, an integration count of 1024 times, and a broadband decoupling method. The chemical shift was set such that the ¹³ C signal of hexamethyldisiloxane was set to 1.98 ppm, and the other chemical shifts of signals due to ¹³ C were based on this.

[Calculation method of the number of unsaturated ends]
^{In 1} H-NMR, proton signals of unsaturated bonds of structural formula (1-a) 1-propenyl and structural formula (1-f) 1-butenyl are 5.08 to 4.85 ppm in the ¹ H-NMR spectrum. And 5.86-5.69 ppm signals are detected. Therefore, the number of terminal vinyl groups [Vi] is the number of 1-propenyl and 1-butenyl combined, the amount of unsaturated bonds per 1000 monomers in total, and the signal intensity of the ¹ H-NMR spectrum. Ask from.
In ¹ H-NMR, the proton signal of the unsaturated bond of structural formula (1-b) propyl-vinylidene and structural formula (1-j) butyl-vinylidene is 4.79 to 4.65 ppm in the ¹ H-NMR spectrum. It is detected by overlapping the signal. Therefore, the number of terminal vinylidene groups [Vd] is the total number of propyl-vinylidene and butyl-vinylidene, the amount of unsaturated bonds per 1000 monomers in total, and the signal intensity of ¹ H-NMR spectrum. Ask from.
Structural formula (1-a) + Structural formula (1-f): [Vi] = Ivi × 1000 / Itotal
Structural formula (1-b) + Structural formula (1-j): [Vd] = Ivd × 1000 / Itotal
Similarly, the number of i-butenyl groups [i-butenyl], the number of vinylene terminals [terminal vinylene], and the number of internal vinylidenes [internal vinylidene] can be obtained from the following equations.
Structural formula (1-d): [i-butenyl] = Iibu × 1000 / Itotal
Structural formula (1-g): [terminal vinylene] = Ivnl × 1000 / Itotal
Structural formula (1-m): [Internal vinylidene] = Iivd × 1000 / Itotal
Here, Ivi, Ivd, Iibu, Ivnl, and Iivd are structural formula (1-a) + structural formula (1-f), structural formula (1-b) + structural formula (1-j), and structural formula, respectively. It represents the characteristic value of a signal based on (1-d), structural formula (1-g), and structural formula (1-m), and is an amount represented by the following formula.
Ivi = (I _5.08-4.85 + I _5.86-5.69 ) / 3
Ivd = (I _4.79-4.65 ) / 2,
Iibu = I _5.30-5.08 ,
Ivnl = (I _5.58-5.30 ) / 2,
Iivd = (I _{4.85 to 4.79} ) / 2
I indicates the integrated intensity, and the subscript number of I indicates the range of chemical shift. For example, I _5.08 to 4.85 indicates the integrated intensity of the signal detected between 5.08 ppm and 4.85 ppm.
Itotal is an amount represented by the following equation.
Itotal = IC2 + IC3 + IC4 + Ivi + Ivd + Iibu + Ivnl + Iivd
IC2 is a characteristic value of a signal based on ethylene, IC3 is a characteristic value of a signal based on propylene, and IC4 is a characteristic value of a signal based on 1-butene, and is an amount represented by the following formula.
IC2 = ¼ × {(Imain × [C2] × 2) / ([C2] × 2 + [C3] × 3 + [C4] × 4)}
IC3 = 1/6 × {(Imain × [C3] × 3) / ([C2] × 2 + [C3] × 3 + [C4] × 4)}
IC4 = 1/8 × {(Imain × [C4] × 4) / ([C2] × 2 + [C3] × 3 + [C4] × 4)}
[C2], the ethylene content was calculated by ¹³ C-NMR described below (mol%), [C3] is a propylene content was calculated by ¹³ C-NMR described below (mol%), [C4] is below ¹³ C The 1-butene content (mol%) calculated by -NMR is shown.
“Imain” is the sum of proton signals at the polymer main chain and saturated terminal detected at 4.00 to 0.00 pm in the ¹ H-NMR spectrum.

[Calculation method of the number of saturated ends]
The number of saturated ends below is determined from the following formula using the signal intensity of the ¹³ C-NMR spectrum as the number per 1000 monomers.
Structural formula (1-c): [i-butyl] = Ii-butyl × 1000 / Itotal-C
Structural formula (1-e): [n-butyl] = Inbu × 1000 / Itotal-C
Structural formula (1-h): [n-propyl] = Inpr × 1000 / Itotal-C
Structural formula (1-i): [i-pentyl] = Ii-pen × 1000 / Itotal-C
Structural formula (1-k): [2,3-dimethylbutyl] = I2,3-dim × 1000 / Itotal-C
Structural formula (1-l): [3,4-dimethylpentyl] = I3,4-dim × 1000 / Itotal-C

  Furthermore, in the terminal vinyl group-containing polypropylene of the present invention, in addition to the structure based on the regular 1,2 insertion of propylene inside the polymer, the following 2,1 bond based on the irregular insertion of propylene, Can have 3 bonds. In addition, when 1-butene is used as a comonomer, it can have the following 1,4 bond structure based on an irregular insertion in addition to a structure based on a regular 1,2 insertion.

Here, Ii-butyl, Inbu, Inpr, Ii-pen, I2,3-dim, and I3,4-dim are structural formula (1-c), structural formula (1-e), and structural formula (1- h), a characteristic value of a signal based on the structural formula (1-i), the structural formula (1-k), and the structural formula (1-l), and is an amount represented by the following formula.
Ii-butyl = (I _23.80-23.70 + I _25.80-25.70 ) / 2
Inbu = I _14.06-14.02
Inpr = (I _{14.44 to 14.42} + I _{30.46 to 30.45} ) / 2
Ii-pen = (I _30.70-30.50 + I _42.00-41.80 ) / 2
I2,3-dim = (I _{16.21 to 16.17} + I _{31.86 to 31.81} ) / 2
I3,4-dim = I _12.0-11.60
Further, Itotal-C is an amount represented by the following formula.
Itotal-C = Ii-butyl + Inbu + Inpr + Ii-pen + I2,3-dim + I3,4-dim + IE + I1,2-P + I2,1-P + I1,3-P + I1,2-B + I1,4-B
IE is the characteristic value of the signal based on the bond of ethylene, I1,2-P is the characteristic value of the signal based on the bond of 1,2 inserted propylene, and I2,1-P is the bond of the propylene with 2,1 insertion. The characteristic value of the signal based on I1,3-P is the characteristic value of the signal based on the bond of 1,3-inserted propylene, I1,2-B is the characteristic of the signal based on the bond of 1,2-inserted 1-butene The value I1,4-B represents the characteristic value of the signal based on the binding of 1,4-inserted 1-butene, and is an amount represented by the following formula.
IE = I _30.20-29.80 / 2 + I _30.40-30.20 / 4-I _25.20-23.80 + I _38.20-37.30 + I _34.15-33.80
I1,2-P = I _{48.80 to 44.50} + I _{43.90 to 42.80} / 2
I2,1-P = (I _{35.72 to 35.63} + I _{35.83 to 35.77} ) / 2
I1,3-P = I _30.82-30.74 / 2
I1,2-B = I _{41.00 to 39.00} + I _{43.90 to 42.80} / 2
I1,4-B = I _34.45-34.15 / 2

[Calculation method of total number of terminals]
The total number of terminals is the total number of terminals per 1000 monomer units calculated by ¹³ C-NMR and ¹ H-NMR, specifically, structural formula (1-a) to structural formula per 1000 monomer units. This is the total number of terminals up to (1-l).

[LCB number calculation method]
The propylene-based polymer of the present invention may have a long chain branched (LCB) structure portion represented by the following structural formula (A).

[In the structural formula (A), P ¹ , P ² and P ³ are propylene polymer residues each having one or more propylene units, and C _br is a branched chain having 7 or more carbon atoms. , And C _a , C _b , and C _c represent methylene carbons adjacent to the methine carbon (C _br ). ]
In the structural formula (A), the main chain of the propylene ^polymer, P _{1 -C} br -P ^{2 lines,} P _{1 -C} br -P ³ lines or ^P 2 _-C br -P ³ lines 3 There is a street. Therefore, in response to _{each, C} br -P ³ _line, is _C br of -P ² lines or _C br -P ¹ line may become the branch chain. P ¹ , P ² , and P ³ may contain a branched carbon (C _br ) different from C _br described in the structural formula (A) in itself.
Here, LCB structure is attributed to 3 methylene carbon (C _{a) at} 44.1 to 43.9 ppm, 44.7 to 44.5 ppm, and 44.9 to 44.7 ppm by ¹³ C-NMR of the propylene-based polymer. , C _b , C _c ) are observed, and are observed as methine carbon (C _br ) at 31.7 to 31.5 ppm. It is characterized in that three methylene carbons close to C _br are observed in three non-equivalent diastereotopics.
The LCB number is the number of methine carbons (C _br ) at the root of a branched chain having 7 or more carbon atoms per 1000 monomer units calculated by ¹³ C-NMR.
A branched chain having more than 6 carbon atoms and a branched chain having 6 or less carbon atoms can be distinguished by the difference in the peak position of the methine carbon at the root of the branch (Macromol. Chem. Phys. 2003, Vol. 204, 1738). Page.)
In the present invention, the LCB number is not particularly limited, but it is usually preferably 0.5 or less.

(3) Polymer shape and properties (coarse powder amount, bulk density)
The terminal vinyl group-containing propylene polymer produced according to the present invention preferably further has the following property (III).
Characteristic (III): The amount of coarse powder is 1% by mass or less

(3-1) Coarse powder amount About the coarse powder amount of the propylene-based polymer, when the amount of coarse powder exceeds 1% by mass, there is a problem that the polymerization tank is contaminated or fouled in bulk polymerization. To do.
With respect to this problem, the present invention can reduce the amount of the coarse powder of the propylene-based polymer to 1% or less, preferably 0.8% by mass or less, more preferably 0.5% by mass or less, and particularly preferably 0%. .3 mass% or less.
The measurement of the amount of coarse powder is carried out using a vibrating sieve particle size measuring device, and the ratio (mass%) of the polymer mass remaining on the sieve having an opening of 2000 μm or more with respect to the total sample mass is specified as the amount of coarse powder. .

(3-2) Bulk density Moreover, the property of the polymer particle of a propylene polymer can be evaluated by a bulk density.
The bulk density is an index that correlates with the average particle diameter of the polymer, the amount of coarse powder due to aggregation, etc., and the higher the bulk density, the better the shape of these polymer particles.
In the present invention, the bulk density of the propylene-based polymer can be 0.30 g / ml or more, preferably 0.40 g / ml or more, more preferably 0.42 g / ml or more, and particularly preferably 0.43 g. / Ml or more.
The bulk density is measured according to ASTM D1895-69.

(4) Melting point Tm (° C)
The terminal vinyl group-containing propylene-based polymer produced according to the present invention preferably further has the following property (IV).
Characteristic (IV): Melting point (Tm) is less than 153 ° C. The melting point of the propylene polymer may be less than 153 ° C., and the lower limit is not particularly limited, but is preferably 100 ° C. or more.
When the melting point is within the above range, solubility in a solvent and affinity with other base materials can be improved.
The melting point was measured by using a DSC6200 manufactured by Seiko Instruments Inc., filling a sheet-like sample piece in a 5 mg aluminum pan, raising the temperature from room temperature to 200 ° C. at a heating rate of 100 ° C./min and holding for 5 minutes. When the crystallization temperature (Tc) is obtained as the maximum crystal peak temperature (° C.) when the temperature is lowered to 20 ° C. at a rate of 20 ° C./min, and then the temperature is raised to 200 ° C. at a rate of 10 ° C./min. The maximum melting temperature (° C.) can be determined.

(5) mm fraction of propylene unit 3 chain The terminal vinyl group-containing propylene polymer obtained by the production method of the present invention has high stereoregularity.
In the present invention, the stereoregularity of the propylene-based polymer is not limited, but the mm fraction (isotactic triad fraction) of the three propylene units calculated by ¹³ C-NMR reaches 95% or more, preferably Is 96% or more, more preferably 97% or more.
It means that it is highly controlled, so that the mm fraction of a component (A) is high. If it is smaller than this value, mechanical properties such as a decrease in the elastic modulus of the product will decrease.

The mm fraction of the propylene unit 3 chain is determined by substituting the integrated intensity of the ¹³ C signal measured by ¹³ C-NMR measurement into the following equation.
mm (%) = Imm × 100 / (Imm + 3 × Imrm)
Here, Imm = I _{23.6 to 21.1} , and Imrrm = I _19.8 to _19.7 .
The ¹³ C-NMR measurement method for determining the mm fraction of the three propylene units can be carried out in the same manner as the above measurement.
Spectral assignment can be made with reference to Polymer Journal, 16, 717 (1984), Asakura Shoten, Macromolecules, 8 卷, 687 (1975) and Polymer, 30, 1350 (1989). it can.

(6) Amount of heterogeneous bond (amount of 2,1 bond, 1,3 bond, and 1,4 bond)
The terminal vinyl group-containing propylene-based polymer obtained by the production method of the present invention has a small amount of heterogeneous bonds, that is, high positional regularity.
Although there is no restriction | limiting in the positional regularity of a polypropylene, It is preferable that the 2,1 bond calculated by < ¹³ > C-NMR is 0.2 mol% or less and a 1,3 bond becomes 0.2 mol% or less.
The 2,1 bond is more preferably 0.15 mol% or less, further preferably 0.12 mol% or less, and particularly preferably 0.10 mol% or less.
The 1,3 bond is more preferably 0.15 mol% or less, further preferably 0.12 mol% or less, and particularly preferably 0.10 mol% or less.
When the amount of the heterogeneous bond is small, characteristics such as mixing efficiency is increased when mixed or applied to other polypropylene or a base material, coating efficiency is improved, and further, it is difficult to peel off as a coating agent.
Further, by controlling so that the regularity (stereo / position) of propylene does not become too high, solubility in a solvent can be enhanced and the reactivity of terminal vinyl can be enhanced.

The amount of heterogeneous bonds (molar concentration) is determined from the following equation using the signal intensity of the ¹³ C-NMR spectrum.
Propylene 2,1 bond (mol%)
= I2,1-P × 100 / (I1,2-P + I2,1-P + I1,3-P + I1,2-B + I1,4-B + IE)
Propylene 1,3 bond (mol%)
= I1,3-P × 100 / (I1,2-P + I2,1-P + I1,3-P + I1,2-B + I1,4-B + IE)
Butene 1,4 bond (mol%)
= I1,4-B × 100 / (I1,2-P + I2,1-P + I1,3-P + I1,2-B + I1,4-B + IE)

(7) Content of comonomer unit other than propylene When the terminal vinyl group-containing propylene polymer of the present invention is a copolymer of propylene and a comonomer selected from the group consisting of ethylene and α-olefin, The content of structural units derived from the comonomer is preferably 1.5 mol% or more.
Comonomers enter the propylene chain that is regularly (stereo / positional) inserted to change the primary structure. As one result, it has the effect of lowering the melting point.
Therefore, by increasing the comonomer content, the crystallinity does not become too high, the solubility in the solvent can be increased, and the reactivity of the terminal vinyl can be increased.
On the other hand, the propylene chain inserted regularly (three-dimensional / position) does not become too short, and when mixed or applied to other polypropylenes or substrates, the mixing efficiency is improved, the coating efficiency is improved, and the coating agent is improved. From the viewpoint of making it difficult to peel off, the terminal vinyl group-containing propylene-based polymer of the present invention is derived from the comonomer when it is a copolymer of propylene and a comonomer selected from the group consisting of ethylene and α-olefin. The content of the structural unit is preferably 50 mol% or less.

When 1-butene is used as a comonomer, the preferable butene content is 1.5 mol% or more, more preferably 1.8 mol% or more, and further preferably 2.0 mol% or more.
Further, in order to improve the balance between isotactic chain length and crystallinity, it is preferably 10 mol% or less, more preferably 7 mol% or less, and further preferably 5 mol% or less.

The content (molar concentration) of the comonomer unit is determined from the following formula using the signal intensity of the ¹³ C-NMR spectrum.
Ethylene content [C2] (mol%)
= IE × 100 / (I1,2-P + I2,1-P + I1,3-P + I1,2-B + I1,4-B + IE)
Propylene content [C3] (mol%)
= (I1,2-P + I2,1-P + I1,3-P) × 100 / (I1,2-P + I2,1-P + I1,3-P + I1,2-B + I1,4-B + IE)
1-butene content [C4] (mol%)
= (I1,2-B + I1,4-B) × 100 / (I1,2-P + I2,1-P + I1,3-P + I1,2-B + I1,4-B + IE)
Here, IE, I1,2-P, I2,1-P, I1,3-P, I1,2-B, and I1,4-B are as described above.

(8) MFR
The terminal vinyl group-containing propylene polymer produced according to the present invention preferably has a melt flow rate (MFR) measured at 230 ° C. and a load of 2.16 kgf of 470 g / 10 min or more. Although the upper limit of MFR is not specifically limited, It is preferable that it is 10,000 g / 10min or less.
When MFR is within the above range, solubility in a solvent and affinity with other base materials can be improved.
MFR can be measured according to the melt flow rate (test conditions: 230 ° C., load 2.16 kgf) of the polypropylene test method of JIS K6758.

5. Applications of terminal vinyl group-containing propylene polymers Conventionally, when polymerizing under high temperature and high pressure conditions to synthesize propylene polymers having a small molecular weight, polymer particles having excellent shape and properties are obtained. It was difficult.
In the present invention, it is considered that the reaction rate is increased by homopolymerizing or copolymerizing propylene using a catalyst containing the specific metallocene compound represented by the general formula (1). It can be synthesized under relatively low temperature and low pressure conditions.
Further, the present invention can easily produce a propylene-based polymer having a small molecular weight and excellent shape and properties of the polymer particles, particularly when the present invention is carried out by bulk polymerization. The effect of improving the shape and properties of the polymer particles is high.
Since the terminal vinyl group-containing propylene-based polymer of the present invention is a propylene homopolymer or propylene copolymer whose terminal structure is highly controlled so as to contain a high proportion of vinyl terminal structures, macromer, It can be used as a raw material for paints, primers, surface modifiers, coating materials, and the like.
The terminal vinyl group-containing propylene-based polymer of the present invention may contain a known antioxidant, ultraviolet absorber, antistatic agent, nucleating agent, lubricant, flame retardant, antiblocking agent, colorant, inorganic or After blending various additives such as organic fillers and various synthetic resins, it can be used as pellets cut into granules after heating and melt-kneading using a melt-kneader.

EXAMPLES Next, although an Example demonstrates this invention further more concretely, this invention is not limited to a following example.
In addition, the physical-property measurement, analysis, etc. in a following example follow the following method.

(1) Melt flow rate (MFR):
It was measured according to the melt flow rate (test condition: 230 ° C., load 2.16 kgf) of the polypropylene test method of JIS K6758. The unit is g / 10 minutes.
(2) Molecular weight and molecular weight distribution (Mw, Mn, Mw / Mn):
It was measured by the method described in the present specification by gel permeation chromatography (GPC).
(3) Melting point (Tm):
Using a Seiko Instruments DSC6200, the sheet-shaped sample piece was packed in a 5 mg aluminum pan, heated from room temperature to 200 ° C. at a heating rate of 100 ° C./minute, held for 5 minutes, and then 10 ° C./minute. The crystallization temperature (Tc) is obtained as the maximum crystal peak temperature (° C.) when the temperature is lowered to 20 ° C. and crystallized, and then the maximum melting temperature when the temperature is raised to 200 ° C. at 10 ° C./min. The melting point (Tm) was determined as the peak temperature (° C.).
(4) mm fraction of propylene unit 3 chain:
Using a Bruker BioSpin AV400 NMR apparatus equipped with a 10 mmφ cryoprobe, the measurement was performed by the method described in the present specification. The unit is%.
(5) Catalytic activity (CE) (g / ghr)
The catalyst activity is a value per unit time obtained by dividing the polymer yield (g) by the amount of catalyst introduced (g) (value excluding the prepolymerized polymer).
(6) Composition analysis:
The composition of the ion-exchange layered silicate was measured with a fluorescent X-ray by preparing a calibration curve by chemical analysis according to the JIS method.
(7) Measuring method of bulk density (BD) The bulk density of the polymer particles was measured according to ASTM D1895-69.
(8) Coarse powder amount:
A vibration sieve particle size measuring device was used for measuring the amount of coarse powder in the polymer particles. Shake each sieve with an opening of 100 μm, 150 μm, 212 μm, 350 μm, 500 μm, 710 μm, 850 μm, 1,000 μm, 1,180 μm, 1,400 μm, 1,700 μm, 2,000 μm, 2,800 μm, 3,000 μm Using a machine, vibration classification was performed for 10 minutes or more, and the ratio (mass%) of the polymer mass on the sieve of 2000 μm or more to the total sample mass was specified as the amount of coarse powder.

[Example 1]
(1) Synthesis of Complex (Complex 1) rac-dichloro [1,1′-dimethylsilylenebis {2- (5-t-butyl-2-furyl) -4- (4-isopropyl-phenyl) -indenyl}] Hafnium was synthesized according to the method of Example 13 of JP2009-299046 and Example 1 of JP2009-91512A.

(2) Preparation of catalyst (2-a) Chemical treatment of ion-exchanged layered silicate To a 1 L three-necked flask equipped with a stirring blade and a reflux device, 645.1 g of distilled water and 82.6 g of 98% sulfuric acid were added. The temperature was raised to 95 ° C.
Commercially available montmorillonite (Mizusawa Chemical Co., Ltd. Benclay KK, Al = 9.78 mass%, Si = 31.79 mass%, Mg = 3.18 mass%, Al / Si (molar ratio) = 0.320, 100 g) was added and reacted at 95 ° C. for 320 minutes. After 320 minutes, 0.5 L of distilled water was added to stop the reaction, and filtration was performed to obtain 255 g of a cake-like solid.
1 g of this cake contained 0.31 g of chemically treated montmorillonite (intermediate). The chemical composition of the chemically treated montmorillonite (intermediate) was Al = 7.68 mass%, Si = 36.05 mass% Mg = 2.13 mass%, and Al / Si (molar ratio) = 0.222.
Distilled water (1545 g) was added to the cake to make a slurry, and the temperature was raised to 40 ° C. 5.734 g of lithium hydroxide hydrate was added as a solid, and reacted at 40 ° C. for 1 hour. After 1 hour, the reaction slurry was filtered and washed 3 times with 1 L of distilled water to obtain a cake-like solid again.
When the recovered cake was dried, 80 g of chemically treated montmorillonite was obtained. The chemical composition of this chemically treated montmorillonite is Al = 7.68 mass%, Si = 36.05 mass%, Mg = 2.13 mass%, Al / Si (molar ratio) = 0.222, Li = 0.53. It was mass%.

(2-b) Prepolymerization Into a 1 L three-necked flask, 20 g of the obtained chemically treated montmorillonite was added, and 131 mL of heptane was added to form a slurry. To this, 50 mmol of triisobutylaluminum (concentration 143.4 mg / mL heptane solution was added). 69 mL) was added and stirred for 1 hour. After 1 hour, it was washed to 1/100 with heptane to make the total volume 100 mL.
The slurry solution containing this chemically treated montmorillonite was kept at 50 ° C., and 4.2 mmol of tri-normal octyl aluminum (10.7 mL of a heptane solution having a concentration of 143.4 mg / mL) was added thereto and stirred for 20 minutes.
There, rac-dichloro [1,1′-dimethylsilylenebis {2- (5-tert-butyl-2-furyl) -4- (4-isopropyl-phenyl) -indenyl}] hafnium 0.3 mmol (toluene 50 mL) And the mixture was stirred for 20 minutes while maintaining the temperature at 50 ° C.
Thereafter, 350 mL of heptane was added, and the slurry was introduced into a 1 L autoclave.
After the internal temperature of the autoclave was set to 40 ° C., propylene was fed at a rate of 10 g / hour, and prepolymerization was performed while maintaining the temperature at 40 ° C. for 4 hours. Thereafter, the propylene feed was stopped, and residual polymerization was carried out for 1 hour at 40 ° C.
After removing the supernatant of the resulting catalyst slurry by decantation, the prepolymerized catalyst was washed by adding decantation again with heptane. To the portion remaining after the decantation, 12 mmol of triisobutylaluminum (16.6 mL of a heptane solution having a concentration of 143.4 mg / mL) was added and stirred for 10 minutes. This solid was dried under reduced pressure at 40 ° C. for 2 hours to obtain 49.8 g of a dry prepolymerized catalyst. The prepolymerization ratio (value obtained by dividing the amount of prepolymerized polymer by the amount of solid catalyst) was 1.49. This prepolymerized catalyst was designated as Catalyst 1.

(3) Polymerization After 3L autoclave was heated and dried well by circulating nitrogen, the inside of the tank was replaced with propylene and cooled to room temperature. After introducing 2.86 mL of a heptane solution of triisobutylaluminum (140 mg / mL) and 750 g of liquid propylene, the temperature was raised to 75 ° C. Thereafter, 200 mg of the catalyst 1 in a mass excluding the prepolymerized polymer was pumped to the polymerization tank with high-pressure argon to initiate polymerization. After maintaining at 75 ° C. for 1 hour, unreacted propylene was quickly purged to terminate the polymerization. As a result, about 217 g of a propylene homopolymer was obtained.
Table 1 shows the evaluation results of the obtained polymer.

[Example 2]
In Example 1, the same polymerization was performed except that 750 g of liquid propylene was introduced after introducing 160 N (normal) ml of H ₂ into the tank, and 80 mg of catalyst 1 was used in a mass excluding the prepolymerized polymer. .
Table 1 shows the evaluation results of the obtained polymer.

[Example 3]
In Example 1, the same polymerization was performed except that 750 g of liquid propylene was introduced after 240 Nml of H ₂ was introduced into the tank, and 80 mg of catalyst 1 was used in a mass excluding the prepolymerized polymer.
Table 1 shows the evaluation results of the obtained polymer.

[Example 4]
In Example 1, 480 Nml of H ₂ was introduced into the tank, 750 g of liquid propylene was introduced, and the same polymerization was performed except that 50 mg of catalyst 1 was used in a mass excluding the prepolymerized polymer.
Table 1 shows the evaluation results of the obtained polymer.

[Example 5]
In Example 1, the same polymerization was carried out except that 650 g of liquid propylene was introduced after introducing 640 Nml of H ₂ into the tank, and 40 mg of catalyst 1 was used in a mass excluding the prepolymerized polymer.
Table 1 shows the evaluation results of the obtained polymer.

[Example 6]
In Example 1, 960 Nml of H ₂ was introduced into the tank, 750 g of liquid propylene was introduced, and the same polymerization was performed except that 40 mg of catalyst 1 was used in a mass excluding the prepolymerized polymer.
Table 1 shows the evaluation results of the obtained polymer.

[Example 7]
In Example 1, after introducing 750 g of liquid propylene, the same polymerization was performed except that the temperature was raised to 70 ° C. and polymerization was performed at 70 ° C.
Table 1 shows the evaluation results of the obtained polymer.

[Example 8]
In Example 1, after introducing 750 g of liquid propylene, the same polymerization was carried out except that the temperature was raised to 80 ° C. and polymerization was carried out at 80 ° C.
Table 1 shows the evaluation results of the obtained polymer.

[Example 9]
In Example 8, the same polymerization was conducted except that 160 Nml of H ₂ was introduced into the tank, 750 g of liquid propylene was introduced, and 80 mg of catalyst 1 was used in a mass excluding the prepolymerized polymer.
Table 1 shows the evaluation results of the obtained polymer.

[Example 10]
In Example 8, the same polymerization was carried out except that 750 g of liquid propylene was introduced after introducing 240 Nml of H ₂ into the tank, and 80 mg of catalyst 1 was used in a mass excluding the prepolymerized polymer.
Table 1 shows the evaluation results of the obtained polymer.

[Comparative Example 1]
(1) Complex synthesis (Complex 2) rac-dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-isopropyl-phenyl) -indenyl}] hafnium According to the method of Example 13 (1) of JP2009-299046.

(2) Preparation of catalyst In (2-b) prepolymerization of Example 1, instead of (complex 1), rac-dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) was used. ) -4- (4-Isopropyl-phenyl) -indenyl}] hafnium (0.3 mmol) was used in the same manner.
As a result, 54.0 g of a dry prepolymerized catalyst was obtained. The prepolymerization ratio (value obtained by dividing the amount of prepolymerized polymer by the amount of solid catalyst) was 1.70. This prepolymerized catalyst was designated as Catalyst 2.

(3) Polymerization After 3L autoclave was heated and dried well by circulating nitrogen, the inside of the tank was replaced with propylene and cooled to room temperature. After introducing 2.86 mL of a heptane solution of triisobutylaluminum (140 mg / mL) and 750 g of liquid propylene, the temperature was raised to 75 ° C. Thereafter, 200 mg of the catalyst 2 in a mass excluding the prepolymerized polymer was pumped to the polymerization tank with high-pressure argon to start polymerization. After maintaining at 75 ° C. for 1 hour, unreacted propylene was quickly purged to terminate the polymerization. As a result, about 350 g of a propylene homopolymer was obtained.
The evaluation results of the obtained copolymer are shown in Table 1.

[Comparative Example 2]
In Comparative Example 1, after introducing 750 g of liquid propylene, the same polymerization was carried out except that the temperature was raised to 80 ° C. and polymerization was carried out at 80 ° C.
The evaluation results of the obtained copolymer are shown in Table 1.

[Comparative Example 3]
In Comparative Example 1, after introducing 750 g of liquid propylene, the same polymerization was carried out except that the temperature was raised to 85 ° C. and polymerization was carried out at 85 ° C.

[Consideration of Examples]
Examples 1 to 10 show that the problems of the present invention can be solved by using the method of the present invention. The terminal vinyl group-containing propylene-based polymers of these examples have a number average molecular weight (Mn) as low as 33,200 or less and a terminal vinyl ratio (Vi) of 0.7 or more as a sufficient amount of terminal vinyl groups. The propylene unit tri-mm length is more than 95%, the stereoregularity is high, the bulk density is more than 0.348 g / ml, and the amount of coarse powder is about 0-0.2% by mass. Good properties.

From Examples 1 to 6, it can be seen that by increasing the amount of hydrogen used, CE (catalytic activity) is increased and the activity can be increased. At this time, the influence on the molecular weight of the terminal vinyl group-containing propylene polymer obtained and the mm fraction of the three propylene units is small. The terminal vinyl ratio shows a slightly decreasing tendency by increasing the amount of hydrogen used, but still maintains a high ratio. The terminal vinyl ratio is considered to show a decreasing tendency because the rate of chain transfer to hydrogen increases as the amount of hydrogen used increases. By using the catalyst system containing, the decreasing tendency of the terminal vinyl ratio was suppressed.
From Example 7, it can be seen that the number average molecular weight (Mn) is increased by lowering the polymerization temperature compared to Example 1, but the number average molecular weight (Mn) is sufficiently small even when the polymerization temperature is 70 ° C. Under the present circumstances, the influence on the mm fraction of the propylene unit 3 chain of the propylene-type polymer obtained is small.
From Example 8, it can be seen that the molecular weight can be decreased by increasing the temperature relative to Example 1, and that the particle properties are not significantly deteriorated even at a polymerization temperature of 80 ° C. Under the present circumstances, the influence on the mm fraction of the propylene unit 3 chain of the propylene-type polymer obtained is small.
Examples 1, 7, and 8 show that the molecular weight can be controlled by controlling the polymerization temperature. The present invention is characterized in that a terminal vinyl group-containing propylene polymer having a number average molecular weight (Mn) of less than 50,000 is obtained. The polymerization temperatures and number average molecular weights of Examples 1, 7, and 8 ( From the relationship with Mn), it is considered that the molecular weight can be satisfied by setting the polymerization temperature to about 50 ° C. or higher in the same polymerization system.
From Examples 8 to 9, it can be seen that, even under conditions where the polymerization temperature is high, the activity can be increased by increasing the amount of hydrogen used, as in Examples 1 to 6. From this, it is considered that the polymerization activity can be increased by increasing the amount of hydrogen used even in a polymerization system having a low polymerization activity due to a low polymerization temperature as in Example 7.

For these examples, as shown in Comparative Examples, metallocenes other than the metallocene compound represented by the general formula (1) in the present invention as described in Patent Document 1 (Japanese Patent Laid-Open No. 2009-299046) are used. In a conventional production method using a catalyst system containing a compound, it is difficult to obtain a propylene polymer having a small molecular weight, a high terminal vinyl ratio, and a good polymer shape and properties.
In Comparative Example 1, the molecular weight was not lowered sufficiently. Comparative Examples 2 and 3 are examples in which the polymerization temperature was increased in order to reduce the molecular weight relative to Comparative Example 1 in accordance with the knowledge of Examples 1, 7, and 8.
Comparative Example 2 is an example in which the polymerization temperature is set to 80 ° C. and the molecular weight is controlled to about 42,000 which is smaller than 50,000. However, the amount of coarse powder is increased to 2.7%, and the particle property is considerably deteriorated. Admitted.
Further, Comparative Example 3 is an example in which the polymerization temperature was 85 ° C. and the molecular weight was reduced to a level corresponding to the value of the example, but the amount of coarse powder increased to 14.5%, and the particle property was significantly deteriorated. Was recognized. In a general commercial scale polymerization facility, if the amount of coarse powder exceeds 1%, the polymerization tank may be contaminated or fouling may occur.

Claims (7)

Using an olefin polymerization catalyst containing the following component (A), component (B) and component (C), propylene is homopolymerized, or a comonomer selected from the group consisting of propylene and ethylene and α-olefin is co-polymerized. A method for producing a terminal vinyl group-containing propylene polymer, characterized by producing a propylene polymer having the following characteristics (I) and (II) by polymerization.
Characteristic (I) Number average molecular weight measured by GPC is less than 50,000 Characteristic (II) Terminal vinyl ratio is 0.7 or more Component (A): Metallocene compound represented by the following general formula (1)
[R ¹¹ and R ¹² are each independently a heterocyclic group constituting a 5-membered ring having at least one hydrocarbon group having 3 or more carbon atoms which may have a hetero atom as a substituent (provided that the 5-membered The hetero atom of the heterocyclic group constituting the ring is not directly bonded to the alkadienyl group.
R ¹³ and R ¹⁴ are each independently an aryl group having a substituent only at the 4-position, and the substituent contains at least one atom selected from the group consisting of a hetero atom and a halogen atom. Or a hydrocarbon group having 3 to 6 carbon atoms.
X ¹¹ and Y ¹¹ are independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms. Represents an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, an amino group, or a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms.
Q ¹¹ has a divalent hydrocarbon group having 1 to 20 carbon atoms, a silylene group that may have a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms. Represents an optionally germinylene group.
However, the substituent of the heterocyclic group constituting the 5-membered ring is not the same as the substituent of the aryl group, and the substituent having the largest total number of carbon atoms and heteroatoms among the substituents of the heterocyclic group. The total number of groups is larger than the total number of carbon atoms and heteroatoms that the substituents of the aryl group have. ]
Component (B): Compound that reacts with component (A) to form an ion pair or ion-exchangeable layered silicate component (C): Organoaluminum compound In the metallocene compound represented by the general formula (1), R ¹¹ and R ¹² are independently any of the following general formulas (2-1), (2-2), and (2-3): The method for producing a terminal vinyl group-containing propylene-based polymer according to claim 1, wherein:
[R ²¹ and R ²² are each independently a hydrogen atom or a hydrocarbon group having 3 or more carbon atoms which may have a hetero atom, and at least one of R ²¹ and R ²² has a hetero atom. Represents a hydrocarbon group having 3 or more carbon atoms. However, the hetero atom of the hydrocarbon group is not directly bonded to the heterocyclic group constituting the 5-membered ring. R ²¹ and R ²² are not bonded to form a ring. ] In the metallocene compound represented by the general formula (1), R ¹¹ and R ¹² are each independently a heterocyclic group constituting a 5-membered ring having a substituent only at the 5-position, and the substituent is A hydrocarbon group having 3 or more carbon atoms which may have a hetero atom (however, a hetero atom of a heterocyclic group constituting a 5-membered ring is not directly bonded to an alkadienyl group), 3. A method for producing a terminal vinyl group-containing propylene polymer according to 1 or 2. In the metallocene compound represented by the general formula (1), the heterocyclic group represented by R ¹¹ and R ¹² has a tertiary hydrocarbon group as a substituent, and is represented by R ¹³ and R ^14. The method for producing a terminal vinyl group-containing propylene polymer according to any one of claims 1 to 3, wherein the aryl group has a secondary hydrocarbon group as a substituent. The method for producing a terminal vinyl group-containing propylene polymer according to any one of claims 1 to 4, wherein the propylene polymer further has the following property (III).
Characteristic (III) The amount of coarse powder is 1% by mass The method for producing a terminal vinyl group-containing propylene polymer according to any one of claims 1 to 5, wherein the propylene polymer further has the following property (IV).
Characteristic (IV) Melting point (Tm) less than 153 ° C The terminal vinyl group-containing propylene-based heavy according to any one of claims 1 to 6, wherein the amount of hydrogen used at the time of polymerization is more than 0 and not more than 2.0 × 10 ^-4 as a feed mass ratio of propylene. Manufacturing method of coalescence.