JP7218768B2 - Method for producing propylene-based polymer containing terminal vinyl group - Google Patents

Description

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

Polypropylene has high chemical stability, excellent mechanical properties, and is inexpensive, so it is widely used as a living material, an industrial material, and the like. Furthermore, attempts are being made to improve the functionality of polypropylene having unsaturated bonds by utilizing the reactivity resulting from the unsaturated bonds. Vinyl-terminated propylene polymers (vinyl-terminated polypropylene polymers) are expected to be used as macromers and raw materials for functionalization.
In a propylene polymer containing a terminal vinyl group, it is believed that the polymer growth termination reaction in the propylene polymerization reaction is caused by β-methyl elimination rather than the usual β-hydrogen elimination (see Non-Patent Document 1). ). However, under the polymerization conditions (catalyst component, etc.) that cause β-methyl elimination, as disclosed in Non-Patent Document 1, only atactic propylene-based polymers with no stereoregularity can be obtained. was the victim.
As a method for obtaining a vinyl-terminated propylene-based polymer having stereoregularity, a method using a chiral stereorigid transition metal compound typified by dimethylsilylenebis(2-methyl-4-phenylindenyl)zirconium dichloride (patented Claim 10 of Document 1, see Non-Patent Document 2), represented by 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 five-membered heterocyclic ring at the 2-position of the indene ring and an aryl group at the 4-position (see claim 1 of Patent Document 2) has been proposed. .

By the way, a compound obtained by functionalizing a terminal vinyl group-containing propylene-based polymer is considered to be suitable for uses such as paints and primers. In such applications, the vinyl-terminated propylene-based polymer and the compound obtained by functionalizing the vinyl-terminated propylene-based polymer should be soluble in solvents and have high affinity with other substrates. is preferred. In order to improve solubility in solvents and compatibility with other substrates, the vinyl-terminated propylene-based polymer and the compound obtained by functionalizing the vinyl-terminated propylene-based polymer should have a low molecular weight. is desirable.
In the method of Patent Document 1, the number average molecular weight (Mn) is 2,000 daltons to 50,000 daltons, 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 polymer having a is obtained. However, this method requires slurry polymerization at relatively high temperature and low pressure in order to obtain a terminal vinyl structure with high selectivity. Under such polymerization conditions, the resulting propylene-based polymer does not have sufficiently high stereoregularity.
According to the method of Patent Document 2, a terminal vinyl group-containing propylene polymer having high stereoregularity can be obtained. However, in the method of Patent Document 2, as can be seen from the fact that, for example, the number average molecular weight of all examples exceeds 50,000, in Patent Document 2, a terminal vinyl group-containing propylene-based polymer having a low molecular weight can be efficiently produced. It doesn't say how to do it.

Japanese Patent Publication No. 2001-525461 JP 2009-299046 A

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

When the present inventors investigated the method for producing a terminal vinyl group-containing propylene polymer according to Patent Document 2, the method of Patent Document 2 produced a terminal vinyl group-containing propylene polymer having a low molecular weight and high stereoregularity. It turned out that there was a problem to be solved in order to manufacture .
For example, in bulk polymerization, the polymerization must be carried out at a high temperature to relatively increase the chain transfer reaction, which poses the problem of deteriorating the shape and properties of the polymer particles.
Moreover, in slurry polymerization, propylene must be polymerized at a low pressure to relatively suppress the propagation reaction, which poses a problem of halving the polymerization activity.
Accordingly, an object of the present invention is to provide a method for highly active production of a vinyl-terminated propylene polymer having a low molecular weight, a high vinyl terminal ratio and good particle properties.

The method for producing a vinyl-terminated propylene-based polymer of the present invention comprises homopolymerizing propylene or and a comonomer selected from the group consisting of ethylene and α-olefins to produce a propylene-based polymer having the following characteristics (I) and (II).
Property (I) Number average molecular weight measured by GPC is less than 50,000 Property (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 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 heteroatom as a substituent (provided that the 5-membered The heteroatom 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, the substituent containing at least one atom selected from the group consisting of heteroatoms and halogen atoms; is 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 optionally having a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms. represents an optional germylene group.
However, 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 substituent having the largest total number of carbon atoms and heteroatoms The total number of groups is greater than the total number of carbon atoms and heteroatoms possessed by the substituents of the aryl group. ]
Component (B): a compound or ion-exchange layered silicate that reacts with component (A) to form an ion pair Component (C): organoaluminum compound

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

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

In the method for producing a vinyl-terminated propylene-based 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 membered ring, wherein the substituent is a hydrocarbon group having 3 or more carbon atoms which may have a heteroatom (provided that the heteroatom of the heterocyclic group constituting the 5-membered ring is not directly bonded to the alkadienyl group).

The method for producing a vinyl-terminated propylene-based polymer of the present invention is characterized in that, in the metallocene compound represented by the general formula (1), the heterocyclic groups represented by R ¹¹ and R ¹² are tertiary carbonized as substituents. Having a hydrogen group, the aryl group represented by R ¹³ and R ¹⁴ preferably has a secondary hydrocarbon group as a substituent.

In the method for producing a terminal vinyl group-containing propylene-based polymer of the present invention, the propylene-based polymer preferably further has the following property (III).
Characteristic (III) Coarse powder content of 1% by mass or less In the method for producing a vinyl-terminated propylene-based polymer of the present invention, the propylene-based polymer preferably further has the following characteristic (IV).
Characteristic (IV) Melting point (Tm) of less than 153° C. In the method for producing a vinyl-terminated propylene-based polymer of the present invention, the amount of hydrogen used during polymerization is more than 0 and 2.0 as a feed mass ratio of propylene. ×10 ⁻⁴ or less is preferable.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a method for highly active production of a vinyl-terminated propylene polymer having a low molecular weight, a high vinyl terminal ratio and good particle properties.

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

The method for producing a vinyl-terminated propylene-based polymer of the present invention comprises homopolymerizing propylene or and a comonomer selected from the group consisting of ethylene and α-olefins 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 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 heteroatom as a substituent (provided that the 5-membered The heteroatom 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, the substituent containing at least one atom selected from the group consisting of heteroatoms and halogen atoms; is 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 optionally having a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms. represents an optional germylene group.
However, 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 substituent having the largest total number of carbon atoms and heteroatoms The total number of groups is greater than the total number of carbon atoms and heteroatoms possessed by the substituents of the aryl group. ]
Component (B): A compound or ion-exchange layered silicate that reacts with Component (A) to form an ion pair Component (C): Organoaluminum compound

The invention is described in detail below.
1. Olefin polymerization catalyst (1) component (A)
Component (A) is a metallocene compound represented by the above general formula (1).
In general formula (1), R ¹¹ and R ¹² are each independently a heterocyclic group constituting a 5-membered ring having, as a substituent, a hydrocarbon group having 3 or more carbon atoms which may have a heteroatom. However, the heteroatom of the heterocyclic group constituting the 5-membered ring is not directly bonded to the alkadienyl group.
By introducing a suitable size substituent on the heterocyclic group of R ¹¹ and R ¹² , the orientation of the inserted propylene is regularly controlled. Furthermore, this substituent makes it easier for the methyl group at the β-position of the growing polymer chain to face the vacant coordination field on the transition metal, making it easier for the β-methyl elimination reaction to proceed. can be obtained.

R ¹¹ and R ¹² are preferably the same as each other.
In addition, in R ¹¹ and R ¹² , the carbon next to the heteroatom of the heterocyclic group constituting the 5-membered ring is preferably bonded to the alkadienyl group in general formula (1).
The number of carbon atoms in the hydrocarbon group may be 3 or more, preferably 7 or less, more preferably 6 or less, still more preferably 5 or less, and particularly preferably 4.
Heteroatoms also include silicon, oxygen, sulfur, nitrogen, boron, phosphorus, and the like, which may be present within the carbon chain and interposed between carbon-carbon bonds.
In addition, R ¹¹ and R ¹² are independently heterocyclic groups constituting a 5-membered ring having a substituent only at the 5-position, wherein the substituent has 3 carbon atoms and may have a hetero atom. The above hydrocarbon groups are preferred (provided that the heteroatom 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.

Preferred structures of R ¹¹ and R ¹² include a five-membered heterocyclic ring structure represented by any of the following general formulas (2-1), (2-2) or (2-3).

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

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

In 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. is a hydrocarbon group having 3 to 6 carbon atoms which may contain an atom of
R ¹³ and R ¹⁴ are preferably the same as each other.
The aryl group is preferably a phenyl group.
Heteroatoms include silicon, oxygen, sulfur, nitrogen, boron, phosphorus, and the like.
Also, when the hydrocarbon group contains heteroatoms, such heteroatoms may be present within the carbon chain and interposed between carbon-carbon bonds.
A halogen atom may be a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.
The number of carbon atoms in the hydrocarbon group may be 3 or more and 6 or less, preferably 5 or less, more preferably 4 or less, still more preferably 3.
The hydrocarbon group having 3 to 6 carbon atoms as a substituent of the aryl group may be any of alkyl, cycloalkyl and aromatic hydrocarbon groups, but is preferably a secondary hydrocarbon group.

Preferred structures of R ¹³ and R ¹⁴ include structures having a substituent at the 4-position on the phenyl group represented by the following general formula (3).
4-R ³¹ -Ph- General 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 hetero atoms and halogen atoms. 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 substituents of the heterocyclic group constituting the 5-membered ring and the substituents 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 greater than the total number of carbon atoms and heteroatoms possessed by the substituents of the aryl group.
That is, when there are multiple non-identical substituents on the heterocyclic group (R ¹¹ and R ¹² ) (for example, when the 4- and 5-positions on the heterocyclic group have substituents with different structures), each Maximum total number of carbon atoms and heteroatoms in a substituent When compared, the total number of carbon atoms and heteroatoms possessed by 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 possessed by the substituent on the aryl group. greater than
In addition, when only one substituent exists on the heterocyclic group, the said substituent is a substituent with the largest said total number. Further, the substituent of the heterocyclic group and the substituent of the aryl group may not have a heteroatom. Furthermore, the substituent of the aryl group may have no carbon atoms, and when it has no carbon atoms, the number of carbon atoms is defined as zero.
A preferred specific example is that the substituents on the heterocyclic groups R ¹¹ and R ¹² are t-butyl groups (4 carbon atoms and 0 heteroatoms for a total number of 4), and the aryl group R ¹³ and the 4-position substituent on R ¹⁴ is an i-propyl group (3 carbon atoms and 0 heteroatoms for a total of 3).

INDUSTRIAL APPLICABILITY The present invention provides a method for highly active production of a vinyl-terminated propylene polymer having a low molecular weight, a high vinyl terminal ratio and good particle properties.
The reason why the high activity is obtained is not necessarily clear, but by introducing substituents having 3 or more carbon atoms on the aryl groups R ¹³ and R ¹⁴ , the electron density of the transition metal changes, resulting in propylene It is thought that the rate of insertion reaction into is increased and the growth rate is increased.
In addition, as another activity-enhancing action, the substituent on the aryl group, due to its bulkiness, allows the growing polymer chain to become the 6-membered ring portion of one indene ring ligand on the transition metal in general formula (1). encourage you to avoid As a result, the orientation of the next inserted propylene is controlled both by the growing polymer chain pointing away from this 6-membered ring moiety and also by the heterocyclic groups R ¹¹ and R ¹² , resulting in regio- and stereoregularity. Propylene insertion occurs spontaneously.
At this time, the heterocyclic groups R ¹¹ and R ¹² simultaneously control the direction of the methyl group at the β position of the growing polymer chain. by combining the substituents on R ¹³ and R ¹⁴ that are aryl groups and the substituents on R ¹¹ and R ¹² that are heterocyclic groups to control both stereoregularity and regioregularity there is
Ultimately, the combinatorial effects of each substituent control both the propagation and β-methyl elimination kinetics, resulting in a polymer chain of a specific length and thus a specific molecular weight. be done.
Therefore, in the present invention, the substituents on R ¹¹ and R ¹² that are heterocyclic groups and the substituents on R ¹³ and R ¹⁴ that are aryl groups are combined with specific substituents to allow the growth reaction and By balancing the termination reaction due to β-methyl elimination, a vinyl-terminated propylene-based polymer having a specific molecular weight (number average molecular weight of less than 50,000) can be obtained with high regularity and high activity.

The above X ¹¹ and Y ¹¹ are each independently ligands that form σ bonds with Hf, and form active metallocenes capable of olefin polymerization together with component (B) and component (C).
Therefore, the types of ligands for X ¹¹ and Y ¹¹ are not limited as long as this purpose is achieved.
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. is preferred, and chlorine, bromine, methyl, ethyl, isopropyl and phenyl groups are particularly preferred.

The above Q ¹¹ has a divalent hydrocarbon group having 1 to 20 carbon atoms, which may contain a divalent halogen, and a hydrocarbon group having 1 to 20 carbon atoms, which binds two five-membered rings. represents an optional silylene group or germylene group.
When two hydrocarbon groups are present on the above-mentioned silylene group or germylene group, they may combine with each other to form a ring structure.
Specific examples of Q ¹¹ above include alkylene groups such as methylene, methylmethylene, dimethylmethylene and 1,2-ethylene;
Arylalkylene groups such as diphenylmethylene;
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;
Alkyloligosilylene groups such as tetramethyldisilylene;
germylene group;
an alkylgermylene group in which the silicon of the silylene group having a divalent hydrocarbon group of 1 to 20 carbon atoms is substituted with germanium;
(alkyl) (aryl) germylene group;
An arylgermylene group and the like can be mentioned.
Among these, a silylene group having a hydrocarbon group of 1 to 20 carbon atoms or a germylene group having a hydrocarbon group of 1 to 20 carbon atoms is preferable, and an alkylsilylene group and an alkylgermylene group are particularly preferable.

Among the compounds represented by the general formula (1), the following compounds can be exemplified as preferable compounds.
(1) dichloro[1,1′-dimethylsilylenebis{2-(5-t-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.
Component (B) may be used alone or in combination of two or more. Preferred are ion-exchange layered silicates.

(2-1) Compounds Forming Ion Pairs with Component (A) Examples of compounds that form ion pairs by reacting with component (A) include aluminum oxy compounds and boron compounds. Specific examples include compounds represented by the following general formulas (I) to (III).

In the general formulas (I) and (II) above, 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, a plurality of R ^a may be the same or different. In addition, p represents an integer of 0-40, preferably 2-30.
The compounds represented by general formulas (I) and (II) are compounds also called aluminoxanes, and among these, methylaluminoxane and methylisobutylaluminoxane are preferred. A plurality of types of the above aluminoxanes may be used in combination within each group and between each group. And the above aluminoxanes can be prepared under various known conditions.
In 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 a mixture of one trialkylaluminum or two or more trialkylaluminums and an alkylboronic acid represented by the general formula R ^b B(OH) ₂ at a ratio of 10:1 to It can be obtained by a 1:1 (molar ratio) reaction.
Boron compounds include complexes of cations such as carbonium cations and ammonium cations with organic boron compounds such as triphenylboron, tris(3,5-difluorophenyl)boron and tris(pentafluorophenyl)boron, or Various organoboron compounds such as tris(pentafluorophenyl)boron can be mentioned.

(2-2) Ion-exchangeable phyllosilicate Ion-exchangeable phyllosilicate (hereinafter sometimes simply abbreviated as silicate) is a layer composed of ionic bonds and the like stacked in parallel with each other with bonding force. A silicate compound that has a crystal structure, contains interlayer ions between layers, and contains exchangeable interlayer ions.
Most silicates are naturally produced mainly as main components of clay minerals. It is common to disperse/swell in water and purify by the difference in sedimentation speed. , cristobalite, etc.). Depending on the type, amount, particle size, crystallinity, and state of dispersion of these contaminants, they may be more preferable than pure silicates, and such complexes are also included in the component (B) ion-exchange layered silicate. .
In addition, the silicate used in the present invention is not limited to naturally occurring silicates, and may be artificially synthesized.

Specific examples of ion-exchange layered silicates include layered silicates having a 1:1 type structure or a 2:1 type structure described in Haruo Shiramizu, "Clay Mineralogy", Asakura Shoten (1988). mentioned.
The 1:1 type structure refers to a structure based on stacking of one layer of tetrahedral sheet and one layer of octahedral sheet, as described in "Clay Mineralogy" and the like.
The 2:1 type structure refers to a structure based on stacking two layers of tetrahedral sheets sandwiching one layer of octahedral sheets.
Specific examples of ion-exchange layered silicates having a 1:1 type structure include kaolin group silicates such as dickite, nacrite, kaolinite, metahalloysite and halloysite, and serpentine group silicates such as chrysotile, lizardite and antigorite. Salt etc. are mentioned.
Specific examples of ion-exchangeable layered silicates having a 2:1 structure include smectite group silicates such as montmorillonite, beidellite, nontronite, saponite, hectorite, and stevensite; vermiculite group silicates such as vermiculite; and mica. mica group silicates such as illite, sericite, and glauconite; attapulgite, sepiolite, palygorskite, bentonite, pyrophyllite, talc, chlorite group; These may form a mixed layer.
Among these, the ion-exchange layered silicate having a 2:1 type structure as the main component is preferred. More preferably, the main component is a smectite group silicate, and even more preferably, the main component is montmorillonite.
The type of the interlayer cation (the cation contained between the layers of the ion-exchangeable layered silicate) is not particularly limited. 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, gold, etc. preferred in some respects.

(2-3) Treatment of ion-exchangeable phyllosilicate The ion-exchangeable phyllosilicate may be used in a dry state, or may be used in a liquid slurry state.
Further, the shape of the ion-exchangeable layered silicate is not particularly limited, and may be a shape produced naturally or a shape at the time of artificial synthesis. A processed ion-exchange layered silicate may also be used.
Of these, the use of a granulated ion-exchangeable phyllosilicate is particularly preferred because it provides good polymer particle properties when the ion-exchangeable phyllosilicate is used as a catalyst component.
For the method of treating the ion-exchange layered silicate, the descriptions in paragraphs 0042 to 0071 of JP-A-2009-299046 can be referred to.

Component (B) preferably used in the present invention is a chemically treated ion-exchange layered silicate, and has 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 appears to be an indicator of the acid treatment strength of the clay parts.
Aluminum and silicon in the ion-exchange layered silicate are measured by a method of preparing a calibration curve by chemical analysis according to the JIS method and quantifying with fluorescent X-rays.

(3) Component (C)
Component (C) used in the present invention is an organoaluminum compound, preferably an organoaluminum compound represented by the following general formula (4).
(AlR _n X _3-n ) _m General formula (4)
[In the above general formula (4), R represents an alkyl group having 1 to 20 carbon atoms, X represents a halogen, hydrogen, an alkoxy group or an amino group, n is 1 to 3, m is 1 to 2 each represents an integer of ]
An organic aluminum compound can be used individually or in combination of multiple types.
Specific examples of organoaluminum compounds include trimethylaluminum, triethylaluminum, tri-normal-propylaluminum, tri-normal-butylaluminum, triisobutylaluminum, tri-normal-hexylaluminum, tri-normal-octylaluminum, tri-normal-decyl-aluminum, diethylaluminum chloride, and diethylaluminum. sesquichloride, diethylaluminum hydride, diethylaluminum ethoxide, diethylaluminum dimethylamide, diisobutylaluminum hydride, diisobutylaluminum chloride and the like. Among these, trialkylaluminums and alkylaluminum hydrides where m=1 and n=3 are preferred. More preferably, R is a trialkylaluminum having 1 to 8 carbon atoms.

(4) Preparation of Catalyst The olefin polymerization catalyst preferably used in the present invention contains the component (A), component (B) and component (C). These can be obtained by contacting them inside or outside the polymerization tank. The olefin polymerization catalyst may be prepolymerized in the presence of olefin.
The amount of component (A), component (B) and component (C) to be used is arbitrary.
For example, the amount of component (A) used relative to component (B) is preferably in the range of 0.1 μmol to 1000 μmol, more preferably 0.5 μmol to 500 μmol, per 1 g of component (B).
The amount of component (C) used relative to component (A) is preferably 0.01 to 5×10 ⁶ , more preferably 0, in terms of the molar ratio of component (C) aluminum to component (A) transition metal. .1 to 1×10 ⁴ .
The order of contacting the component (A), the component (B) and the component (C) is arbitrary, and after contacting two components among these, the remaining one component may be contacted, or three The components may be contacted simultaneously. In these contacts, a solvent may be used for sufficient contact. Examples of solvents include aliphatic saturated hydrocarbons, aromatic hydrocarbons, aliphatic unsaturated hydrocarbons, halides thereof, and prepolymerized monomers. Specific examples of aliphatic saturated hydrocarbons and aromatic hydrocarbons include hexane, heptane, and toluene. Moreover, propylene can be used as a solvent for the prepolymerized monomer.

(5) Prepolymerization The olefin polymerization catalyst is preferably subjected to prepolymerization, which involves contacting an olefin and polymerizing a small amount. Prepolymerization can improve the catalytic activity and reduce the production cost.
The olefin to be used is not particularly limited, but ethylene, propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, 3-methyl-1-butene, vinylcycloalkane, styrene, etc. It can be exemplified, preferably propylene.
The olefin can be fed to the prepolymerization tank at a constant rate or at a constant pressure, a combination thereof, or a stepwise change.
Although the prepolymerization temperature and prepolymerization time are not particularly limited, they are preferably in the range of -20°C to 100°C and 5 minutes to 24 hours.
The mass ratio of the prepolymerized polymer to the component (B) is preferably 0.01-100, more preferably 0.1-50.
In addition, component (C) can also be added during prepolymerization.
It is also possible to coexist a polymer such as polyethylene or polypropylene, or an inorganic oxide solid such as silica or titania during or after the contact of the above components.
The catalyst may be dried after prepolymerization. The drying method is not particularly limited, but examples include drying under reduced pressure, drying by heating, and drying by circulating a dry gas. These methods may be used alone, or two or more methods may be used in combination. may be used. In the drying step, the catalyst may be stirred, vibrated, fluidized, or allowed to stand still.

2. Monomer The monomer used is propylene alone or a combination of propylene and a comonomer selected from the group consisting of ethylene and α-olefins.
As the α-olefin, for example, an α-olefin having 4 to 10 carbon atoms can be used. More specific examples include 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, 3-methyl-1-butene, vinylcyclohexane, and styrene. Ethylene and/or α-olefin to be copolymerized with propylene may be of one type or a combination of two or more types. One or two selected from ethylene and 1-butene are preferred.
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 method may be adopted as long as the catalyst for olefin polymerization and the monomer are efficiently brought into contact with each other. 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 vapor phase polymerization method that keeps each monomer in a gaseous state without substantially using a liquid solvent. etc. can be adopted.
Further, as the polymerization method, a method of performing continuous polymerization, batch polymerization, or preliminary polymerization is also applied.
In addition, the number of polymerization stages may be one, and a mode such as two stages of bulk polymerization, gas phase polymerization after bulk polymerization, or two stages of gas phase polymerization is also possible. .
Among them, it is preferable to perform one-step bulk polymerization using propylene as a solvent.

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

In the case of the production method disclosed in the above-mentioned Patent Document 2 (JP-A-2009-299046), by relatively increasing the β-methyl elimination reaction rate by performing bulk polymerization at a higher temperature, a terminal vinyl with a low molecular weight A group-containing polypropylene can be obtained, but on the other hand, the 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 or lumps, and the temperature exceeds the critical temperature of propylene as a solvent. As a result, there is a problem that the shape and properties of the polymer particles are deteriorated.
In response to such problems, the present invention provides a 5-membered heterocyclic ring having a bisindenylhafnium complex structure and having a specific substituent at the 2-position of the indene ring, which is a ligand, and Polymerization is carried out in a temperature range suitable for bulk polymerization using a catalyst system containing a metallocene compound substituted with an aryl group having a specific substituent at the 4-position. A terminal vinyl group-containing polypropylene can be obtained.
Additionally, hydrogen can be used supplementarily during the polymerization process to improve activity.
The reason for the improvement in activity is thought to be the dormant active sites, such as π allyl-transition metal complexes as side reactions and immediately after propylene 2,1 insertion, but these are regenerated by hydrogen. considered to be activated.
For many transition metal complex catalysts, the chain transfer rate to hydrogen is fast and acts as an effective chain transfer agent to produce saturated ends, thus making terminal vinyl structures less likely.
However, in the production method of the present invention, surprisingly, even if hydrogen is added, the action as a chain transfer agent is poor and the vinyl terminal ratio is still kept high due to the action of reactivation.
Therefore, in the production method of the present invention, the activity is improved and the vinyl terminal ratio is kept high by supplementary use of hydrogen during the polymerization process.

The amount of hydrogen used in the polymerization is 0 to 2.0×10 ⁻⁴ , preferably more than 0 and 2.0×10 ⁻⁴ or less, more preferably 2.0×, in terms of the feed mass ratio of hydrogen to propylene. The range is 10 ⁻⁵ to 1.5×10 ⁻⁴ , more preferably 3.0×10 ⁻⁵ to 1.0×10 ⁻⁴ .
When bulk polymerization is performed, the concentration of the gas phase portion is on average 0 to 10000 ppm, preferably 100 to 8000 ppm, more preferably 200 to 1000 ppm, thereby improving the activity and producing the target polymer. Obtainable.

4. Vinyl-Terminated Propylene-Based Polymer The vinyl-terminated propylene-based polymer produced by the present invention is a propylene homopolymer or a copolymer of propylene and a comonomer selected from the group consisting of ethylene and α-olefins. be.
According to the present invention, by using the propylene polymerization catalyst described above to produce a vinyl-terminated propylene-based polymer having a low molecular weight, a vinyl-terminated polymer having a high vinyl-terminated ratio and favorable shape and properties of the polymer can be obtained. A group-containing propylene-based polymer can be produced with high activity.
The terminal vinyl group-containing propylene-based polymer produced according to the present invention will be described below.

(1) Number Average Molecular Weight The terminal vinyl group-containing propylene-based polymer produced according to the present invention has the following properties (I).
Characteristic (I): The number average molecular weight (Mn) of the terminal vinyl group-containing propylene-based polymer of the present invention measured by GPC is less than 50,000 and is 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. In addition, since the obtained propylene-based polymer has an increased amount of terminal vinyl groups per unit mass, there is also 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 5,000 or more, more preferably 10,000 or more, and still more preferably 15,000 or more. Within the above range, the particle properties are good.
In the present invention, as a catalyst component for polymerization, a 5-membered heterocyclic ring having a bisindenylhafnium complex structure and having a specific substituent at the 2-position of the indene ring, which is a ligand, and a 4 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, which is a termination reaction, it is relatively low temperature and has a low molecular weight terminal vinyl. A group-containing propylene-based polymer can be easily obtained. The rate of elimination reaction can also be controlled by changing the polymerization temperature, the concentration of propylene, and the pressure. For example, in the complexes shown in Examples, the higher the polymerization temperature, the smaller the number average molecular weight (Mn).

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 equipment are as follows.
Apparatus: Waters GPC (ALC/GPC, 150C)
Detector: FOXBORO MIRAN, 1A, IR detector (measurement wavelength: 3.42 μm)
Column: Showa Denko AD806M/S (3 columns)
Mobile phase solvent: o-dichlorobenzene (ODCB)
Measurement temperature: 140°C
Flow rate: 1.0 mL/min Injection volume: 0.2 mL

For sample preparation, the sample and ODCB (containing 0.5 mg/mL dibutylhydroxytoluene (BHT)) were used to prepare a 1 mg/mL solution, which was dissolved at 140°C for about 1 hour. Let me do it.
In addition, the baseline and interval of the obtained chromatogram are performed as shown in FIG.
Further, conversion from the retention volume obtained by GPC measurement to molecular weight is performed using a previously prepared standard polystyrene calibration curve. The standard polystyrene used is the following brand manufactured by Tosoh Corporation.
Brand: F380, F288, F128, F80, F40, F20, F10, F4, F1, A5000, A2500, A1000
A calibration curve is generated by injecting 0.2 mL of a solution dissolved in ODCB (containing 0.5 mg/mL of BHT) at 0.5 mg/mL each. A calibration curve uses a cubic equation obtained by approximation using the least squares method.
The following numerical values are 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-based polymer produced according to the present invention has the following properties (II).
Characteristic (II) The terminal vinyl ratio is 0.7 or more. In the present invention, the terminal vinyl ratio means the ratio of chains having a vinyl group at the terminal to the total polymer chains of the terminal vinyl group-containing propylene polymer. It is calculated by the following formula.
(Terminal vinyl rate) = {[Vi] / ((total number of terminals) - LCB number)} x 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 branched chains 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. It is more preferably 0.8 or more, and ideally 1.0 (all polymer chains have terminal vinyl groups). Stereoregularity can also be improved at the same time by increasing the terminal vinyl ratio and making it within the above range.

(2-1) Relationship between Reaction Mechanism and Terminal Structure In the present invention, the relationship between the reaction mechanism and the resulting terminal structure when obtaining a propylene-based polymer having a terminal vinyl ratio of 0.7 or more is as follows. .
In the polymerization of propylene, β-hydrogen elimination generally occurs, and a terminal of a vinylidene structure (propyl-vinylidene structure) represented by the following structural formula (1-b) is generated.
In addition, when hydrogen is used, chain transfer usually occurs preferentially to hydrogen to form the terminal of the i-butyl structure represented by the following structural formula (1-c).
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, resulting in a vinyl structure (1-propenyl structure) represented by the following structural formula (1-a). (Reference: Macromol. Rapid Commun. 2000, 21, 1103-1107).
Moreover, in the polymerization of propylene, the following terminal structure is generated due to the reaction mechanism. After propylene insertion and β-hydrogen elimination, the terminal of the i-butenyl structure represented by the following structural formula (1-d) is generated via a π-allyl intermediate that can be further abstracted from the γ-position.
In addition, propylene may undergo random 2,1 insertion, but after such irregular bonding, chain transfer to hydrogen, β-hydrogen elimination, and π allyl intermediates lead to When hydrogen is eliminated, 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) ( 2-butenyl structure) ends are generated. Here, the 1-butenyl structure (structural formula (1-f)) is included in the terminal vinyl group of the present invention.
Furthermore, when ethylene and 1-butene are used as comonomers in the present invention, the following ends are produced mechanically.
Chain transfer to hydrogen after insertion of ethylene produces an n-propyl structure terminal represented by the following structural formula (1-h).
When β-hydrogen elimination occurs after ethylene insertion, a terminal of a 1-propenyl structure represented by the following structural formula (1-a) is generated.
After insertion of 1-butene, chain transfer to hydrogen produces an i-pentyl structure terminal represented by the following structural formula (1-i).
After 1-butene insertion, β-hydrogen elimination occurs to form a terminal butyl-vinylidene structure represented by the following structural formula (1-j).

The starting end is always a saturated hydrocarbon end, and unsaturated bonds do not appear at both ends. This means that when modifying the terminal vinyl group-containing polypropylene of the present invention, 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. Both ends may be modified, and the form will be different from the terminal vinyl group-containing polypropylene of the present invention.

Therefore, in order to increase the terminal vinyl ratio, the reactions that produce structural formulas (1-b) to (1-e) and (1-g) to (1-j) are suppressed, and structural formula (1-a) , (1-f) are preferred.
Among the polymerization conditions, with respect to the catalyst, as described above, a 5-membered heterocyclic ring having a bisindenylhafnium complex structure and having a specific substituent at the 2-position of the indene ring, which is a ligand, and the 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 produces structural formula (1-a) can be promoted.
Moreover, when an olefin polymerization catalyst containing such a metallocene compound is used, even when hydrogen is used, although the activity increases, the β-methyl elimination reaction occurs preferentially, and the vinyl Structure (1-propenyl structure): Structural formula (1-a) is mainly produced. This selectivity can also be controlled by varying the polymerization temperature. For example, in the olefin polymerization catalyst containing the metallocene compound shown in the Examples, the higher the polymerization temperature, the higher the terminal vinyl fraction.

(2-2) Method for Identifying Terminal Vinyl Ratio ¹ H-NMR and ¹³ C-NMR are carried out by the method described below to identify the terminal vinyl ratio.
[Sample preparation and measurement conditions]
200 mg of a sample was combined with 2.4 ml of o-dichlorobenzene/deuterobrominated benzene (C ₆ D ₅ Br) = 4/1 (volume ratio) and hexamethyldisiloxane as a reference substance for chemical shift, and an NMR sample with an inner diameter of 10 mmφ. It was placed in a tube and uniformly melted with a block heater at 150°C.
The NMR measurement was performed using an AV400 type NMR apparatus (Bruker Biospin Co., Ltd.) equipped with a 10 mmφ cryoprobe.
¹ H-NMR was used to quantify unsaturated ends. The measurement conditions of ¹ H-NMR were a sample temperature of 120° C., a pulse angle of 4.5°, a pulse interval of 2 seconds, and 512 integration times. The chemical shift was set at 0.09 ppm for the hexamethyldisiloxane proton signal and the chemical shifts for the signals due to other protons were referenced to this.
¹³ C-NMR was used to quantify saturated ends. 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, and an accumulation number of 1024 times, and measurement was performed by a broadband decoupling method. The chemical shift was set to 1.98 ppm for the ¹³ C signal of hexamethyldisiloxane and the chemical shifts of the other ¹³ C signals were referenced to this.

[Method for calculating the number of unsaturated ends]
In ¹ H-NMR, the 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 the signals of 5.86 to 5.69 ppm. Therefore, the number of terminal vinyl groups [Vi] is the total number of 1-propenyl and ¹ -butenyl, and the amount of unsaturated bonds per 1000 monomers in total. Ask from
In ¹ H-NMR, the proton signals of unsaturated bonds of structural formula (1-b) propyl-vinylidene and structural formula (1-j) butyl-vinylidene are 4.79 to 4.65 ppm in the ¹ H-NMR spectrum. is detected overlapping with the signal of Therefore, the number of terminal vinylidene groups [Vd] is the total number of propyl-vinylidene and butyl-vinylidene, and the amount of unsaturated bonds per 1000 monomers in total is expressed by the following formula using the signal intensity of the 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 ends [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 respectively structural formula (1-a) + structural formula (1-f), structural formula (1-b) + structural formula (1-j), structural formula (1-d), Structural Formula (1-g), and Structural Formula (1-m), representing characteristic values of signals based on the following formulas.
Iv = ( _I5.08-4.85 + _I5.86-5.69 )/3,
Ivd = (I _4.79-4.65 )/2,
Iibu=I _5.30-5.08 ,
Ivnl = ( _I5.58-5.30 )/2,
Iivd=(I _4.85-4.79 )/2
I indicates the integrated intensity, and the numerical value subscripted to I indicates the chemical shift range. For example, I 5.08-4.85 indicates the integrated intensity of signals detected between _{5.08 ppm and 4.85} ppm.
Also, Itotal is an amount represented by the following formula.
I total = IC2 + IC3 + IC4 + Ivi + Ivd + Iibu + Ivnl + Iivd
IC2 represents the characteristic value of the signal based on ethylene, IC3 represents the characteristic value of the signal based on propylene, and IC4 represents the characteristic value of the signal based on 1-butene, and the amount is represented by the following formula.
IC2 = 1/4 x {(Imain x [C2] x 2)/([C2] x 2 + [C3] x 3 + [C4] x 4)}
IC3 = 1/6 x {(Imain x [C3] x 3)/([C2] x 2 + [C3] x 3 + [C4] x 4)}
IC4 = 1/8 x {(Imain x [C4] x 4)/([C2] x 2 + [C3] x 3 + [C4] x 4)}
[C2] is the ethylene content (mol%) calculated by ¹³ C-NMR described later, [C3] is the propylene content (mol%) calculated by ¹³ C-NMR described later, and [C4] is ¹³ C described later. - Indicates the 1-butene content (mol%) calculated by NMR.
Imain is the total sum of proton signals detected at 4.00 to 0.00 pm in the ¹ H-NMR spectrum of the polymer main chain and the saturated end.

[Method for calculating the number of saturated ends]
The number of saturated ends below is calculated 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-dime×1000/Itotal-C
Structural formula (1-l): [3,4-dimethylpentyl]=I3,4-dime×1000/Itotal-C

Further, in the vinyl-terminated polypropylene of the present invention, in addition to the structure based on regular 1,2 insertion of propylene inside the polymer, the following 2,1 bonds based on irregular insertion of propylene, 1, It can have 3 bonds. When 1-butene is used as a comonomer, it can have the following 1,4 bond structure based on irregular insertion in addition to the structure based on regular 1,2 insertion.

Here, Ii-butyl, Inbu, Inpr, Ii-pen, I2,3-dime, and I3,4-dime are structural formula (1-c), structural formula (1-e), structural formula (1- h), representing characteristic values of signals based on Structural Formula (1-i), Structural Formula (1-k), and Structural Formula (1-l), and is the amount represented by the following formula.
Ii-butyl = ( _I23.80-23.70 + _I25.80-25.70 )/2
Inbu =I _14.06-14.02
Inpr = (I _14.44-14.42 +I _30.46-30.45 )/2
Ii-pen = (I _30.70-30.50 +I _42.00-41.80 )/2
I2,3-dime=( _I16.21-16.17 + _I31.86-31.81 )/2
I3,4-dime =I _12.0-11.60
Also, Itotal-C is an amount represented by the following formula.
Itotal-C=Ii-butyl+Inbu+Inpr+Ii-pen+I2,3-dime+I3,4-dime+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 the 1,2-inserted propylene, and I2,1-P is the characteristic value of the signal based on the bond of the 2,1-inserted propylene. I1,3-P is the characteristic value of the signal based on the binding of 1,3-inserted propylene, and I1,2-B is the characteristic value of the signal based on the binding of 1-butene with 1,2-insertion. The value, I1,4-B, represents the characteristic value of the signal based on the binding of 1-butene with a 1,4 insertion and is the quantity shown in 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 _48.80-44.50 + I _43.90-42.80 /2
I2,1-P = ( _I35.72-35.63 + _I35.83-35.77 )/2
I1,3-P =I _30.82-30.74 /2
I1, 2-B = I _41.00-39.00 + I _43.90-42.80 /2
I1,4-B=I _34.45-34.15 /2

[Method for calculating the 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. It is the total number of ends up to (1-l).

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

[In the structural formula (A), P ¹ , P ² and P ³ are propylene-based 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 , C _c indicate the methylene carbons adjacent to the methine carbon (C _br ). ]
In Structural Formula (A), the main chain of the propylene-based polymer is three lines of the P ¹ -C _br -P ² line, the P ¹ -C _br -P ³ line, or the P ² -C _br -P ³ line. there is a street. Thus, correspondingly, the line C _br -P ³ , the line C _br -P ² or the line C _br -P ¹ can be said branched chain. P ¹ , P ² , P ³ may themselves contain branching carbons (C _br ) other than the C _br described in Structural Formula (A).
Here, the LCB structure is assigned three methylene carbons ⁽ C _a , C _b , C _c ) are observed as methine carbon (C _br ) at 31.7-31.5 ppm. It is characteristic that the three methylene carbons adjacent to _Cbr are diastereotopicly separated into three non-equivalent carbons.
The LCB number is the number of methine carbons (C _br ) at the base of branched chains having 7 or more carbon atoms per 1000 monomer units calculated by ¹³ C-NMR.
A branched chain with more than 6 carbon atoms and a branched chain with 6 or less carbon atoms can be distinguished from each other by the difference in the peak position of the methine carbon at the base of the branch (Macromol. Chem. Phys. 2003, Vol. 204, 1738 See page).
In the present invention, the LCB number is not particularly limited, but is usually preferably 0.5 or less.

(3) Polymer shape and properties (coarse powder amount, bulk density)
The terminal vinyl group-containing propylene-based 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) Amount of Coarse Particles Regarding the amount of coarse particles of the propylene-based polymer, when the amount of coarse particles exceeds 1% by mass, problems such as contamination of the polymerization tank and fouling occur in bulk polymerization. do.
To solve this problem, the present invention can reduce the amount of 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% by mass. .3% by mass or less.
The amount of coarse powder is measured using a vibrating sieve particle size analyzer, and the ratio (% by mass) of the polymer mass remaining on the sieve with an opening of 2000 μm or more to the total sample mass is specified as the amount of coarse powder. .

(3-2) Bulk Density The properties of the polymer particles of the propylene-based polymer can be evaluated by bulk density.
The bulk density is an index that correlates with the average particle size of the polymer and the amount of coarse particles due to aggregation and the like, 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.
Bulk density is measured according to ASTM D1895-69.

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

(5) mm fraction of 3 chains of propylene units The terminal vinyl group-containing propylene-based 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 3 chains of propylene units calculated by ¹³ C-NMR reaches 95% or more, which is preferable. is 96% or more, more preferably 97% or more.
A higher mm fraction of component (A) means a higher degree of control. If it is less than this value, the mechanical properties such as the elastic modulus of the product are lowered.

The mm fraction of 3 chains of propylene units is obtained by substituting the integrated intensity of the ¹³ C signal measured by ¹³ C-NMR measurement into the following equation.
mm (%) = Imm x 100/(Imm + 3 x Imrrm)
Here, Imm=I _{23.6 to 21.1} and Imrrm=I _{19.8 to 19.7} .
The ¹³ C-NMR measurement method for obtaining the mm fraction of the propylene unit tricycles can be performed in the same manner as the above measurement.
Spectral attribution can be performed with reference to Polymer Journal, Vol. 16, p.717 (1984), Asakura Shoten, Macromolecules, Volume 8, p.687 (1975), and Polymer, Vol. 30, p. 1350 (1989). can.

(6) Heterologous bond amount (2,1 bond and 1,3 bond, and 1,4 bond amount)
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 regioregularity.
Although the regioregularity of polypropylene is not limited, it is preferable that the 2,1 bond and the 1,3 bond be 0.2 mol % or less and 0.2 mol % or less, respectively, as calculated by ¹³ C-NMR.
The 2,1 bond is more preferably 0.15 mol % or less, still more preferably 0.12 mol % or less, and particularly preferably 0.10 mol % or less.
The 1,3 bond content is more preferably 0.15 mol % or less, still more preferably 0.12 mol % or less, and particularly preferably 0.10 mol % or less.
If the amount of heterogeneous bonds is small, when mixed or applied to other polypropylene or base material, the mixing efficiency will be improved, the coating efficiency will be improved, and it will be difficult to peel off as a coating agent.
Also, by controlling the regularity (steric/positional) of propylene so that it does not become too high, the solubility in a solvent can be increased and the reactivity of the terminal vinyl can be increased.

The heterologous binding amount (molar concentration) is determined from the following formula 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 units other than propylene When the vinyl-terminated propylene-based polymer of the present invention is a copolymer of propylene and a comonomer selected from the group consisting of ethylene and α-olefins, The content of structural units derived from the comonomer is preferably 1.5 mol % or more.
The comonomer enters into the regularly (sterically/positionally) inserted propylene chains to alter the primary structure. One result is the effect of lowering the melting point.
Therefore, by increasing the comonomer content, the crystallinity is not too high, the solubility in solvents can be increased, and the reactivity of the terminal vinyl can be increased.
On the other hand, the regularly (sterically/positionally) inserted propylene chain does not become too short, and when mixed or applied to other polypropylene or substrate, it improves the mixing efficiency, improves the coating efficiency, and can be used as a coating agent. From the viewpoint of making peeling difficult, the vinyl-terminated 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-olefins. The content of structural units is preferably 50 mol % or less.

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

The content (molar concentration) of the comonomer unit is obtained 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 vinyl-terminated propylene polymer produced by the present invention preferably has a melt flow rate (MFR) of 470 g/10 minutes or more measured at 230° C. under a load of 2.16 kgf. Although the upper limit of MFR is not particularly limited, it is preferably 10000 g/10 minutes or less.
When the MFR is within the above range, the solubility in solvents and the compatibility with other base materials can be improved.
The MFR can be measured according to the melt flow rate of the polypropylene test method of JIS K6758 (test conditions: 230°C, load 2.16 kgf).

5. Applications of propylene-based polymers containing terminal vinyl groups Conventionally, in order to synthesize propylene-based polymers with small molecular weights, polymer particles with excellent shape and properties are obtained when polymerization is carried out under conditions of high temperature and high pressure. It was difficult.
The present invention is thought to increase the reaction rate by homopolymerizing or copolymerizing propylene using a catalyst containing a specific metallocene compound represented by the general formula (1), and a propylene polymer having a small molecular weight. It can be synthesized under conditions of relatively low temperature and low pressure.
In addition, according to the present invention, a propylene-based polymer having a small molecular weight and excellent polymer particle shape and properties can be easily produced. It is highly effective in improving the shape and properties of polymer particles.
The vinyl-terminated 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 percentage of vinyl terminal structures. 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 optionally contain known antioxidants, ultraviolet absorbers, antistatic agents, nucleating agents, lubricants, flame retardants, antiblocking agents, colorants, inorganic substances or After blending various additives such as organic fillers and various synthetic resins, the mixture is heated and melt-kneaded using a melt-kneader, and can be used as pellets that are further cut into granules.

EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples.
Physical property measurements, analyzes, etc. in the following examples were carried out according to the following methods.

(1) Melt flow rate (MFR):
It was measured according to the melt flow rate of the polypropylene test method of JIS K6758 (test conditions: 230°C, load 2.16 kgf). The unit is g/10 minutes.
(2) Molecular weight and molecular weight distribution (Mw, Mn, Mw/Mn):
It was measured by gel permeation chromatography (GPC) by the method described in the specification above.
(3) Melting point (Tm):
Using DSC6200 manufactured by Seiko Instruments Inc., 5 mg of the sheet-shaped sample piece was packed in an aluminum pan, heated from room temperature to 200 ° C. at a temperature increase rate of 100 ° C./min, held for 5 minutes, and then heated at 10 ° C./min. to determine the crystallization temperature (Tc) as the maximum crystal peak temperature (°C) when crystallized, and then raise the temperature to 200°C at 10°C/min. The melting point (Tm) was determined as the peak temperature (°C).
(4) mm fraction of 3 chains of propylene units:
Using an AV400 type NMR apparatus (Bruker Biospin Co., Ltd.) equipped with a cryoprobe of 10 mmφ, measurement was performed by the method described in the above specification. The unit is %.
(5) catalytic activity (CE) (g/ghr)
The catalytic activity is a value per unit time obtained by dividing the polymer yield (g) by the introduced catalyst amount (g) (value excluding the prepolymerized polymer).
(6) Composition analysis:
The composition of the ion-exchange layered silicate was measured by fluorescent X-rays after preparing a calibration curve by chemical analysis according to the JIS method.
(7) Method for Measuring Bulk Density (BD) The bulk density of polymer particles was measured according to ASTM D1895-69.
(8) Amount of coarse powder:
A vibrating sieve particle size analyzer was used to measure the amount of coarse powder in the polymer particles. Shake sieves with openings 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, and 3,000 μm. The sample was subjected to vibration classification for 10 minutes or more using a machine, and the ratio (% by 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 complexes (Complex 1) rac-dichloro[1,1′-dimethylsilylenebis{2-(5-t-butyl-2-furyl)-4-(4-isopropyl-phenyl)-indenyl}] Hafnium was synthesized according to the methods of Example 13 of JP-A-2009-299046 and Example 1 of JP-A-2009-91512.

(2) Preparation of catalyst (2-a) Chemical treatment of ion-exchange layered silicate 645.1 g of distilled water and 82.6 g of 98% sulfuric acid were added to a 1 L three-necked flask equipped with a stirring blade and a reflux device. , and the temperature was raised to 95°C.
Commercially available montmorillonite (Benclay KK manufactured by Mizusawa Chemical Industry Co., Ltd., Al = 9.78 mass%, Si = 31.79 mass%, Mg = 3.18 mass%, Al / Si (molar ratio) = 0.320, An average particle size of 14 μm) was added, and the reaction was allowed to proceed at 95° C. for 320 minutes. After 320 minutes, 0.5 L of distilled water was added to stop the reaction and filtered to obtain 255 g of a solid cake.
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 wt%, Si = 36.05 wt%, Mg = 2.13 wt%, Al/Si (molar ratio) = 0.222.
1545 g of distilled water was added to the above cake to form 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 with 1 L of distilled water three times to obtain a cake-like solid again.
The collected cake was dried to obtain 80 g of chemically treated montmorillonite. 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 % by mass.

(2-b) Prepolymerization 20 g of the obtained chemically treated montmorillonite was placed in a 1 L three-necked flask, 131 mL of heptane was added to form a slurry, and 50 mmol of triisobutyl aluminum (concentration of 143.4 mg/mL heptane solution was added thereto). 69 mL) was added and stirred for 1 hour. After 1 hour, it was washed with heptane to 1/100 and the total volume was brought to 100 mL.
The slurry solution containing this chemically treated montmorillonite was kept at 50° C., and 4.2 mmol of tri-normal octylaluminum (10.7 mL of a heptane solution with a concentration of 143.4 mg/mL) was added thereto and stirred for 20 minutes.
Thereto, 0.3 mmol of rac-dichloro[1,1′-dimethylsilylenebis{2-(5-t-butyl-2-furyl)-4-(4-isopropyl-phenyl)-indenyl}]hafnium (50 mL of toluene ) was added, and the mixture was stirred for 20 minutes while maintaining the temperature at 50°C.
An additional 350 mL of heptane was then added and the slurry was introduced into a 1 L autoclave.
After the internal temperature of the autoclave was adjusted to 40° C., propylene was fed at a rate of 10 g/hour, and prepolymerization was carried out while maintaining the temperature at 40° C. for 4 hours. After that, the propylene feed was stopped, and residual polymerization was carried out at 40° C. for 1 hour.
After removing the supernatant of the resulting catalyst slurry by decantation, the prepolymerized catalyst was washed by adding heptane again and decanting. 12 mmol of triisobutylaluminum (16.6 mL of a heptane solution with a concentration of 143.4 mg/mL) was added to the portion remaining after the decantation, and the mixture was stirred for 10 minutes. By drying this solid under reduced pressure at 40° C. for 2 hours, 49.8 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 1.49. This prepolymerized catalyst was referred to as catalyst 1.

(3) Polymerization A 3-liter autoclave was heated and dried by circulating nitrogen, and then the inside of the vessel was replaced with propylene and cooled to room temperature. After introducing 2.86 mL of a heptane solution (140 mg/mL) of triisobutylaluminum and 750 g of liquid propylene, the temperature was raised to 75°C. After that, 200 mg of the catalyst 1, excluding the prepolymerized polymer, was pressure-fed into the polymerization tank with high-pressure argon to initiate polymerization. After holding at 75° C. for 1 hour, unreacted propylene was quickly purged to terminate the polymerization. About 217 g of propylene homopolymer was obtained.
Table 1 shows the evaluation results of the obtained polymer.

[Example 2]
Polymerization was carried out in the same manner as in Example 1, except that 750 g of liquid propylene was introduced after 160 N (normal) ml of H ₂ was introduced into the tank, and 80 mg of catalyst 1 was used, excluding the prepolymerized polymer. .
Table 1 shows the evaluation results of the obtained polymer.

[Example 3]
Polymerization was carried out in the same manner as in Example 1, 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, excluding the prepolymerized polymer.
Table 1 shows the evaluation results of the obtained polymer.

[Example 4]
Polymerization was carried out in the same manner as in Example 1 except that 750 g of liquid propylene was introduced into the vessel after 480 Nml of H ₂ was introduced, and 50 mg of catalyst 1 was used, excluding the prepolymerized polymer.
Table 1 shows the evaluation results of the obtained polymer.

[Example 5]
Polymerization was carried out in the same manner as in Example 1, except that 750 g of liquid propylene was introduced after 640 Nml of H ₂ was introduced into the tank, and 40 mg of catalyst 1 was used, excluding the prepolymerized polymer.
Table 1 shows the evaluation results of the obtained polymer.

[Example 6]
Polymerization was carried out in the same manner as in Example 1, except that 750 g of liquid propylene was introduced after 960 Nml of H ₂ was introduced into the vessel, and 40 mg of catalyst 1 was used, excluding the prepolymerized polymer.
Table 1 shows the evaluation results of the obtained polymer.

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

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

[Example 9]
Polymerization was carried out in the same manner as in Example 8, except that 750 g of liquid propylene was introduced into the tank after 160 Nml of H ₂ was introduced, and 80 mg of catalyst 1 was used, excluding the prepolymerized polymer.
Table 1 shows the evaluation results of the obtained polymer.

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

[Comparative Example 1]
(1) Synthesis of complex (Complex 2) rac-dichloro[1,1′-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(4-isopropyl-phenyl)-indenyl}]hafnium , synthesized according to the method of Example 13 (1) of JP-A-2009-299046.

(2) Adjustment of catalyst In (2-b) prepolymerization of Example 1, instead of (complex 1), rac-dichloro[1,1′-dimethylsilylenebis{2-(5-methyl-2-furyl )-4-(4-isopropyl-phenyl)-indenyl}]hafnium (0.3 mmol) was used.
As a result, 54.0 g of 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 A 3-liter autoclave was heated and dried by circulating nitrogen, and then the inside of the vessel was replaced with propylene and cooled to room temperature. After introducing 2.86 mL of a heptane solution (140 mg/mL) of triisobutylaluminum and 750 g of liquid propylene, the temperature was raised to 75°C. After that, 200 mg of the above catalyst 2, excluding the prepolymerized polymer, was pressure-fed into the polymerization tank with high-pressure argon to initiate polymerization. After holding at 75° C. for 1 hour, unreacted propylene was quickly purged to terminate the polymerization. About 350 g of propylene homopolymer was obtained.
Table 1 shows the evaluation results of the obtained copolymer.

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

[Comparative Example 3]
Polymerization was carried out in the same manner as in Comparative Example 1, except that after introducing 750 g of liquid propylene, the temperature was raised to 85°C and the 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 sufficiently low number average molecular weight (Mn) of 33,200 or less, and a terminal vinyl ratio (Vi) of 0.7 or more. , the mm fraction of 3 chains of propylene units exceeds 95%, the stereoregularity is high, the bulk density exceeds 0.348 g / ml, and the amount of coarse powder is about 0 to 0.2% by mass. Good properties.

From Examples 1 to 6, it can be seen that the CE (catalytic activity) increases and the activity can be enhanced by increasing the amount of hydrogen used. In this case, the effect on the molecular weight of the terminal vinyl group-containing propylene polymer obtained and the mm fraction of the propylene unit tricycle is small. The terminal vinyl percentage tends to decrease slightly with an increase in the amount of hydrogen used, but still retains a high percentage. It is thought that as the amount of hydrogen used increases, the rate of terminal vinyl tends to decrease due to an increase in the proportion of chain transfer to hydrogen. By using the catalyst system containing, the decreasing tendency of the terminal vinyl fraction 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 if the polymerization temperature is 70°C. In this case, the effect on the mm fraction of the tri-chain of propylene units in the obtained propylene-based polymer is small.
From Example 8, it can be seen that the molecular weight can be reduced by raising the temperature as compared with Example 1, and that even if the polymerization temperature is 80° C., the particle properties are not significantly deteriorated. In this case, the effect on the mm fraction of the tri-chain of propylene units in the obtained propylene-based polymer is small.
Examples 1, 7 and 8 show that molecular weight can be controlled by controlling polymerization temperature. The present invention is characterized by obtaining a terminal vinyl group-containing propylene polymer having a number average molecular weight (Mn) of less than 50,000. Mn), it is considered possible to satisfy the regulation of the molecular weight in the same polymerization system by setting the polymerization temperature to about 50° C. or higher.
From Examples 8 and 9, it can be seen that the activity can be increased by increasing the amount of hydrogen used, as in Examples 1 to 6, even under conditions of high polymerization temperature. From this, it is considered that even in a polymerization system having low polymerization activity due to a low polymerization temperature, as in Example 7, the polymerization activity can be enhanced by increasing the amount of hydrogen used.

In contrast to these Examples, as shown in Comparative Examples, a metallocene other than the metallocene compound represented by the general formula (1) in the present invention as described in Patent Document 1 (Japanese Patent Application Laid-Open No. 2009-299046) It is difficult to obtain a propylene-based polymer having a low molecular weight, a high vinyl terminal ratio, and good polymer shape and properties by conventional production methods using a catalyst system containing a compound.
In Comparative Example 1, the molecular weight was not sufficiently reduced. Comparative Examples 2 and 3 are examples in which the polymerization temperature was raised relative to Comparative Example 1 in accordance with the findings of Examples 1, 7 and 8 in order to reduce the molecular weight.
Comparative Example 2 is an example in which the polymerization temperature is 80° C. and the molecular weight is controlled to about 42,000, which is less than 50,000. Admitted.
Furthermore, 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 properties significantly deteriorated. was accepted. In general commercial-scale polymerization equipment, if the amount of coarse powder exceeds 1%, problems such as contamination of the polymerization tank and fouling may occur.

Claims (8)

Number average molecular weight measured by GPC is 5,000 to 30,000, terminal vinyl ratio is 0.7 or more, bulk density is 0.30 g/ml to less than 0.40 g/ml, using a vibrating sieve particle size analyzer. Polymer particles of a terminal vinyl group-containing propylene-based polymer having a coarse powder content, which is the ratio of the polymer mass remaining on a sieve with a mesh size of 2000 μm or more, to the total sample mass measured as measured by the above method . The polymer particles of the terminal vinyl group-containing propylene-based polymer according to claim 1, having a melting point (Tm) of less than 153°C. 3. Polymer particles of the terminal vinyl group-containing propylene polymer according to claim 1 or 2, which are raw materials for macromers, paints, primers, surface modifiers or coating materials. A macromer comprising polymer particles of the vinyl-terminated propylene polymer according to claim 1 or 2. A paint comprising polymer particles of the terminal vinyl group-containing propylene polymer according to claim 1 or 2. A primer comprising polymer particles of the terminal vinyl group-containing propylene polymer according to claim 1 or 2. A surface modifier comprising polymer particles of the terminal vinyl group-containing propylene polymer according to claim 1 or 2. A coating material comprising polymer particles of the terminal vinyl group-containing propylene polymer according to claim 1 or 2.

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