JP5337401B2 - Cross-linked olefin polymer and process for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a crosslinked olefin polymer which is flexible and includes a high degree of crosslinking. <P>SOLUTION: There is provided a crosslinked olefin polymer of a degree of crosslinking of 20% or higher obtained by the crosslinking reaction of an &alpha;-olefin polymer which satisfies the following requirements (A) and (B): (A) it is an &alpha;-olefin polymer selected from among a homopolymer of an 8-30C &alpha;-olefin, a copolymer of at least two 8-30C &alpha;-olefins, and a copolymer which is a copolymer of an 8-30C &alpha;-olefin and ethylene and/or propylene, wherein the amount of 8-30C &alpha;-olefin units is 50 mol% or more and the amount of ethylene and/or propylene unit is below 50 mol% and (B) it has an intrinsic viscosity [&eta;] of 0.1-4.0 dl/g. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to a crosslinked olefin polymer using an α-olefin polymer having 8 to 30 carbon atoms and a method for producing the same, and more specifically, impact absorbers, pressure-sensitive adhesives, oil absorbents, and sealing and adhesion of electronic components. The present invention relates to a crosslinked olefin polymer using an α-olefin polymer having 8 to 30 carbon atoms, which is suitable for uses such as an agent, and a method for producing the same.

  In the field of polymer chemistry, techniques for improving physical properties by controlling the molecular structure (for example, formation of a branched structure or a crosslinked structure) are known, and are currently used in various fields. Furthermore, since the olefin polymer has the advantages of being resistant to acids and alkalis and being inexpensive, attempts have been made to impart a branched structure or a crosslinked structure to the olefin polymer.

  For example, Patent Document 1 discloses a branched polymer obtained by performing a polymerization reaction of an α-olefin using a specific catalyst and an adhesive composition containing the polymer. Patent Document 2 discloses a crosslinked olefin polymer obtained by a reaction between a specific α-olefin polymer and a crosslinking agent. Patent Document 3 discloses a technique of obtaining a pressure-sensitive adhesive by crosslinking a mixture of an α-olefin monomer and a polymer thereof with an electron beam.

  All of the above techniques relate to olefin polymers having a branched structure or a crosslinked structure, and are expected to be used in adhesives and the like. However, the techniques described in the above documents have problems in terms of efficiency and uniformity with respect to the formation of a crosslinked structure, which has been a cause of reducing the performance of the resulting crosslinked olefin polymer. Specifically, regarding the technique described in Patent Document 1, since a high molecular weight polymer is used, melting is difficult, and it is necessary to perform a crosslinking reaction in a solution. Regarding the technique described in Patent Document 2, it is presumed that a sufficient cross-linking structure is not shown according to the disclosure of the examples, but it is desired to achieve a higher cross-linking rate depending on the application. Regarding the technique described in Patent Document 3, uniform mixing is difficult in the cross-linking reaction, and there is a possibility that monomers remain or a non-uniform cross-linked structure is formed.

JP 2000-512683 A JP 2006-131784 A US Pat. No. 5,121,882

  The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a crosslinked olefin polymer that is soft and has a high crosslinking rate.

As a result of intensive studies, the present inventors have found that a crosslinked olefin polymer having the above properties can be obtained by performing a crosslinking reaction using a relatively low molecular weight polymer using a specific α-olefin as a raw material. I found it. The present invention has been completed based on such findings.
That is, the present invention provides the following crosslinked olefin polymer and a method for producing the same.
1. A crosslinked olefin polymer having a crosslinking rate of 20% or more, obtained by a crosslinking reaction of an α-olefin polymer satisfying the following (A) and (B):
(A) A homopolymer of an α-olefin having 8 to 30 carbon atoms, a copolymer of two or more α-olefins having 8 to 30 carbon atoms, and an α-olefin having 8 to 30 carbon atoms and ethylene and / or propylene An α-olefin polymer selected from the group consisting of an α-olefin unit having 8 to 30 carbon atoms and having an ethylene unit and / or propylene unit of less than 50 mol%. (B) Intrinsic viscosity [η] is 0.1 to 4.0 dl / g
2. The crosslinked olefin polymer according to 1 above, wherein the α-olefin polymer is produced using a metallocene catalyst,
3. The above is obtained by using 0.1 to 10% by mass of a peroxide based on the total amount of the mixture before the crosslinking reaction, and performing the crosslinking reaction at a temperature higher than the one-hour half-life temperature of the peroxide. The crosslinked olefin polymer according to 1 or 2,
4). A cross-linked olefin weight which performs a cross-linking reaction using 0.1 to 10% by mass of a radical generator based on the total amount of the mixture before the cross-linking reaction, using an α-olefin polymer satisfying the following (A) and (B) as a raw material. Production method of coalescence,
(A) A homopolymer of an α-olefin having 8 to 30 carbon atoms, a copolymer of two or more α-olefins having 8 to 30 carbon atoms, and an α-olefin having 8 to 30 carbon atoms and ethylene and / or propylene An α-olefin polymer selected from the group consisting of an α-olefin unit having 8 to 30 carbon atoms and having an ethylene unit and / or propylene unit of less than 50 mol%. (B) Intrinsic viscosity [η] is 0.1 to 4.0 dl / g
5. The method for producing a crosslinked olefin polymer according to 4 above, wherein a crosslinking reaction is performed using a peroxide as a radical generator.
6). 6. The method for producing a crosslinked olefin polymer according to 5 above, wherein the crosslinking reaction is performed at a temperature higher than the one-hour half-life temperature of the peroxide,
7). The method for producing a crosslinked olefin polymer according to any one of the above 4 to 6, wherein the crosslinking reaction is performed in an atmosphere having an oxygen concentration of 5 vol% or less.

  In the present invention, the use of a specific α-olefin polymer as a raw material improves the uniformity and efficiency during the crosslinking reaction, and the crosslinked olefin polymer has a uniform and high crosslinking rate. Therefore, the crosslinked olefin polymer of the present invention is soft and has a characteristic of excellent shape memory property, and is used in applications such as shock absorbers, pressure-sensitive adhesives, oil absorbents, electronic component sealing and adhesives. Preferably used.

  The crosslinked olefin polymer of the present invention can be obtained by subjecting a specific α-olefin polymer to a crosslinking reaction. The α-olefin polymer includes a homopolymer of an α-olefin having 8 to 30 carbon atoms, a copolymer of two or more α-olefins having 8 to 30 carbon atoms, and an α-olefin having 8 to 30 carbon atoms. An α-olefin polymer selected from copolymers with ethylene and / or propylene is used.

  Specific examples of the α-olefin having 8 to 30 carbon atoms used in the present invention include 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, Hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicocene, 1-docosene, 1-tetracocene and the like can be mentioned.

  The carbon number of the α-olefin is more preferably 8-20, and particularly preferably 8-14. When the number of carbon atoms of the α-olefin is less than 8, the crosslinking rate of the crosslinked olefin polymer may be reduced. The physical properties of the crosslinked olefin polymer may be reduced.

  In the present invention, a copolymer may be used in addition to the α-olefin homopolymer having 8 to 30 carbon atoms. By using a copolymer, it becomes easy to control the melting point (processability) and crystallinity (solubility) of the polymer, and it becomes easy to adjust the production conditions of the crosslinked olefin polymer and to control the physical properties of the crosslinked olefin polymer. .

  In the present invention, when using a copolymer of an α-olefin having 8 to 30 carbon atoms and ethylene and / or propylene, the content of the α-olefin unit having 8 to 30 carbon atoms is 50 mol% or more, The content of ethylene units and / or propylene units is less than 50 mol%. The content of the α-olefin unit having 8 to 30 carbon atoms is preferably 70 to 100 mol%, more preferably 85 to 100 mol%. When the content of the α-olefin unit having 8 to 30 carbon atoms is 50 mol% or more, the α-olefin polymer has an appropriate melting point or glass transition temperature, so that the radical generator is mixed at a low temperature of about room temperature. High crosslinking rate can be achieved when heated and crosslinked.

  The intrinsic viscosity [η] of the α-olefin polymer used in the present invention is 0.1 to 4.0 dl / g, preferably 0.2 to 3.0 dl / g, more preferably 0.3 to 2.5 dl / g. It is. If [η] is less than 0.1 dl / g, the crosslinking rate may decrease. On the other hand, when it exceeds 4.0 dl / g, the uniformity at the time of performing the crosslinking reaction is lowered, and the dispersibility of the radical generator is likely to be lowered. Moreover, since the melting point tends to be high and melting becomes difficult, the reaction conditions for the crosslinking reaction are limited.

  The α-olefin polymer used in the present invention has a molecular weight distribution (Mw / Mn) measured by the GPC method of preferably 3.5 or less, more preferably 3.0 or less, and particularly preferably 2.5 or less. By being 3.5 or less, crosslinking efficiency can be increased.

In addition, said molecular weight distribution (Mw / Mn) is the value computed from the weight average molecular weight Mw and number average molecular weight Mn of polystyrene conversion measured with the following apparatus and conditions by GPC method.
GPC measuring device column: TOSO GMHHR-H (S) HT
Detector: RI detector for liquid chromatogram WATERS 150C
Measurement conditions Solvent: 1,2,4-trichlorobenzene Measurement temperature: 145 ° C
Flow rate: 1.0 ml / min Sample concentration: 2.2 mg / ml Injection volume: 160 microliter Calibration curve: Universal Calibration
Analysis program: HT-GPC (Ver.1.0)

The α-olefin polymer used in the present invention preferably has an isotactic structure, and the stereoregularity index value MM derived from the α-olefin chain portion is preferably 50 mol% or more, more preferably 50 to 90 mol%, More preferably, it is 55-85 mol%, Most preferably, it is 55-80 mol%. When MM is 50 mol% or more, the crystallinity of the α-olefin polymer is improved, the stickiness is small, and the handling in the work before cross-linking becomes easy. In particular, when the purpose is to control the melting point and the mixing property, it is preferable to define the upper limit value of MM as described above. Thus, the crosslinked olefin polymer of the present invention can be obtained because the α-olefin polymer has an appropriate stereoregularity.
When MM is 80% or more, 1-octene is preferably used as the α-olefin. By using 1-octene, the melting point is not lost, and the workability before crosslinking is facilitated.

The stereoregularity index value MM is the T.W. Asakura, M .; Demura, Y .; It was determined in accordance with the method proposed in “Macromolecules, 24, 2334 (1991)” reported by Nishiyama. That is, MM can be obtained by utilizing the fact that CH ₂ carbon at the α position of the side chain is split and observed reflecting the difference in stereoregularity in the ¹³ C-NMR spectrum. A larger MM value indicates higher isotacticity. ^{The 13} C-NMR measurement was performed with the following apparatus and conditions.

Apparatus: JNM-EX400 type ¹³ C-NMR apparatus manufactured by JEOL Ltd. Method: Proton complete decoupling method Concentration: 230 mg / ml
Solvent: 90:10 (volume ratio) mixed solvent of 1,2,4-trichlorobenzene and heavy benzene Measurement temperature: 130 ° C.
Pulse width: 45 °
Integration count: 10,000 times

Further, the stereoregularity index value MM was calculated as follows. That is, six large absorption peaks based on the mixed solvent are observed at 127 to 135 ppm, and among these peaks, the fourth peak value from the low magnetic field side is set to 131.1 ppm, which is used as a reference for chemical shift. At this time, an absorption peak based on CH ₂ carbon at the α-position of the side chain is observed in the vicinity of 34 to 37 ppm. At this time, MM (mol%) is calculated | required using the following formula | equation.
MM = [(36.2 to 35.3 ppm integrated intensity) / (36.2 to 34.5 ppm integrated intensity)] × 100

  The α-olefin polymer used in the present invention preferably has a melting point of 50 ° C. or lower, more preferably 40 ° C. or lower when the melting point is not observed or is observed. By satisfying the above conditions, mixing with the radical generator is facilitated during the crosslinking reaction, and workability is improved.

  The melting point is determined by the following method. That is, using a differential scanning calorimeter (DSC), the copolymer was held at 190 ° C. for 5 minutes in a nitrogen atmosphere, then cooled to −50 ° C. at 5 ° C./min, and held at −50 ° C. for 5 minutes. The melting point (Tm) is determined from a melting endothermic curve obtained by raising the temperature to 190 ° C. at a rate of 10 ° C./min.

The α-olefin polymer used in the present invention can be produced using a metallocene catalyst shown below, and among them, a C ₂ symmetric and C ₁ symmetric transition metal compound capable of synthesizing an isotactic polymer, among others. Is preferably used. That is, (A) a transition metal compound represented by the following general formula (I), and (B) (B-1) a transition metal compound of component (A) or a derivative thereof to react with an ionic complex In this method, an α-olefin is polymerized in the presence of a polymerization catalyst containing a compound that can be formed and (B-2) at least one component selected from aluminoxane.

[Wherein M represents a metal element of Groups 3 to 10 of the periodic table or a lanthanoid series, and E ¹ and E ² represent a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, and a heterocyclopentadienyl group, respectively. , A substituted heterocyclopentadienyl group, an amide group, a phosphide group, a hydrocarbon group and a silicon-containing group, which form a cross-linked structure via A ¹ and A ² In addition, they may be the same as or different from each other, X represents a sigma-binding ligand, and when there are a plurality of X, the plurality of X may be the same or different, and other X, E ¹ , It may be cross-linked with E ² or Y. Y represents a Lewis base, and when there are a plurality of Y, the plurality of Y may be the same or different, and may be cross-linked with other Y, E ¹ , E ² or X, and A ¹ and A ² are A divalent bridging group that binds two ligands, a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a germanium-containing group, a tin-containing group , -O -, - CO -, - S -, - SO 2 -, - Se -, - NR 1 -, - PR 1 -, - P (O) R 1 -, - BR 1 - or -AlR ¹ - R ¹ represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, which may be the same as or different from each other. q represents an integer of 1 to 5 and represents [(M valence) -2], and r represents an integer of 0 to 3. ]

In the above general formula (I), M represents a metal element of Groups 3 to 10 of the periodic table or a lanthanoid series, and specific examples include titanium, zirconium, hafnium, yttrium, vanadium, chromium, manganese, nickel, cobalt, palladium. Among them, titanium, zirconium and hafnium are preferable from the viewpoint of olefin copolymerization activity.
E ¹ and E ² are respectively substituted cyclopentadienyl group, indenyl group, substituted indenyl group, heterocyclopentadienyl group, substituted heterocyclopentadienyl group, amide group (—N <), phosphine group (—P <), Hydrocarbon group [>CR-,> C <] and silicon-containing group [>SiR-,> Si <] (where R is hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, or a heteroatom-containing group) A ligand selected from among (A), and a crosslinked structure is formed via A ¹ and A ² . E ¹ and E ² may be the same as or different from each other. As E ¹ and E ² , a substituted cyclopentadienyl group, an indenyl group and a substituted indenyl group are preferable.

X represents a σ-bonding ligand, and when there are a plurality of X, the plurality of Xs may be the same or different and may be cross-linked with other X, E ¹ , E ² or Y. . Specific examples of X include a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an amide group having 1 to 20 carbon atoms, carbon Examples thereof include a silicon-containing group having 1 to 20 carbon atoms, a phosphide group having 1 to 20 carbon atoms, a sulfide group having 1 to 20 carbon atoms, and an acyl group having 1 to 20 carbon atoms.
On the other hand, Y represents a Lewis base, and when there are a plurality of Y, the plurality of Y may be the same or different, and may be cross-linked with other Y, E ¹ , E ² or X. Specific examples of the Lewis base of Y include amines, ethers, phosphines, thioethers and the like.

Next, A ¹ and A ² are divalent bridging groups for bonding two ligands, which are a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, and a silicon-containing group. Group, germanium-containing group, tin-containing group, —O—, —CO—, —S—, —SO ₂ —, —Se—, —NR ¹ —, —PR ¹ —, —P (O) R ¹ —, —BR ¹ — or —AlR ¹ —, wherein R ¹ represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, May be different.
Examples of such a crosslinking group include a general formula

(D is carbon, silicon or tin, R ² and R ³ are each a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, which may be the same or different from each other, and are bonded to each other to form a ring structure. (E represents an integer of 1 to 4)
Specific examples thereof include methylene group, ethylene group, ethylidene group, propylidene group, isopropylidene group, cyclohexylidene group, 1,2-cyclohexylene group, vinylidene group (CH ₂ = C =), a dimethylsilylene group, a diphenylsilylene group, a methylphenylsilylene group, a dimethylgermylene group, a dimethylstannylene group, a tetramethyldisylylene group, and a diphenyldisilylene group. Among these, an ethylene group, an isopropylidene group, and a dimethylsilylene group are preferable.
q represents an integer of 1 to 5 and represents [(M valence) -2], and r represents an integer of 0 to 3.
Among the transition metal compounds represented by the general formula (I), the general formula (II)

The transition metal compound which makes the ligand the double bridge type biscyclopentadienyl derivative represented by these is preferable.
In the above general formula (II), M, A ¹ , A ² , q and r are the same as those in the general formula (I).
X ¹ represents a σ-bonding ligand, and when plural X ^1, a plurality of X ¹ may be the same or different, may be crosslinked with other X ¹ or Y ^1. Specific examples of X ¹ include the same examples as those exemplified in the description of X in formula (I).
Y ¹ represents a Lewis base, if Y ¹ is plural, Y ¹ may be the same or different, may be crosslinked with other Y ¹ or X ^1. Specific examples of Y ¹ are the same as those exemplified in the description of Y in the general formula (I).
R ^{4 to} R ⁹ each represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, or a heteroatom-containing group. One must not be a hydrogen atom. R ^{4 to} R ⁹ may be the same as or different from each other, and adjacent groups may be bonded to each other to form a ring. Among these, it is preferable that R ⁶ and R ⁷ form a ring and R ⁸ and R ⁹ form a ring. As R ⁴ and R ⁵ , a group containing a hetero atom such as oxygen, halogen, or silicon is preferable because of high copolymerization activity.

The transition metal compound having the double-bridged biscyclopentadienyl derivative as a ligand preferably contains silicon in the bridging group between the ligands.
Specific examples of the transition metal compound represented by the general formula (I) include (1,2′-ethylene) (2,1′-ethylene) -bis (indenyl) zirconium dichloride, (1,2′-methylene). (2,1′-methylene) -bis (indenyl) zirconium dichloride, (1,2′-isopropylidene) (2,1′-isopropylidene) -bis (indenyl) zirconium dichloride, (1,2′-ethylene) (2,1′-ethylene) -bis (3-methylindenyl) zirconium dichloride, (1,2′-ethylene) (2,1′-ethylene) -bis (4,5-benzoindenyl) zirconium dichloride, (1,2′-ethylene) (2,1′-ethylene) -bis (4-isopropylindenyl) zirconium dichloride, (1,2′-ethylene) (2,1′-ethylene)- (5,6-dimethylindenyl) zirconium dichloride, (1,2'-ethylene) (2,1'-ethylene) -bis (4,7-diisopropylindenyl) zirconium dichloride, (1,2'-ethylene ) (2,1′-ethylene) -bis (4-phenylindenyl) zirconium dichloride, (1,2′-ethylene) (2,1′-ethylene) -bis (3-methyl-4-isopropylindenyl) Zirconium dichloride, (1,2'-ethylene) (2,1'-ethylene) -bis (5,6-benzoindenyl) zirconium dichloride, (1,2'-ethylene) (2,1'-isopropylidene) -Bis (indenyl) zirconium dichloride, (1,2'-methylene) (2,1'-ethylene) -bis (indenyl) zirconium dichloride, (1,2'-me Len) (2,1'-isopropylidene) -bis (indenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) bis (indenyl) zirconium dichloride, (1,2'- Dimethylsilylene) (2,1′-dimethylsilylene) bis (3-methylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (3-n-butylindenyl) ) Zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) bis (3-i-propylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'- Dimethylsilylene) bis (3-trimethylsilylmethylindenyl) zirconium dichloride, (1,2'-dimethylsilyl) ) (2,1′-dimethylsilylene) bis (3-phenylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (4,5-benzoindenyl) Zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) bis (4-isopropylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) Bis (5,6-dimethylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) bis (4,7-di-i-propylindenyl) zirconium dichloride, (1 , 2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (4-phenylindenyl) zirconium dichloride, 1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (3-methyl-4-i-propylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethyl Silylene) bis (5,6-benzoindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-isopropylidene) -bis (indenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1′-isopropylidene) -bis (3-methylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-isopropylidene) -bis (3-i-propylindenyl) Zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-isopropylidene) -bis (3-n-butylindenyl) zirco Nium dichloride, (1,2′-dimethylsilylene) (2,1′-isopropylidene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-isopropylidene) Ridene) -bis (3-trimethylsilylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-isopropylidene) -bis (3-phenylindenyl) zirconium dichloride, (1,2'- Dimethylsilylene) (2,1′-methylene) -bis (indenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-methylene) -bis (3-methylindenyl) zirconium dichloride, (1 , 2′-dimethylsilylene) (2,1′-methylene) -bis (3-i-propylindenyl) zyl Nium dichloride, (1,2'-dimethylsilylene) (2,1'-methylene) -bis (3-n-butylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-methylene ) -Bis (3-trimethylsilylmethylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-methylene) -bis (3-trimethylsilylindenyl) zirconium dichloride, (1,2'-diphenyl) Silylene) (2,1′-methylene) -bis (indenyl) zirconium dichloride, (1,2′-diphenylsilylene) (2,1′-methylene) -bis (3-methylindenyl) zirconium dichloride, (1, 2'-diphenylsilylene) (2,1'-methylene) -bis (3-i-propylindenyl) zirconium dichrome (1,2'-diphenylsilylene) (2,1'-methylene) -bis (3-n-butylindenyl) zirconium dichloride, (1,2'-diphenylsilylene) (2,1'-methylene) -Bis (3-trimethylsilylmethylindenyl) zirconium dichloride, (1,2'-diphenylsilylene) (2,1'-methylene) -bis (3-trimethylsilylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) ) (2,1'-dimethylsilylene) (3-methylcyclopentadienyl) (3'-methylcyclopentadienyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-isopropylidene) (3-methylcyclopentadienyl) (3′-methylcyclopentadienyl) zirconium dichloride, (1,2′-dimethyl) Lucylylene) (2,1′-ethylene) (3-methylcyclopentadienyl) (3′-methylcyclopentadienyl) zirconium dichloride, (1,2′-ethylene) (2,1′-methylene) (3 -Methylcyclopentadienyl) (3'-methylcyclopentadienyl) zirconium dichloride, (1,2'-ethylene) (2,1'-isopropylidene) (3-methylcyclopentadienyl) (3'- Methylcyclopentadienyl) zirconium dichloride, (1,2'-methylene) (2,1'-methylene) (3-methylcyclopentadienyl) (3'-methylcyclopentadienyl) zirconium dichloride, (1, 2'-methylene) (2,1'-isopropylidene) (3-methylcyclopentadienyl) (3'-methylcyclopentadienyl) zirconium Chloride, (1,2'-isopropylidene) (2,1'-isopropylidene) (3-methylcyclopentadienyl) (3'-methylcyclopentadienyl) zirconium dichloride, (1,2'-dimethylsilylene) ) (2,1′-dimethylsilylene) (3,4-dimethylcyclopentadienyl) (3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1 '-Isopropylidene) (3,4-dimethylcyclopentadienyl) (3', 4'-dimethylcyclopentadienyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-ethylene) ( 3,4-dimethylcyclopentadienyl) (3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride, (1,2′-ethylene) (2 1'-methylene) (3,4-dimethylcyclopentadienyl) (3 ', 4'-dimethylcyclopentadienyl) zirconium dichloride, (1,2'-ethylene) (2,1'-isopropylidene) ( 3,4-dimethylcyclopentadienyl) (3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride, (1,2′-methylene) (2,1′-methylene) (3,4-dimethylcyclopenta Dienyl) (3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride, (1,2′-methylene) (2,1′-isopropylidene) (3,4-dimethylcyclopentadienyl) (3 ′ , 4′-dimethylcyclopentadienyl) zirconium dichloride, (1,2′-isopropylidene) (2,1′-isopropylidene) (3,4-dimethylcyclopentadiene) Enyl) (3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) (3-methyl-5-ethylcyclopentadienyl) ( 3'-methyl-5'-ethylcyclopentadienyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) (3-methyl-5-ethylcyclopentadienyl) (3 '-Methyl-5'-ethylcyclopentadienyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) (3-methyl-5-isopropylcyclopentadienyl) (3'-Methyl-5'-isopropylcyclopentadienyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) (3-Methyl-5-n-butylcyclopentadienyl) (3′-methyl-5′-n-butylcyclopentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′- Dimethylsilylene) (3-methyl-5-phenylcyclopentadienyl) (3′-methyl-5′-phenylcyclopentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-isopropylidene ) (3-Methyl-5-ethylcyclopentadienyl) (3'-methyl-5'-ethylcyclopentadienyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-isopropylidene) (3-methyl-5-i-propylcyclopentadienyl) (3'-methyl-5'-i-propylcyclopentadienyl) zirconium dichloride, ( , 2′-dimethylsilylene) (2,1′-isopropylidene) (3-methyl-5-n-butylcyclopentadienyl) (3′-methyl-5′-n-butylcyclopentadienyl) zirconium dichloride , (1,2′-dimethylsilylene) (2,1′-isopropylidene) (3-methyl-5-phenylcyclopentadienyl) (3′-methyl-5′-phenylcyclopentadienyl) zirconium dichloride, ( 1,2′-dimethylsilylene) (2,1′-ethylene) (3-methyl-5-ethylcyclopentadienyl) (3′-methyl-5′-ethylcyclopentadienyl) zirconium dichloride, (1, 2'-dimethylsilylene) (2,1'-ethylene) (3-methyl-5-i-propylcyclopentadienyl) (3'-methyl-5'-i-propylcyclopen Dienyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-ethylene) (3-methyl-5-n-butylcyclopentadienyl) (3′-methyl-5′-n-butylcyclo) Pentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-ethylene) (3-methyl-5-phenylcyclopentadienyl) (3′-methyl-5′-phenylcyclopentadiene) Enyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-methylene) (3-methyl-5-ethylcyclopentadienyl) (3'-methyl-5'-ethylcyclopentadienyl) zirconium Dichloride, (1,2'-dimethylsilylene) (2,1'-methylene) (3-methyl-5-i-propylcyclopentadi

Enyl) (3'-methyl-5'-i-propylcyclopentadienyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-methylene) (3-methyl-5-n-butylcyclo) Pentadienyl) (3'-methyl-5'-n-butylcyclopentadienyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-methylene) (3-methyl-5-phenylcyclo Pentadienyl) (3'-methyl-5'-phenylcyclopentadienyl) zirconium dichloride, (1,2'-ethylene) (2,1'-methylene) (3-methyl-5-i-propylcyclopenta Dienyl) (3′-methyl-5′-i-propylcyclopentadienyl) zirconium dichloride, (1,2′-ethylene) (2,1′-isopropylidene) (3-methyl-5 -I-propylcyclopentadienyl) (3'-methyl-5'-i-propylcyclopentadienyl) zirconium dichloride, (1,2'-methylene) (2,1'-methylene) (3-methyl- 5-i-propylcyclopentadienyl) (3′-methyl-5′-i-propylcyclopentadienyl) zirconium dichloride, (1,2′-methylene) (2,1′-isopropylidene) (3- Methyl-5-i-propylcyclopentadienyl) (3'-methyl-5'-i-propylcyclopentadienyl) zirconium dichloride, (1,1'-dimethylsilylene) (2,2'-dimethylsilylene) Bisindenylzirconium dichloride, (1,1′-diphenylsilylene) (2,2′-dimethylsilylene) bisindenylzirconium dichloride, (1,1′-dichloride Tylsilylene) (2,2′-dimethylsilylene) bisindenylzirconium dichloride, (1,1′-diisopropylsilylene) (2,2′-dimethylsilylene) bisindenylzirconium dichloride, (1,1′-dimethylsilylene) (2,2′-Diisopropylsilylene) bisindenylzirconium dichloride, (1,1′-dimethylsilyleneindenyl) (2,2′-dimethylsilylene-3-trimethylsilylindenyl) zirconium dichloride, (1,1′- Diphenylsilyleneindenyl) (2,2′-diphenylsilylene-3-trimethylsilylindenyl) zirconium dichloride, (1,1′-diphenylsilyleneindenyl) (2,2′-dimethylsilylene-3-trimethylsilylindenyl) zirconium Dichloride, (1,1'-dimethyl Silylene) (2,2′-dimethylsilylene) (indenyl) (3-trimethylsilylindenyl) zirconium dichloride, (1,1′-diphenylsilylene) (2,2′-diphenylsilylene) (indenyl) (3-trimethylsilylindene Nyl) zirconium dichloride, (1,1′-diphenylsilylene) (2,2′-dimethylsilylene) (indenyl) (3-trimethylsilylindenyl) zirconium dichloride, (1,1′-dimethylsilylene) (2,2 ′ -Diphenylsilylene) (indenyl) (3-trimethylsilylindenyl) zirconium dichloride, (1,1'-diisopropylsilylene) (2,2'-dimethylsilylene) (indenyl) (3-trimethylsilylindenyl) zirconium dichloride, (1 , 1'-dimethylsilylene) ( , 2′-Diisopropylsilylene) (indenyl) (3-trimethylsilylindenyl) zirconium dichloride, (1,1′-diisopropylsilylene) (2,2′-diisopropylpropylsilylene) (indenyl) (3-trimethylsilylindenyl) Zirconium dichloride, (1,1′-dimethylsilylene) (2,2′-dimethylsilylene) (indenyl) (3-trimethylsilylmethylindenyl) zirconium dichloride, (1,1′-diphenylsilylene) (2,2′- Diphenylsilylene) (indenyl) (3-trimethylsilylmethylindenyl) zirconium dichloride, (1,1′-diphenylsilylene) (2,2′-dimethylsilylene) (indenyl) (3-trimethylsilylmethylindenyl) zirconium dichloride, 1,1'-jime Lucylylene) (2,2′-diphenylsilylene) (indenyl) (3-trimethylsilylmethylindenyl) zirconium dichloride, (1,1′-diisopropylsilylene) (2,2′-dimethylsilylene) (indenyl) (3-trimethylsilyl) Methylindenyl) zirconium dichloride, (1,1′-dimethylsilylene) (2,2′-diisopropylsilylene) (indenyl) (3-trimethylsilylmethylindenyl) zirconium dichloride, (1,1′-diisopropylsilylene) (2 , 2'-diisopropylsilylene) (indenyl) (3-trimethylsilylmethylindenyl) zirconium dichloride and the like, and those obtained by substituting zirconium in these compounds with titanium or hafnium. Of course, it is not limited to these.

  Further, it may be an analogous compound of another group or a lanthanoid series metal element. In the above compound, (1,1 ′ −) (2,2′−) may be (1,2 ′ −) (2,1′−), or (1,2 ′ −) (2 , 1'-) may be (1, 1'-) (2, 2'-).

Next, as the component (B-1) in the component (B), any component can be used as long as it can form an ionic complex by reacting with the transition metal compound of the component (A). The following general formulas (III) and (IV)
([L ¹ −R ¹⁰ ] ^{k +} ) _a ([Z] ⁻ ) _b (III)
([L ² ] ^{k +} ) _a ([Z] ⁻ ) _b (IV)
(However, L ² is ^{M 2, R 11 R 12 M} 3, R 13 3 C or R ¹⁴ M ^3.)
[In the formulas (III) and (IV), L ¹ is a Lewis base, [Z] ⁻ is a non-coordinating anion [Z ¹ ] ⁻ and [Z ² ] ⁻ , where [Z ¹ ] ⁻ is a plurality of Anion in which the group is bonded to the element, that is, [M ¹ G ¹ G ² ... G ^f ] ⁻ (where M ¹ is an element of Group 5 to 15 of the periodic table, preferably Group 13 to 15 of the periodic table. G ^{1 to} G ^f are each a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a dialkylamino group having 2 to 40 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or 6 to 20 carbon atoms. Aryl group having 6 to 20 carbon atoms, alkyl aryl group having 7 to 40 carbon atoms, arylalkyl group having 7 to 40 carbon atoms, halogen-substituted hydrocarbon group having 1 to 20 carbon atoms, 1 to carbon atoms 20 acyloxy groups, organic metalloid groups, or carbon atoms containing 2 to 20 heteroatoms Two or more may form a ring .f of showing the original .G ¹ ~G ^f represents an integer of [(valence of central metal M ¹⁾ +1].), [Z ^{2] -} the logarithm of the reciprocal of the acid dissociation constant (pKa) -10 below Bronsted acid alone or Bronsted acid and Lewis acid combination of conjugate base or generally conjugate base of an acid defined as super acid, Indicates. In addition, a Lewis base may be coordinated. R ¹⁰ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group or an arylalkyl group, and R ¹¹ and R ¹² are each a cyclopentadienyl group or a substituted group. cyclopentadienyl group, an indenyl group or a fluorenyl group, R ¹³ represents an alkyl group, an aryl group, alkylaryl group or arylalkyl group having 1 to 20 carbon atoms. R ¹⁴ represents a macrocyclic ligand such as tetraphenylporphyrin or phthalocyanine. k is an ionic valence of [L ¹ −R ¹⁰ ], [L ² ], an integer of 1 to 3, a is an integer of 1 or more, and b = (k × a). M ² includes elements in groups 1 to ³ , 11 to 13, and 17 of the periodic table, and M ³ represents elements 7 to 12 in the periodic table. ]
What is represented by these can be used conveniently.

Here, specific examples of L ¹ include ammonia, methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine, N, N-dimethylaniline, trimethylamine, triethylamine, tri-n-butylamine, methyldiphenylamine, Amines such as pyridine, p-bromo-N, N-dimethylaniline, p-nitro-N, N-dimethylaniline, phosphines such as triethylphosphine, triphenylphosphine, diphenylphosphine, thioethers such as tetrahydrothiophene, benzoic acid Examples thereof include esters such as ethyl acid, and nitriles such as acetonitrile and benzonitrile.

Specific examples of R ¹⁰ include hydrogen, methyl group, ethyl group, benzyl group, and trityl group. Specific examples of R ¹¹ and R ¹² include cyclopentadienyl group and methylcyclopentadienyl group. , Ethylcyclopentadienyl group, pentamethylcyclopentadienyl group, and the like.
Specific examples of R ¹³ include a phenyl group, a p-tolyl group, and a p-methoxyphenyl group. Specific examples of R ¹⁴ include tetraphenylporphyrin, phthalocyanine, and the like.
Specific examples of M ² include Li, Na, K, Ag, Cu, Br, I, and I _3. Specific examples of M ³ include Mn, Fe, Co, Ni, and Zn. And so on.

In [Z ¹ ] ⁻ , that is, [M ¹ G ¹ G ² ... G ^f ], specific examples of M ¹ include B, Al, Si, P, As, Sb, etc., preferably B and Al are Can be mentioned.
Specific examples of G ¹ and G ^{2 to} G ^f include a dimethylamino group and a diethylamino group as a dialkylamino group, a methoxy group, an ethoxy group, an n-butoxy group, a phenoxy group as an alkoxy group or an aryloxy group, and the like. Hydrocarbon groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-octyl, n-eicosyl, phenyl, p-tolyl, benzyl, 4-t -Butylphenyl group, 3,5-dimethylphenyl group, etc., fluorine, chlorine, bromine, iodine as halogen atoms, p-fluorophenyl group, 3,5-difluorophenyl group, pentachlorophenyl group as heteroatom-containing hydrocarbon groups, 3,4,5-trifluorophenyl group, pentafluorophenyl group, 3,5-bis (trifluoro Oromechiru) phenyl group, such as bis (trimethylsilyl) methyl group, pentamethyl antimony group as organic metalloid group, trimethylsilyl group, trimethylgermyl group, diphenylarsine group, dicyclohexyl antimony group, such as diphenyl boron and the like.

Specific examples of a non-coordinating anion, that is, a Bronsted acid alone having a pKa of −10 or less, or a conjugate base [Z ² ] ⁻ of a combination of Bronsted acid and Lewis acid include a trifluoromethanesulfonate anion ( CF ₃ SO ₃ ) ⁻ , bis (trifluoromethanesulfonyl) methyl anion, bis (trifluoromethanesulfonyl) benzyl anion, bis (trifluoromethanesulfonyl) amide, perchlorate anion (ClO ₄ ) ⁻ , trifluoroacetate anion (CF ₃ CO ₂ ) ⁻ , hexafluoroantimony anion (SbF ₆ ) ⁻ , fluorosulfonic acid anion (FSO ₃ ) ⁻ , chlorosulfonic acid anion (ClSO ₃ ) ⁻ , fluorosulfonic acid anion / 5-antimony fluoride (FSO ₃ / SbF) ₅₎ ^-, fluorosulfonic acid anion / - fluoride arsenic ^{_{(FSO 3 / AsF 5) -}} , trifluoromethanesulfonic acid / antimony pentafluoride _{(CF 3 SO 3 / SbF 5} ) - and the like.

Specific examples of the ionic compound that reacts with the transition metal compound of the component (A) to form an ionic complex, that is, (B-1) component compound, include triethylammonium tetraphenylborate, tetraphenylboric acid. Tri-n-butylammonium, trimethylammonium tetraphenylborate, tetraethylammonium tetraphenylborate, methyl (tri-n-butyl) ammonium tetraphenylborate, benzyl (tri-n-butyl) ammonium tetraphenylborate, dimethyldiphenyl tetraphenylborate Ammonium, triphenyl (methyl) ammonium tetraphenylborate, trimethylanilinium tetraphenylborate, methylpyridinium tetraphenylborate, benzylpyridinium tetraphenylborate, tetraphenylboron Methyl (2-cyanopyridinium), tetrakis (pentafluorophenyl) triethylammonium borate, tetrakis (pentafluorophenyl) tri-n-butylammonium borate, tetrakis (pentafluorophenyl) triphenylammonium borate, tetrakis (pentafluorophenyl) boric acid Tetra-n-butylammonium, tetrakis (pentafluorophenyl) tetraethylammonium borate, tetrakis (pentafluorophenyl) benzyl benzyl (tri-n-butyl) borate, tetrakis (pentafluorophenyl) methyldiphenylammonium borate, tetrakis (pentafluorophenyl) ) Triphenyl (methyl) ammonium borate, methylanilinium tetrakis (pentafluorophenyl) borate, Tet Dimethylanilinium kiss (pentafluorophenyl) borate, trimethylanilinium tetrakis (pentafluorophenyl) borate, methylpyridinium tetrakis (pentafluorophenyl) borate, benzylpyridinium tetrakis (pentafluorophenyl) borate, methyl tetrakis (pentafluorophenyl) borate (2-cyanopyridinium), benzyl tetrakis (pentafluorophenyl) borate (2-cyanopyridinium), tetrakis (pentafluorophenyl) methyl borate (4-cyanopyridinium), tetrakis (pentafluorophenyl) triphenylphosphonium borate, tetrakis [ Bis (3,5-ditrifluoromethyl) phenyl] dimethylanilinium borate, ferrocenium tetraphenylborate, tetraphenylboron Acid silver, triphenyl tetraphenylborate, tetraphenylporphyrin manganese tetraphenylborate, ferrocenium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) boric acid (1,1′-dimethylferrocenium), tetrakis (pentafluorophenyl) Decamethylferrocenium borate, silver tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) trityl borate, lithium tetrakis (pentafluorophenyl) borate, sodium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) boric acid Tetraphenylporphyrin manganese, silver tetrafluoroborate, silver hexafluorophosphate, silver hexafluoroarsenate, silver perchlorate, silver trifluoroacetate, triflu Examples thereof include silver olomethanesulfonate.
(B-1) may be used alone or in combination of two or more.
On the other hand, as the aluminoxane of the component (B-2), the general formula (V)

(Wherein R ¹⁵ represents a hydrocarbon group such as an alkyl group, alkenyl group, aryl group or arylalkyl group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms or a halogen atom, and w represents an average degree of polymerization. Usually, it is an integer of 2-50, preferably 2-40, wherein each R ¹⁵ may be the same or different.
A chain aluminoxane represented by the general formula (VI)

(In the formula, R ¹⁵ and w are the same as those in the general formula (V).)
The cyclic aluminoxane shown by these can be mentioned.

Examples of the method for producing the aluminoxane include a method in which an alkylaluminum is brought into contact with a condensing agent such as water, but the means is not particularly limited and may be reacted according to a known method.
For example, (a) a method in which an organoaluminum compound is dissolved in an organic solvent and contacting it with water, (b) a method in which an organoaluminum compound is initially added during polymerization, and water is added later, (c) a metal There are a method of reacting water adsorbed on a salt or the like with water adsorbed on an inorganic or organic substance with an organoaluminum compound, and (d) a method of reacting a tetraalkyldialuminoxane with a trialkylaluminum and further reacting with water. .
The aluminoxane may be insoluble in toluene. These aluminoxanes may be used alone or in combination of two or more.

  The use ratio of (A) catalyst component to (B) catalyst component is preferably 10: 1 to 1: 100 in molar ratio when (B-1) compound is used as (B) catalyst component. The range of 2: 1 to 1:10 is desirable, and if it is within the above range, the catalyst cost per unit mass polymer does not become so high and is practical. When the compound (B-2) is used, the molar ratio is preferably 1: 1 to 1: 1000000, more preferably 1:10 to 1: 10000. If it exists in this range, the catalyst cost per unit mass polymer will not become so high, and it is practical. Moreover, (B-1) and (B-2) can also be used individually or in combination of 2 or more types as a catalyst component (B).

Moreover, in addition to the said (A) component and (B) component, the polymerization catalyst at the time of manufacturing the alpha-olefin polymer used by this invention can use an organoaluminum compound as (C) component.
Here, as the organoaluminum compound of the component (C), the general formula (VII)
R ¹⁶ _v AlJ _3-v (VII)
[Wherein, R ¹⁶ represents an alkyl group having 1 to 10 carbon atoms, J represents a hydrogen atom, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a halogen atom, and v represents 1 to 3 carbon atoms. (It is an integer)
The compound shown by these is used.
Specific examples of the compound represented by the general formula (VII) include trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, dimethylaluminum chloride, diethylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, dimethylaluminum fluoride. , Diisobutylaluminum hydride, diethylaluminum hydride, ethylaluminum sesquichloride and the like. These organoaluminum compounds may be used alone or in combination of two or more.

The use ratio of the catalyst component (A) to the catalyst component (C) is preferably 1: 1 to 1: 10000, more preferably 1: 5 to 1: 2000, still more preferably 1:10 to 1 in terms of molar ratio. : The range of 1000 is desirable.
By using the catalyst component (C), the copolymerization activity per transition metal can be improved. However, if the amount is too large, the organoaluminum compound is wasted and a large amount remains in the copolymer, which is not preferable. .
In the production of the α-olefin polymer used in the present invention, at least one catalyst component can be supported on a suitable carrier and used. The type of the carrier is not particularly limited, and any of inorganic oxide carriers, other inorganic carriers, and organic carriers can be used. In particular, inorganic oxide carriers or other inorganic carriers are preferable.

In the α-olefin polymer used in the present invention, the polymerization method is not particularly limited, and any method such as a slurry polymerization method, a gas phase polymerization method, a bulk polymerization method, a solution polymerization method, and a suspension polymerization method may be used. However, a slurry polymerization method and a gas phase polymerization method are particularly preferable.
About polymerization conditions, superposition | polymerization temperature is -100-250 degreeC normally, Preferably it is -50-200 degreeC, More preferably, it is 0-130 degreeC.
The polymerization time is usually 5 minutes to 10 hours, and the reaction pressure is preferably normal pressure to 20 MPa (gauge), more preferably normal pressure to 10 MPa (gauge).

In the method for producing an α-olefin polymer used in the present invention, it is preferable to add hydrogen since polymerization activity is improved. When hydrogen is used, it is usually from normal pressure to 5 MPa (gauge), preferably from normal pressure to 3 MPa (gauge), more preferably from normal pressure to 2 MPa (gauge).
When using a polymerization solvent, for example, aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene, alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclohexane, and aliphatic hydrocarbons such as pentane, hexane, heptane, and octane , Halogenated hydrocarbons such as chloroform and dichloromethane can be used. These solvents may be used alone or in combination of two or more. Moreover, you may use monomers, such as an alpha olefin, as a solvent. Depending on the polymerization method, it can be carried out without solvent.

  In the polymerization, prepolymerization can be performed using the polymerization catalyst. The prepolymerization can be performed, for example, by bringing a metallocene catalyst into contact with a small amount of olefin, but the method is not particularly limited, and a known method can be used. Although there is no restriction | limiting in particular about the olefin used for prepolymerization, It is advantageous to use the olefin chosen from ethylene, propylene, and a C8-C30 alpha olefin.

The prepolymerization temperature is usually -20 to 200 ° C, preferably -10 to 130 ° C, more preferably 0 to 80 ° C. In the prepolymerization, an aliphatic hydrocarbon, aromatic hydrocarbon, monomer or the like can be used as a solvent. Of these, aliphatic hydrocarbons are particularly preferred. Moreover, you may perform prepolymerization without a solvent.
In the prepolymerization, the intrinsic viscosity [η] (measured in 135 ° C. decalin) of the prepolymerized product is 0.1 deciliter / g or more, and the amount of the prepolymerized product per 1 mmol of the transition metal component in the catalyst is 1. It is desirable to adjust conditions so that it may become -10000g, especially 10-1000g. In addition, the method for adjusting the molecular weight of the polymer includes selection of the type of each catalyst component, the amount used, and the copolymerization temperature, and further polymerization in the presence of hydrogen. An inert gas such as nitrogen may be present.
By the above method, the alpha olefin polymer used by this invention can be obtained efficiently.

  The crosslinked olefin polymer of the present invention can be obtained by crosslinking reaction of the α-olefin polymer obtained by the above method. In the crosslinking reaction, for example, a radical can be generated by a radical generator or electron beam irradiation.

  Examples of the radical generator include various peroxides. Examples of the peroxide include benzoyl peroxide, di-t-butyl peroxide, acetyl peroxide, t-butyl perbenzoate, and methyl ethyl ketone peroxide. Commercially available products include Perhexin 25B, Perbutyl D, Perbutyl C, Perhexa 25B, Park Mill D, Perbutyl P, Perbutyl H, Perhexyl H, Park Mill H, Per Octa H, Park Mill P, Permenta H, Perbutyl SM, Parmek N, manufactured by Nippon Oil & Fats. , Peromer AC, Perhexa V, Perhexa 22, Perhexa CD, Pertetra A, Perhexa C, Perhexa 3M, Perhexa HC, Perhexa TMH, Perbutyl IF, Perbutyl Z, Perbutyl A, Perhexyl Z, Perhexa 25Z, Perbutyl E, Perbutyl L, Perhexa 25MT, perbutyl I, perbutyl 355, perbutyl MA, perhexyl I, perbutyl IB, perbutyl O, perhexyl O, percyclo O, perhexa 250, perocta O, perbuchi PV, perhexyl PV, perbutyl ND, perhexyl ND, percyclo ND, per octa ND, park mill ND, die par ND, parroyl SOP, parroyl OPP, parroyl MBP, parroyl EEP, parroyl IPP, parroyl NPP, parroyl TCP, parroyl IB, parroyl SA, Parroyl S, Parroyl O, Parroyl L, Parroyl 355, Nyper BW, Nyper BMT, Nyper CS and the like can be mentioned.

  Examples of the radical generator other than the peroxide include persulfates such as ammonium persulfate and potassium persulfate. A redox initiator in which the peroxide is combined with cobalt naphthenate or aromatic amine can also be used. Further, for example, azo compounds such as 2,2′-azobisisobutyronitrile and 2,2′-azo-di- (2,4-dimethylvaleronitrile) can be used.

The radical generator of the present invention may be one that generates radicals by ultraviolet irradiation. For example, in addition to benzoin such as benzoin and benzoin methyl ether and derivatives thereof, 4,4′-bis (dimethylamino) benzophenone, 2- Examples include chloroanthracene, 2-methylanthraquinone, thioxanthone, diphenyl disulfide, dimethyldithiocarbamate, and the like. In this case, the ultraviolet intensity is usually 1 to 100 mJ / cm ² .

  The amount of the radical generator used is not particularly limited and is appropriately selected according to the physical properties of the target crosslinked olefin polymer. The content in the mixture before the crosslinking reaction is usually 0.1 to 10% by mass. Preferably, it is 0.5-8 mass%. When the content is 0.1% by mass or more, the amount of cross-linking becomes sufficient, so that the effect of cross-linking is expressed. On the other hand, if it is 10% by mass or less, the process for removing the residual radical generator is unnecessary, which is industrially advantageous.

  As the radical generator, a liquid or a solid can be used as it is, but it can also be used by dissolving or suspending in an organic solvent as required from the viewpoint of safety. In this case, the solvent is selected depending on the reaction temperature, but hexane, heptane, octane, decane, toluene, xylene, cyclohexane and the like are used.

  In the case of generating radicals by electron beam irradiation, a conventionally known method can be used. In the case of an electron beam, an acceleration voltage of 0.1 to 10 MeV and an irradiation dose of 1 to 500 kGy are appropriate. An example of the radiation source is a tungsten filament.

  In the crosslinking reaction performed in the present invention, it is preferable to use a radical generator, and it is more preferable to use a peroxide.

  The crosslinking method is not particularly limited. For example, the α-olefin polymer and the radical generator are continuously melt-kneaded and reacted using a roll mill, a Banbury mixer, an extruder, or the like, or Solvent-free or in hydrocarbon solvents such as butane, pentane, hexane, heptane, cyclohexane, and toluene, halogenated hydrocarbon solvents such as chlorobenzene, dichlorobenzene, and trichlorobenzene, and appropriate organic solvents such as liquefied α-olefins In this method, a batch reaction method can be used.

  The crosslinked olefin polymer of the present invention uses a polymer having a relatively low molecular weight using a specific α-olefin as a raw material. Furthermore, the α-olefin polymer has an appropriate stereoregularity. Therefore, since the melting point of the α-olefin polymer can be lowered, the crosslinking reaction can be performed by melting without using a solvent, which is advantageous in terms of reaction efficiency, and a high crosslinking rate is expected to be obtained. Is done. In addition, since the α-olefin polymer is soft, the ease of mixing during the crosslinking reaction is expected to affect the high crosslinking rate. For the above reasons, when improving to achieve a high crosslinking rate, it is preferable to perform the crosslinking reaction by melting without using a solvent.

The reaction temperature can be appropriately determined according to the purpose, but in the case of melting, it is usually 10 to 200 ° C., preferably 20 to 180 ° C., and in the case of solution reaction, usually 10 to 100 ° C., preferably 10 to 60 ° C. ° C. Since the α-olefin polymer of the present invention has a relatively low melting point, a high temperature is not necessarily required for melting. Therefore, the hydrocarbon chain is not easily cleaved as a side reaction at the time of crosslinking, and the desired crosslinked olefin polymer can be obtained.
Moreover, in order to raise a crosslinking rate, it is preferable that it is higher than the 1-hour half life temperature of a radical generating agent, More preferably, it is 10 degreeC or more higher temperature, Furthermore, 20 degreeC or more higher temperature is preferable.

  In the present invention, in order to improve the crosslinking rate, the oxygen concentration in the reaction system is preferably controlled, the crosslinking reaction is preferably performed in an atmosphere having an oxygen concentration of 5 vol% or less, and more preferably 1 vol% or less.

The crosslinked olefin polymer of the present invention obtained by the above method has a crosslinking rate of 20% or more. In the present invention, the crosslinking rate is determined by the following calculation formula (I).
Crosslinking rate (%) = mass (g) / 1 g × 100 (I) of n-heptane insoluble part after drying
Here, the mass of the n-heptane insoluble part after drying is that 1 g of the crosslinked olefin polymer is immersed in 10 g of n-heptane at 65 ° C. for 30 minutes, and the n-heptane insoluble part is separated by filtration, and 80 ° C. The mass after drying under reduced pressure for 1 hour.
The crosslinking rate of the crosslinked olefin polymer of the present invention is preferably 30% or more, more preferably 50% or more, and particularly preferably 80% or more. In addition, when controlling a crosslinking rate at the time of a crosslinking reaction, it can carry out by adjusting the kind and quantity of a radical generator, temperature, oxygen concentration, etc. as mentioned above.

  The crosslinked olefin polymer of the present invention is soft and can achieve a high crosslinking rate. That is, it has a characteristic that it is soft and has excellent shape memory properties, and is suitably used in applications such as shock absorbers, pressure-sensitive adhesives, oil absorbents, electronic component sealing and adhesives.

  EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.

[Stereoregularity index value MM]
It calculated | required by said method.
[Intrinsic viscosity [η]]
It calculated | required by said method.
[Molecular weight distribution (Mw / Mn)]
It calculated | required by said method.
[Melting point]
It calculated | required by said method.

[Measurement method of crosslinking rate]
A 20 mL sample bottle was mixed with 1 g of a crosslinked olefin polymer and 10 g of n-heptane, capped, and then placed in a 65 ° C. hot water bath. After 30 minutes separation using a filter paper, drying was performed under reduced pressure at 80 ° C. for 1 hour, and the mass of the remaining crosslinked olefin polymer (heptane insoluble part) was measured. The crosslinking rate was calculated from the following formula.
Crosslinking rate (%) = mass (g) / 1 g × 100 of n-heptane insoluble part after drying
The filter paper used was 5 types A described in JIS P3801: 1995 [filtering time (s) is 70 or less, wet burst strength (kPa) is 1.47 or more, precipitation retention is iron hydroxide]. .

[Measurement method of deformation rate after heating load]
The crosslinked olefin polymer cut out to about 4 mm × 10 mm × 10 mm was sandwiched between two 2.0 cm square Teflon (registered trademark) sheets so that the distance between the sheets was about 4 mm. A weight was placed and left at 150 ° C. for 1 hour. Thereafter, the weight was removed, the sheet interval was measured, and the deformation rate after heating and weighting was calculated from the following formula.
Deformation rate after heating load = {(distance between sheets before heating load−distance between sheets when weight is removed after heating load) / distance between sheets before heating load} × 100

Production Example 1
Production of (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) bis (3-trimethylsilylmethylindenyl) zirconium dichloride (1,2'-dimethylsilylene) (2,1'-dimethyl) in a Schlenk bottle Silylene) bis (indene) lithium salt (3.0 g, 6.97 mmol) was dissolved in 50 ml of THF (tetrahydrofuran) and cooled to -78 ° C. 2.1 ml (14.2 mmol) of iodomethyltrimethylsilane was slowly added dropwise and stirred at room temperature for 12 hours.
The solvent was distilled off, 50 ml of ether was added, and the mixture was washed with a saturated ammonium chloride solution. After liquid separation, the organic phase is dried and the solvent is removed to obtain 3.04 g (5.88 mmol) of (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) bis (3-trimethylsilylmethylindene). (Yield 84%).
Next, in a Schlenk bottle under a nitrogen stream, 3.04 g (5.88 mmol) of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (3-trimethylsilylmethylindene) obtained above and 50 ml of ether was added. The mixture was cooled to −78 ° C., and a hexane solution of n-BuLi (1.54M, 7.6 ml (1.7 mmol)) was added dropwise. After raising to room temperature and stirring for 12 hours, ether was distilled off. The obtained solid was washed with 40 ml of hexane to obtain 3.06 g (5.07 mmol) of the lithium salt as an ether adduct (yield 73%).
The results of measurement by ¹ H-NMR (90 MHz, THF-d ₈ ) are as follows.
δ: 0.04 (s, 18H, trimethylsilyl), 0.48 (s, 12H, dimethylsilylene), 1.10 (t, 6H, methyl), 2.59 (s, 4H, methylene), 3.38 (q, 4H, methylene), 6.2- 7.7 (m, 8H, Ar-H)
Under a nitrogen stream, the lithium salt obtained above was dissolved in 50 ml of toluene. The mixture was cooled to -78 ° C, and a suspension of 1.2 g (5.1 mmol) of zirconium tetrachloride, which had been cooled to -78 ° C in advance, in toluene (20 ml) was added dropwise thereto. After dropping, the mixture was stirred at room temperature for 6 hours. The solvent of the reaction solution was distilled off. The resulting residue was recrystallized from dichloromethane to obtain 0.9 g (1.33 mmol) of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (3-trimethylsilylmethylindenyl) zirconium dichloride. ) Was obtained (yield 26%).
The results of measurement by ¹ H-NMR (90 MHz, CDCl ₃ ) are as follows.
δ: 0.0 (s, 18H, trimethylsilyl), 1.02, 1.12 (s, 12H, dimethylsilylene), 2.51 (dd, 4H, methylene), 7.1-7.6 (m, 8H, Ar-H)

Production Example 2
Production of solid catalyst 16 g of diethyl magnesium was charged into a three-flask with a stirrer having an internal volume of 500 ml purged with nitrogen, and then 80 ml of dehydrated octane was added. The mixture was heated to 40 ° C., 2.4 ml of silicon tetrachloride was added, stirred for 20 minutes, and 3.4 ml of di-n-butyl phthalate (DNBP) was added. The solution was heated to 80 ° C., and 77 ml of titanium tetrachloride was subsequently added dropwise using a dropping funnel. The internal temperature was set to 125 ° C. for 2 hours. Then, stirring was stopped, solid was settled, and the supernatant liquid was extracted. 100 ml of dehydrated octane was added, and the temperature was raised to 125 ° C. while stirring and held for 1 minute. Then, stirring was stopped, the solid was allowed to settle, and the supernatant was extracted. This washing operation was repeated 7 times. Next, 122 ml of titanium tetrachloride was added to bring the internal temperature to 125 ° C. and contacted for 2 hours. Thereafter, washing with dehydrated octane at 125 ° C. was repeated 6 times to obtain a solid catalyst component.

Example 1
(1) Production of 1-octene polymer Into an autoclave with a stirrer having an internal volume of 1 L, which had been dried by heating, 400 mL of 1-octene was charged in a nitrogen stream, and then 0.25 mL (2.0 mmol / 2.0 mmol / h) of a heptane solution of triisobutylaluminum. mL). Thereafter, the temperature was raised to 90 ° C. while stirring at 400 rpm, and 2.0 μmol (10 μmol / l) of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (3-trimethylsilylmethylindenyl) zirconium dichloride was obtained. To a toluene solution (0.2 mL) and dimethylanilinium tetrakis (pentafluorophenyl borate) were added 8.0 μmol (20 μmol / mL heptane slurry, 0.4 mL). Then, 0.15 MPa of hydrogen was introduced, and polymerization was performed for 1 hour.
After completion of the polymerization, 3 mL of methanol was added to stop the polymerization reaction. After depressurization, 205 g of 1-octene polymer was obtained by drying the reaction mixture under reduced pressure. The analytical values of the obtained 1-octene polymer are shown in Table 1.

(2) Production of cross-linked 1-octene polymer 4.4 g of 1-octene polymer obtained in (1) above and 0.04 g of Perbutyl C (1 hour half-life temperature: 137.3 ° C.) manufactured by NOF Corporation Was placed in a 20 mL Schlenk bottle and mixed well with a glass rod. Thereafter, nitrogen substitution was performed three times, and nitrogen was circulated so that the 1-octene polymer could maintain a nitrogen atmosphere, and heating was performed using an oil bath at 180 ° C. for 20 minutes to obtain a crosslinked 1-octene polymer. . The physical property values of the crosslinked 1-octene polymer are shown in Table 1.

Example 2
(1) Production of 1-decene polymer Into a heat-dried autoclave with an internal volume of 1 L with a stirrer, 400 mL of 1-decene was charged in a nitrogen stream, and then 0.25 mL (2.0 mmol / 2.0 mmol / h) of a heptane solution of triisobutylaluminum. mL). Thereafter, the temperature was raised to 70 ° C. while stirring at 400 rpm, and 2.0 μmol (10 μmol / l) of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (3-trimethylsilylmethylindenyl) zirconium dichloride was obtained. To a toluene solution (0.2 mL) and dimethylanilinium tetrakis (pentafluorophenyl borate) were added 8.0 μmol (20 μmol / mL heptane slurry, 0.4 mL). Then, 0.1 MPa of hydrogen was introduced and polymerization was performed for 1 hour.
After completion of the polymerization, 3 mL of methanol was added to stop the polymerization reaction. After depressurization, 105 g of 1-decene polymer was obtained by drying the reaction mixture under reduced pressure. The analytical values of the obtained 1-decene polymer are shown in Table 1.

(2) Production of cross-linked 1-decene polymer 4.2 g of 1-decene polymer obtained in (1) above and Perbutyl C manufactured by NOF Corporation (1 hour half-life temperature: 137.3 ° C) 0.04 g Was placed in a 20 mL Schlenk bottle and mixed well with a glass rod. Thereafter, nitrogen substitution was performed three times, and nitrogen was passed so that the 1-decene polymer could maintain the nitrogen atmosphere, and heating was performed using an oil bath at 180 ° C. for 20 minutes to obtain a crosslinked 1-decene polymer. . The physical property values of the crosslinked 1-decene polymer are shown in Table 1.

Example 3
(1) Production of 1-tetradecene polymer After adding 400 mL of 1-tetradecene to a heat-dried autoclave with an internal volume of 1 L under a nitrogen stream, 0.25 mL (2.0 mmol / h) of a heptane solution of triisobutylaluminum. mL). Thereafter, the temperature was raised to 70 ° C. while stirring at 400 rpm, and 2.0 μmol (10 μmol / l) of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (3-trimethylsilylmethylindenyl) zirconium dichloride was obtained. To a toluene solution (0.2 mL) and dimethylanilinium tetrakis (pentafluorophenyl borate) were added 8.0 μmol (20 μmol / mL heptane slurry, 0.4 mL). Then, 0.1 MPa of hydrogen was introduced and polymerization was performed for 1 hour.
After completion of the polymerization, 3 mL of methanol was added to stop the polymerization reaction. After depressurization, 105 g of 1-tetradecene polymer was obtained by drying the reaction mixture under reduced pressure. The analytical values of the obtained 1-tetradecene polymer are shown in Table 1.

(2) Production of cross-linked 1-tetradecene polymer 4.0 g of 1-tetradecene polymer obtained in (1) above and 0.04 g of Perbutyl C manufactured by NOF Corporation (1 hour half-life temperature: 137.3 ° C) Was placed in a 20 mL Schlenk bottle and mixed well with a glass rod. Thereafter, nitrogen substitution was performed three times, and nitrogen was circulated so that the 1-tetradecene polymer could maintain a nitrogen atmosphere, and heating was performed using an oil bath at 180 ° C. for 20 minutes to obtain a crosslinked 1-tetradecene polymer. . The physical property values of the crosslinked 1-tetradecene polymer are shown in Table 1.

Comparative Example 1
(1) Production of 1-octene polymer 400 ml of 1-octene was charged at room temperature into a stainless steel autoclave with a stirrer having an internal volume of 1 L which had been sufficiently dried and replaced with dry nitrogen. Subsequently, 1.0 mmol of triethylaluminum, 16.3 mg of the solid catalyst component prepared in Production Example 2 and 50 μmol of dicyclopentyldimethoxysilane were charged into the autoclave. Thereafter, hydrogen was added to 0.1 MPa, the temperature was raised to 70 ° C., and polymerization was carried out for 1 hour. Next, 5 ml of methanol was added, the polymerization was stopped, hydrogen was depressurized, the temperature was lowered, and the obtained polymerization solution was dried under reduced pressure to obtain 105 g of a 1-octene polymer. The analytical values of the obtained 1-octene polymer are shown in Table 1.

(2) Crosslinking reaction of 1-octene polymer 4.2 g of 1-octene polymer obtained in (1) above and 0.04 g of Perbutyl C (1 hour half-life temperature: 137.3 ° C.) manufactured by NOF Corporation Was placed in a 20 mL Schlenk bottle and mixed well with a glass rod. Thereafter, nitrogen substitution was performed three times, and nitrogen was circulated so that the 1-octene polymer could maintain a nitrogen atmosphere, followed by heating for 20 minutes using an oil bath at 180 ° C., thereby cross-linking the 1-octene polymer. went. However, the viscosity of the 1-octene polymer was high, and it was difficult to uniformly mix the radical generator (perbutyl C). The physical properties of the reaction product are shown in Table 1.

Comparative Example 2
(1) Production of 1-decene polymer 200 ml of 1-decene and 200 ml of dry heptane were charged at room temperature into a stainless steel autoclave with a stirrer having an internal volume of 1 L which had been sufficiently dried and replaced with dry nitrogen. Subsequently, 1.0 mmol of triethylaluminum, 16.3 mg of the solid catalyst component prepared in Production Example 2 and 50 μmol of dicyclopentyldimethoxysilane were charged into the autoclave. Thereafter, hydrogen was added to 0.1 MPa, the temperature was raised to 35 ° C., and polymerization was carried out for 1 hour. Next, 5 ml of methanol was added, the polymerization was stopped, hydrogen was depressurized, the temperature was lowered, and the resulting polymer solution was dried under reduced pressure to obtain 95 g of a 1-decene polymer. The analytical values of the obtained 1-decene polymer are shown in Table 1.

(2) Crosslinking reaction of 1-decene polymer 4.5 g of 1-decene polymer obtained in the above (1) and 0.04 g of Perbutyl C (1 hour half-life temperature: 137.3 ° C.) manufactured by NOF Corporation. Was placed in a 20 mL Schlenk bottle and mixed well with a glass rod. Thereafter, nitrogen substitution was performed three times, and nitrogen was circulated so that the 1-decene polymer could maintain a nitrogen atmosphere, and heating was performed using an oil bath at 180 ° C. for 20 minutes, whereby the crosslinking reaction of the 1-decene polymer was performed. went. However, the 1-decene polymer was hard and the radical generator (perbutyl C) could not be charged uniformly. The physical properties of the reaction product are shown in Table 1.

  According to the present invention, a crosslinked olefin polymer which is soft and has a high crosslinking rate can be obtained. The crosslinked olefin polymer of the present invention is soft and has excellent characteristics of shape memory, and is suitable for applications such as impact absorbers, pressure-sensitive adhesives, oil absorbents, electronic component sealing and adhesives. Used.

Claims (7)

A crosslinked olefin polymer having a crosslinking rate of 20% or more obtained by a crosslinking reaction of an α-olefin polymer satisfying the following (A) to (C) .
(A) A homopolymer of an α-olefin having 8 to 30 carbon atoms, a copolymer of two or more α-olefins having 8 to 30 carbon atoms, and an α-olefin having 8 to 30 carbon atoms and ethylene and / or propylene An α-olefin polymer selected from the group consisting of an α-olefin unit having 8 to 30 carbon atoms and having an ethylene unit and / or propylene unit of less than 50 mol%. (B) Intrinsic viscosity [η] is 0.1 to 4.0 dl / g
(C) Molecular weight distribution (Mw / Mn) measured by GPC method is 3.5 or less   The crosslinked olefin polymer according to claim 1, wherein the α-olefin polymer is produced using a metallocene catalyst.   It is obtained by using 0.1 to 10% by mass of a peroxide based on the total amount of the mixture before the crosslinking reaction, and performing the crosslinking reaction at a temperature higher than the one-hour half-life temperature of the peroxide. Item 3. The crosslinked olefin polymer according to Item 1 or 2. A cross-linked olefin weight which performs a cross-linking reaction using an α-olefin polymer satisfying the following (A) to (C) as a raw material and 0.1 to 10% by mass of a radical generator based on the total amount of the mixture before the cross-linking reaction. Manufacturing method of coalescence.
(A) A homopolymer of an α-olefin having 8 to 30 carbon atoms, a copolymer of two or more α-olefins having 8 to 30 carbon atoms, and an α-olefin having 8 to 30 carbon atoms and ethylene and / or propylene An α-olefin polymer selected from the group consisting of an α-olefin unit having 8 to 30 carbon atoms and having an ethylene unit and / or propylene unit of less than 50 mol%. (B) Intrinsic viscosity [η] is 0.1 to 4.0 dl / g
(C) Molecular weight distribution (Mw / Mn) measured by GPC method is 3.5 or less   The manufacturing method of the crosslinked olefin polymer of Claim 4 which performs a crosslinking reaction using a peroxide as a radical generator.   The method for producing a crosslinked olefin polymer according to claim 5, wherein the crosslinking reaction is performed at a temperature higher than the one-hour half-life temperature of the peroxide.   The method for producing a crosslinked olefin polymer according to any one of claims 4 to 6, wherein the crosslinking reaction is performed in an atmosphere having an oxygen concentration of 5 vol% or less.