JP2008133320A - TERMINAL-MODIFIED POLY-alpha-OLEFIN, METHOD FOR PRODUCING THE SAME AND COMPOSITION CONTAINING THE SAME - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a terminal-modified poly-α-olefin exhibiting high selectivity in hydrosilylation reaction and having balanced heat-resistance, low-temperature meltability and solubility, and to provide a method for producing the polyolefin and a composition containing the polyolefin. <P>SOLUTION: The terminal-modified poly-α-olefin has a residue formed by the reaction of the poly-α-olefin with a silicon compound having an Si-H group on the terminal of a poly-α-olefin satisfying the following requirements (1) to (3): (1) the polyolefin is produced by the polymerization of one or more kinds of 3-28C α-olefins or the copolymerization of one or more kinds of 3-28C α-olefins and ethylene, (2) the meso pentad fraction [mmmm] is 30-80 mol%, and (3) the intrinsic viscosity [η] measured in decalin at 135°C is 0.01-2.5 dl/g. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a terminal-modified poly-α-olefin, a method for producing the same, and a composition containing the same, and more specifically, uses in fields where interfacial adhesion, compatibilization, and crosslinking reaction are required, for example, resins such as polyolefins. End-modified poly α suitable for applications such as modifiers, inorganic material surface treatment agents and inorganic filler treatment agents, coating agents, primer treatment, improved physical properties of resin / inorganic material composites, adhesives, sealing materials and potting materials -Relates to olefins, processes for their production and compositions containing them.

Conventionally, polyolefins such as polyethylene and polypropylene are poorly compatible with polymers other than the same type of polyolefin, and as a resin modifier, mechanical properties such as chemical stability, fluidity, and impact strength are originally improved. Although considered to be large, there is a problem in that the original performance cannot be sufficiently exhibited due to poor compatibility. Moreover, although the modification effect by addition of various fillers is also expected, there is a problem that the familiarity between the polyolefin and the filler is low, and the original properties of the polyolefin are not exhibited. Therefore, further application development of polyolefin can be expected by increasing the compatibility.
On the other hand, the low-order polyolefin obtained by using a metallocene-based catalyst is excellent in flexibility and miscibility with an olefin-based resin due to low regularity, but by solving the above problems, adhesion and Expansion to applications such as compounding with different types of resins is expected.
As a technique for exhibiting the characteristics of polyolefin, a technique for hydrosilylation of carbon-carbon unsaturated bonds is known, and application of hydrosilylation to unsaturated group-containing polymers is also disclosed (for example, patents). References 1-3). Patent Document 1 discloses a technique related to hydrosilylation of residual unsaturated groups of partially hydrogenated polybutadiene. However, since a hydrogenation process is required, the manufacturing process is complicated, and at the same time, the hydrosilylation position is unclear and the structure controllability is lacking. In Patent Documents 2 and 3, hydrosilylation is performed on the residual unsaturated groups of the ethylene / α-olefin / non-conjugated polyene copolymer, but the production process becomes complicated because the unsaturated groups are introduced by copolymerization. The cost will be high.
Moreover, the technique regarding the hydrosilylation of a terminal unsaturated group is also disclosed (for example, refer patent documents 4-7). Patent Document 4 discloses a technique related to a block copolymer of a terminal unsaturated polyolefin and a polymer composed of an anion polymerizable monomer having a terminal unsaturated group, utilizing a hydrosilylation reaction. Patent Document 4 discloses that end-unsaturated polypropylene is obtained by a metallocene catalyst, and highly stereoregular [mm] = 88 mol% polypropylene and atactic polypropylene. However, Patent Document 4 does not describe a medium stereoregular region polypropylene, a polypropylene having both solvent solubility and crystallinity.
Patent Document 5 discloses a hydrosilylation reaction in which a terminal unsaturated group polypropylene is generated by radical decomposition and is used. Patent Document 5 describes a polypropylene produced using a metallocene-based catalyst as a terminal unsaturated group polypropylene, but there is no specific description or illustration.
Patent Documents 6 and 7 disclose a hydrosilylation reaction in the molten state of an unsaturated polymer, and examples of the unsaturated polymer include terminal unsaturated polypropylene produced by radical decomposition. Specifically, a reaction in which a terminal unsaturated group is generated and silylated in a series of reaction processes is disclosed, and the melting reaction temperature at that time is as high as 160 to 230 ° C., and polypropylene is decomposed at the same time. Things coexist. Reaction controllability in the hydrosilylation reaction described in Patent Documents 6 and 7 is low.
Pyrolysis PP is a mixture of terminal saturated, one terminal unsaturated, and both terminal unsaturated, and a modified product added in a block manner to the polyolefin chain terminal targeted by the present application cannot be produced with high purity. In the case of radical or thermal decomposition, it is known that the terminal structure contains one having more than one unsaturated group per molecule. For example, Patent Document 7 describes that the number of terminal unsaturated groups of decomposed polypropylene produced by thermal decomposition is 1.4.

JP 09-59317 A JP 2001-98076 A JP 2003-192724 A JP 07-316225 A JP 2002-522604 A International Publication No. 97/47665 Pamphlet JP-A-6-107442

  The present invention has been made in view of the above circumstances, and has good selectivity (regioselectivity, modified product yield, etc.) in the hydrosilylation reaction and does not require a high-temperature reaction, so that energy costs and side reactions can be suppressed. In addition, an object of the present invention is to provide a terminal-modified polyα-olefin having a good balance between heat resistance, low-temperature melting property and solubility, a method for producing the same, and a composition containing the same.

As a result of extensive research, the present inventors can achieve the object by terminally modified polyα-olefin having a specific residue at a terminal of a specific polyα-olefin and satisfying a specific condition. I found out. The present invention has been completed based on such findings.
That is, the present invention provides the following terminal-modified poly α-olefin, a process for producing the same, and a composition containing the same.
1. The terminal which has the residue produced | generated by reaction of this poly (alpha) -olefin and the silicon compound which has Si-H group in the terminal of the poly (alpha) -olefin which satisfies the following (1)-(3) Modified poly α-olefin.
(1) It is obtained by polymerization of one or more α-olefins having 3 to 28 carbon atoms or copolymerization of ethylene with one or more selected from α-olefins having 3 to 28 carbon atoms.
(2) Mesopentad fraction [mmmm] is in the range of 30 to 80 mol%.
(3) The intrinsic viscosity [η] measured at 135 ° C. in decalin is in the range of 0.01 to 2.5 dl / g.
2. 2. The terminal-modified polyα-olefin according to 1 above, wherein the residue produced by the reaction with the silicon compound having Si—H is the following (I) or (II).
(I) A silicon compound residue represented by the general formula [I].

(In the formula, R ¹ is a monovalent hydrocarbon group having 1 to 12 carbon atoms, and L is selected from a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amide group, an acid amide group, and an aminooxy group. A hydrolyzable group, when there are a plurality of R ¹ or L, the plurality of R ¹ and the plurality of L may be the same or different, a is 0, 1 or 2. -Si is poly α -A binding site with an olefin.
(II) Polysiloxane residue satisfying the following (a) to (c)
(a) It has the structure of the siloxane terminal (A unit) represented by general formula (A), the siloxane main chain (B unit) represented by general formula (B), or both.
(b) The polysiloxane molecular main chain has a siloxane repeating unit (C unit) represented by the general formula (C).

(In the formula, R ^{2 to} R ⁶ each independently represent an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms. * -Si represents a bonding site with a poly α-olefin.)
(c) The number of A units is 0 to 2 / molecule, the number of B units is 0 to 10 / molecule, and A unit and B unit are not 0 at the same time. The total of the A unit, B unit and C unit is 5 to 1500 per molecule, and the polysiloxane terminal other than the bonding site with the poly α-olefin is R ⁷ or OR ⁸ (R ⁷ and R ⁸ are each independently Represents an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms.).
3. 1 or 2 above, wherein the poly α-olefin is a propylene homopolymer or a copolymer of 90% by mass or more of propylene and one or more selected from ethylene and an α-olefin having 4 to 28 carbon atoms. Terminal-modified polyalphaolefin.
4). The poly α-olefin is a 1-butene homopolymer or a copolymer of 90% by mass or more of 1-butene and one or more types selected from ethylene, propylene and an α-olefin having 5 to 28 carbon atoms. 3. The terminal-modified poly α-olefin according to 1 or 2 above.
5. The number of carbon atoms in the presence of a catalyst containing poly (α-olefin) containing (A) a transition metal compound represented by the general formula [II] and (B) a compound capable of reacting with the transition metal compound to form an ionic complex. 5. The polymer according to any one of 1 to 4 above, which is obtained by polymerization of one or more α-olefins having 3 to 28, or copolymerization of one or more α-olefins selected from α-olefins having 3 to 28 carbon atoms with ethylene. Terminally modified polyalphaolefin.

[In the formula, M represents a metal element of Groups 3 to 10 of the periodic table, and E ¹ and E ² represent a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, and a heterocyclopenta, respectively. A ligand selected from a dienyl group, a substituted heterocyclopentadienyl group, an amide group, a phosphine group, a hydrocarbon group and a silicon-containing group is formed, and a crosslinked structure is formed through A ¹ and A ^2. ing. E ¹ and E ² may be the same or different from each other, and at least one of E ¹ and E ² is a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group or a substituted indenyl group. is there. X represents a σ-bonding ligand, and when there are a plurality of Xs, the plurality of Xs may be the same or different, and may be cross-linked with other X, E ¹ , 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. 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, a silicon-containing group, germanium containing group, a tin-containing group, -O -, - CO -, - S -, - SO 2 -, - Se -, - NR -, - PR -, - P (O) R -, - BR- or -AlR R 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. ]
6). In the presence of a catalyst containing a transition metal compound, a polyα-olefin satisfying the following (4) to (7) and one or more silicon compounds selected from the following (III) and (IV) are subjected to a hydrosilylation reaction: The method for producing a terminally modified poly-α-olefin as described in any one of 1 to 5 above.
(4) It is obtained by polymerization of one or more α-olefins having 3 to 28 carbon atoms, or copolymerization of ethylene with one or more selected from α-olefins having 3 to 28 carbon atoms.
(5) Mesopentad fraction [mmmm] is in the range of 30 to 80 mol%.
(6) It has 0.5 to 1.0 vinylidene group as a terminal unsaturated group per molecule.
(7) The intrinsic viscosity [η] measured at 135 ° C. in decalin is in the range of 0.01 to 2.5 dl / g.
(III) A silicon compound represented by the general formula [III].

(Wherein R ¹ is a monovalent hydrocarbon group having 1 to 12 carbon atoms, and L is selected from a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amide group, an acid amide group, and an aminooxy group. A hydrolyzable group, when there are a plurality of R ¹ or L, the plurality of R ¹ and the plurality of L may be the same or different, a is 0, 1 or 2)
(IV) Polysiloxane satisfying the following (d) to (f)
(d) It has the structure of the siloxane terminal (D unit) represented by general formula (D), the siloxane main chain (E unit) represented by general formula (E), or both.
(e) The polysiloxane molecular main chain has a siloxane repeating unit (C unit) represented by the general formula (C).

(In the formula, R ^{2 to} R ⁶ each independently represents an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms.)
(f) The number of D units is 0 to 2 / molecule, the number of E units is 0 to 10 / molecule, and the D unit and the E unit are not 0 at the same time. The total number of D units, E units and C units is 5 to 1500 per molecule, and the polysiloxane terminal is R ⁷ or OR ⁸ (R ⁷ and R ⁸ are each independently an unsubstituted or substituted carbon number of 1 to 12 represents a monovalent hydrocarbon group.).
7). The number of carbon atoms in the presence of a catalyst containing poly (α-olefin) containing (A) a transition metal compound represented by the general formula [II] and (B) a compound capable of reacting with the transition metal compound to form an ionic complex. 7. The terminal-modified polyα-olefin according to 6 above, which is obtained by polymerization of one or more α-olefins having 3 to 28 or copolymerization of ethylene with one or more α-olefins having 3 to 28 carbon atoms. Manufacturing method.

〔式中、Ｍ、Ｅ¹、Ｅ²、Ａ¹、Ａ²、Ｘ、Ｙ、ｑ及びｒは上記と同じである。〕
８． ポリα−オレフィンが、プロピレンホモポリマー、あるいはプロピレン９０質量％以上と、エチレン及び炭素数４〜２８のα−オレフィン１０質量％以下との共重合体であり、示差走査型熱量計（ＤＳＣ）で観測される融点（Ｔｍ、単位：℃）と［ｍｍｍｍ］とが下記式［IV］の関係を満たす上記６又は７記載の末端変性ポリα−オレフィンの製造方法。
１．７６[ｍｍｍｍ]−２５．０≦Ｔｍ≦１．７６[ｍｍｍｍ]＋５．０ ［IV］
９． ハイドロシリレーション反応を、反応温度５０〜１５０℃の範囲において溶融状態で行う上記６〜８のいずれかに記載の末端変性ポリα−オレフィンの製造方法。
１０． ハイドロシリレーション反応を、反応温度−３０〜１５０℃の範囲において溶液状態で行う上記６〜８のいずれかに記載の末端変性ポリα−オレフィンの製造方法。
１１． 上記１〜５のいずれかに記載の末端変性ポリα−オレフィンと、他の樹脂及び無機フィラーから選ばれる一種以上を含む組成物。

[Wherein, M, E ¹ , E ² , A ¹ , A ² , X, Y, q and r are the same as above. ]
8). The poly α-olefin is a propylene homopolymer or a copolymer of 90% by mass or more of propylene and 10% by mass or less of ethylene and an α-olefin having 4 to 28 carbon atoms, and is a differential scanning calorimeter (DSC). 8. The method for producing a terminal-modified polyα-olefin according to the above 6 or 7, wherein the observed melting point (Tm, unit: ° C.) and [mmmm] satisfy the relationship of the following formula [IV].
1.76 [mmmm] -25.0 ≦ Tm ≦ 1.76 [mmmm] +5.0 [IV]
9. The method for producing a terminally modified poly-α-olefin according to any one of the above 6 to 8, wherein the hydrosilylation reaction is performed in a molten state at a reaction temperature in the range of 50 to 150 ° C.
10. 9. The method for producing a terminal-modified polyα-olefin according to any one of 6 to 8 above, wherein the hydrosilylation reaction is performed in a solution state at a reaction temperature in the range of −30 to 150 ° C.
11. The composition containing 1 or more types chosen from the terminal modified poly alpha olefin in any one of said 1-5, and other resin and an inorganic filler.

  According to the method for producing a terminal-modified polyα-olefin of the present invention, terminal modification is performed in a block manner at a low temperature, and the terminal-modified polyα-olefin can be produced with a high modified product yield. The terminal-modified poly α-olefin of the present invention has high solvent solubility and also has heat resistance because it has stereoregularity. Therefore, in addition to the surface treatment of the filler in a molten state, the filler can be surface-treated in a solution or emulsion state. In addition, the poly α-olefin of the present invention is useful for various uses, for example, a modifier, a surface treatment agent for inorganic materials, an inorganic filler treatment agent, and the like.

The terminal-modified poly α-olefin of the present invention is produced by reaction of the poly α-olefin with a silicon compound having a Si—H group at the end of the poly α-olefin satisfying the following (1) to (3). With residues.
(1) It is obtained by polymerization of one or more α-olefins having 3 to 28 carbon atoms or copolymerization of ethylene with one or more selected from α-olefins having 3 to 28 carbon atoms.
Examples of the α-olefin having 3 to 28 carbon atoms include propylene, 1-butene, 1-pentene, 4-methylpentene-1, 1-hexene, 1-octene, 1-decene, 1-undecene, 1-dodecene, -Tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene and the like can be mentioned. These can be used individually by 1 type or in combination of 2 or more types.
When the α-olefin is polymerized alone, an α-olefin having 3 to 8 carbon atoms is preferable, and propylene and 1-butene are particularly preferable. Moreover, as a combination of the monomer in the case of copolymerizing ethylene with one or more selected from α-olefins having 3 to 28 carbon atoms, propylene and ethylene, 1-butene and ethylene are preferable. The combination of two or more of α-olefins having 3 to 28 carbon atoms is selected from one or more selected from propylene and α-olefins having 4 to 28 carbon atoms, 1-butene and α-olefins having 5 to 28 carbon atoms. One or more selected from the above are preferred, and two or more and six or less selected from α-olefins having 16 to 28 carbon atoms can be mentioned. A homopolymerization of an α-olefin having 16 to 28 carbon atoms is also included.
In the terminal-modified poly α-olefin of the present invention, the comonomer content is preferably 10% by mass or less from the viewpoint of maintaining a high concentration of terminal groups.

(2) Mesopentad fraction [mmmm] is in the range of 30 to 80 mol%.
The mesopentad fraction [mmmm], which is a stereoregularity index, is more preferably 30 to 75 mol%, and further preferably 32 to 70 mol%. When the mesopentad fraction is 30 mol% or more, the poly α-olefin becomes crystalline, and thus exhibits heat resistance. Moreover, since the said poly alpha olefin becomes moderately soft as it is 80 mol% or less, the solubility to a solvent becomes favorable and can apply widely to solution reaction etc.

Among the poly α-olefins according to the present invention, a propylene homopolymer, or a copolymer of 90% by mass or more of propylene and one or more selected from ethylene and an α-olefin having 4 to 28 carbon atoms (hereinafter referred to as “below”) These may be referred to as “propylene-based polymers”.) The mesopentad fraction [mmmm], the racemic pentad fraction [rrrr] and the racemic mesoracemi meso fraction [rmrm] described below are A. Zambelli) et al., In accordance with the method proposed in “Macromolecules, 6 , 925 (1973)”, and meso content of pentad units in a polypropylene molecular chain measured by a methyl group signal in a ¹³ C-NMR spectrum. Rate, racemic fraction and racemic meso-racemic meso fraction. As the mesopentad fraction [mmmm] increases, the stereoregularity increases.
The ¹³ C-NMR spectrum can be measured according to the assignment of the peak proposed in “Macromolecules, 8 , 687 (1975)” by A. Zambelli et al. it can. Further, the mesotriad fraction [mm], the racemic triad fraction [rr] and the mesoracemi fraction [mr] described later were also calculated by the above method.

Apparatus: JNM-EX400 type ¹³ C-NMR apparatus manufactured by JEOL Ltd. Method: Proton complete decoupling method Concentration: 220 mg / ml
Solvent: 90:10 (volume ratio) mixed solvent of 1,2,4-trichlorobenzene and heavy benzene Temperature: 130 ° C
Pulse width: 45 °
Pulse repetition time: 4 seconds Integration: 10,000 times

<Calculation formula>
M = (m / S) × 100
R = (γ / S) × 100
S = Pββ + Pαβ + Pαγ
S: Signal intensity of side chain methyl carbon atoms of all propylene units Pββ: 19.8 to 22.5 ppm
Pαβ: 18.0 to 17.5 ppm
Pαγ: 17.5 to 17.1 ppm
γ: Racemic pentad chain: 20.7 to 20.3 ppm
m: Mesopentad chain: 21.7-22.5 ppm

1-butene homopolymer of poly α-olefins according to the present invention, or 1-butene 90% by mass or more, and at least one 10% by mass selected from ethylene, propylene and C-28 α-olefins. The mesopentad fraction [mmmm] of the copolymer (hereinafter sometimes referred to as “1-butene-based polymer”) is “Polymer Journal, 16, 717 (1984)” reported by Asakura et al. J. et al. “Macromol. Chem. Phys., C29, 201 (1989)” reported by Randall et al. It was determined according to the method proposed in “Macromol. Chem. Phys., 198, 1257 (1997)” reported by Busico et al. That is, the signals of methylene group and methine group were measured using ¹³ C nuclear magnetic resonance spectrum to determine the mesopentad fraction in the poly (1-butene) molecule. The stereoregularity index {[mmmm] / [mmrr] + [rmmr]} to be described later is obtained by calculating the mesopentad fraction [mmmm], the mesomesolemic racemic fraction [mmrr], and the racemic mesomesolemic fraction [rmmr] by the above method. Calculated from the measured values.
^{The 13} C nuclear magnetic resonance spectrum was measured using the apparatus and conditions described above.

Of the poly α-olefin according to the present invention, a homopolymer of an α-olefin having 5 or more carbon atoms, or 90% by mass or more of an α-olefin having 5 or more carbon atoms, and 5 or more carbon atoms as a main component of the copolymer. A copolymer of at least one selected from ethylene and an α-olefin having 3 to 28 carbon atoms excluding the α-olefin (hereinafter referred to as “public holiday α-olefin copolymer”) The mesopentad fraction [mmmmmm] is defined as the stereoregularity index value M and is proposed in “Macromolecules, 24, 2334 (1991)” reported by T. Asakura, M. Demura, Y. Nishiyama. That is, the CH ₂ carbon at the side chain α-position derived from the higher α-olefin in the ¹³ C-NMR spectrum. M can be obtained by utilizing the fact that is divided and observed reflecting the difference in stereoregularity, and the larger this value, the higher the isotacticity.
The ¹³ C-NMR measurement apparatus and measurement conditions are the same as described above, and the stereoregularity index value M 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, M (mol%) is calculated | required using the following formula | equation.
M = [(36.2 to 35.3 ppm integrated intensity) / (36.2 to 34.5 ppm integrated intensity)] × 100

(3) The intrinsic viscosity [η] measured at 135 ° C. in decalin is in the range of 0.01 to 2.5 dl / g.
The intrinsic viscosity [η] is calculated by measuring the reduced viscosity (η _SP / c) with a Ubbelohde viscometer in decalin at 135 ° C. and using the following formula (Huggins formula).
η _SP / c = [η] + K [η] ² c
η _SP / c (dl / g): Reduced viscosity [η] (dl / g): Intrinsic viscosity c (g / dl): Polymer concentration K = 0.35 (Haggins constant)
In the poly α-olefin according to the present invention, the intrinsic viscosity [η] is preferably 0.05 to 2.3 dl / g, more preferably 0.07 to 2.2 dl / g, and still more preferably 0.1 to 2. 0.0 dl / g. If the intrinsic viscosity [η] is 0.01 dl / g or more, the molecular weight will not be too low, so that the chemical stability of the poly α-olefin is maintained, and if it is 2.5 dl / g or less, the end group Since the fall of the density | concentration of is suppressed, the characteristic of poly (alpha) -olefin is hold | maintained.

The propylene polymer preferably further satisfies the following (8), and more preferably satisfies the following (9) to (12).
(8) The melting point (Tm, unit: ° C) and [mmmm] observed by a differential scanning calorimeter (DSC) satisfy the following relationship.
1.76 [mmmm] -25.0 ≦ Tm ≦ 1.76 [mmmm] +5.0
[Mmmm] is measured as an average value, and it cannot be clearly distinguished when the stereoregularity distribution is wide or narrow, but by limiting the relationship with the melting point (Tm) to a specific range A preferable highly uniform reactive polypropylene can be defined.
The relational expression is more preferably 1.76 [mmmm] -20.0 ≦ Tm ≦ 1.76 [mmmm] +3.0
More preferably, 1.76 [mmmm] -15.0 ≦ Tm ≦ 1.76 [mmmm] +2.0
It is.
When the melting point (Tm) exceeds (1.76 [mmmm] +5.0), it indicates that there are partially highly stereoregular sites and sites that do not have stereoregularity. Moreover, when melting | fusing point (Tm) does not reach (1.76 [mmmm] -25.0), there exists a possibility of including a large amount of abnormal insertions, such as 2, 1 insertion and a 1, 3- bond.

(9) [rmrm]> 2.5 mol%
When [rmrm] of the propylene-based polymer is less than 2.5 mol%, randomness is increased and transparency is further improved.
(10) [rrrr] / (1- [mmmm]) ≦ 0.1
When [rrrr] / (1- [mmmm]) of the propylene-based polymer is 0.1 or less, stickiness is suppressed.
In addition, melting | fusing point (Tm) is calculated | required by DSC measurement. That is, using a differential scanning calorimeter (DSC-7, manufactured by Perkin Elmer), 10 mg of a sample was melted at 220 ° C. for 3 minutes in a nitrogen atmosphere, and then cooled to −40 ° C. at 10 ° C./min. Furthermore, the melting point (Tm) is the peak top of the peak observed on the highest temperature side of the melting endothermic curve obtained by keeping the temperature at −40 ° C. for 3 minutes and then raising the temperature at 10 ° C./min.

(11) [mm] × [rr] / [mr] ² ≦ 2.0
When the value of [mm] × [rr] / [mr] ² of the propylene-based polymer is 2.0 or less, a decrease in transparency is suppressed and the balance between flexibility and elastic recovery rate is improved. [Mm] × [rr] / [mr] ² is preferably in the range of 1.8 to 0.5, more preferably 1.5 to 0.5.
(12) The component amount (W25) eluting at 25 ° C. or lower in the temperature rising chromatography is 20 to 100% by mass.
In the propylene-based polymer, the component amount (W25) of the propylene-based polymer eluted at 25 ° C. or less in the temperature rising chromatography is preferably 30 to 100% by mass, more preferably 50 to 100% by mass.
W25 is an index indicating whether or not the propylene-based polymer is soft. When this value is small, a component having a high elastic modulus is increased or the nonuniformity of the stereoregular distribution is widened. In the said propylene polymer, a softness | flexibility is maintained as W25 is 20 mass% or more.
W25 is not adsorbed by the packing material at a column temperature of 25 ° C. of TREF (temperature rising elution fractionation) in an elution curve obtained by measurement by temperature rising chromatography with the following operation method, apparatus configuration and measurement conditions. This is the amount (% by mass) of the eluted component.

(1) Operation method The sample solution is introduced into a TREF column adjusted to a temperature of 135 ° C, then gradually cooled to 0 ° C at a temperature decrease rate of 5 ° C / hour, held for 30 minutes, and the sample is crystallized on the surface of the filler. Let Thereafter, the column is heated to 135 ° C. at a temperature increase rate of 40 ° C./hour to obtain an elution curve.
(2) Apparatus configuration TREF column: Silica gel column (4.6φ × 150 mm) manufactured by GL Science
Flow cell: GL Science Co., Ltd., optical path length 1 mm KBr cell Liquid feed pump: Senshu Kagaku Co., Ltd. SSC-3100 pump Valve oven: GL Science Co., Ltd. MODEL 554 oven (high temperature type)
TREF oven: GL Sciences 2 series temperature controller: Rigaku Kogyo REX-C100 temperature controller Detector: Infrared detector for liquid chromatography FOXBORO MIRAN 1A CVF
10-way valve: Barco's electric valve Loop: Barco's 500 μl loop (3) Measurement conditions Solvent: o-dichlorobenzene Sample concentration: 7.5 g / L
Injection volume: 500 μl
Pump flow rate: 2.0 ml / min Detection wave number: 3.41 μm
Column packing material: Chromosolve P (30-60 mesh)
Column temperature distribution: Within ± 0.2 ° C

The 1-butene polymer preferably further satisfies the following (13) and (14) in addition to the above (1) to (3).
(13) A crystalline resin in which a melting point (Tm) by a differential scanning calorimeter (DSC) is not observed or a melting point (Tm) is 0 to 100 ° C. In the 1-butene polymer of the present invention, when a melting point (Tm) is observed, this melting point is preferably 0 to 80 ° C. In addition, melting | fusing point is calculated | required with the measuring method mentioned above.
(14) {[mmmm] / [mmrr] + [rmmr]} ≦ 20
When the stereoregularity index {[mmmm] / [mmrr] + [rmmr]} of the 1-butene polymer is 20 or less, the flexibility is lowered, the low temperature heat sealability is lowered, and the hot tack property is lowered. It is suppressed. This stereoregularity index is preferably 18 or less, more preferably 15 or less.

  The poly α-olefin according to the present invention includes (A) a transition metal compound represented by the general formula [II] and (B) a catalyst containing a compound that can react with the transition metal compound to form an ionic complex. It can manufacture by performing a polymerization reaction below.

In the general formula [II], M represents a metal element belonging to Groups 3 to 10 of the periodic table, and specific examples include titanium, zirconium, hafnium, yttrium, vanadium, chromium, manganese, nickel, cobalt, palladium, and lanthanoid series. A metal etc. are mentioned. Among these, titanium, zirconium and hafnium are preferable from the viewpoint of olefin polymerization activity and the like, and zirconium is most preferable from the viewpoint of yield of terminal vinylidene group and catalytic 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 or different from each other. As E ¹ and E ² , a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group and a substituted indenyl group are preferable, and at least one of E ¹ and E ² is a cyclopentadienyl group, A substituted cyclopentadienyl group, an indenyl group or a substituted indenyl group;
X represents a σ-bonding ligand, and when there are a plurality of Xs, 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, and 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.
Examples of the halogen atom include a chlorine atom, a fluorine atom, a bromine atom and an iodine atom. Specific examples of the hydrocarbon group having 1 to 20 carbon atoms include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, hexyl group, cyclohexyl group and octyl group; vinyl group, propenyl group, cyclohexenyl group and the like. An arylalkyl group such as benzyl group, phenylethyl group, phenylpropyl group; phenyl group, tolyl group, dimethylphenyl group, trimethylphenyl group, ethylphenyl group, propylphenyl group, biphenyl group, naphthyl group, methylnaphthyl group Group, anthracenyl group, aryl group such as phenanthonyl group, and the like. Of these, alkyl groups such as methyl group, ethyl group, and propyl group, and aryl groups such as phenyl group are preferable.

Examples of the alkoxy group having 1 to 20 carbon atoms include alkoxy groups such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group, a phenylmethoxy group, and a phenylethoxy group. Examples of the aryloxy group having 6 to 20 carbon atoms include a phenoxy group, a methylphenoxy group, and a dimethylphenoxy group. Examples of the amide group having 1 to 20 carbon atoms include a dimethylamide group, a diethylamide group, a dipropylamide group, a dibutylamide group, a dicyclohexylamide group, and a methylethylamide group, a divinylamide group, and a dipropenylamide group. And alkenylamide groups such as dicyclohexenylamide group; arylalkylamide groups such as dibenzylamide group, phenylethylamide group and phenylpropylamide group; arylamide groups such as diphenylamide group and dinaphthylamide group.
Examples of the silicon-containing group having 1 to 20 carbon atoms include monohydrocarbon-substituted silyl groups such as methylsilyl group and phenylsilyl group; dihydrocarbon-substituted silyl groups such as dimethylsilyl group and diphenylsilyl group; trimethylsilyl group, triethylsilyl group, Trihydrocarbon-substituted silyl groups such as tripropylsilyl group, tricyclohexylsilyl group, triphenylsilyl group, dimethylphenylsilyl group, methyldiphenylsilyl group, tolylsilylsilyl group and trinaphthylsilyl group; hydrocarbons such as trimethylsilyl ether group A substituted silyl ether group; a silicon-substituted alkyl group such as a trimethylsilylmethyl group; a silicon-substituted aryl group such as a trimethylsilylphenyl group; Of these, a trimethylsilylmethyl group, a phenyldimethylsilylethyl group, and the like are preferable.

  Examples of the phosphide group having 1 to 20 carbon atoms include methyl sulfide groups, ethyl sulfide groups, propyl sulfide groups, butyl sulfide groups, hexyl sulfide groups, cyclohexyl sulfide groups, octyl sulfide groups and the like; vinyl sulfide groups, propenyl sulfides Group, alkenyl sulfide group such as cyclohexenyl sulfide group; arylalkyl sulfide group such as benzyl sulfide group, phenylethyl sulfide group, phenylpropyl sulfide group; phenyl sulfide group, tolyl sulfide group, dimethylphenyl sulfide group, trimethylphenyl sulfide group, Ethyl phenyl sulfide group, propyl phenyl sulfide group, biphenyl sulfide group, naphthyl sulfide group, methyl naphthyl sulfide , Anthracenyl Nils sulfide group, aryl sulfide groups such as phenanthridine Nils sulfide groups.

Examples of the sulfide group having 1 to 20 carbon atoms include alkyl sulfide groups such as methyl sulfide group, ethyl sulfide group, propyl sulfide group, butyl sulfide group, hexyl sulfide group, cyclohexyl sulfide group, octyl sulfide group; vinyl sulfide group, propenyl sulfide Group, alkenyl sulfide group such as cyclohexenyl sulfide group; arylalkyl sulfide group such as benzyl sulfide group, phenylethyl sulfide group, phenylpropyl sulfide group; phenyl sulfide group, tolyl sulfide group, dimethylphenyl sulfide group, trimethylphenyl sulfide group, Ethyl phenyl sulfide group, propyl phenyl sulfide group, biphenyl sulfide group, naphthyl sulfide group, methyl naphthyl sulfide , Anthracenyl Nils sulfide group, an aryl sulfide groups such as phenanthridine Nils sulfide groups.
Examples of the acyl group having 1 to 20 carbon atoms include formyl group, acetyl group, propionyl group, butyryl group, valeryl group, palmitoyl group, thearoyl group, oleoyl group and other alkyl acyl groups, benzoyl group, toluoyl group, salicyloyl group, Examples thereof include arylacyl groups such as cinnamoyl group, naphthoyl group and phthaloyl group, and oxalyl group, malonyl group and succinyl group respectively derived from dicarboxylic acid such as oxalic acid, malonic acid and succinic acid.

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. Examples of the amine include amines having 1 to 20 carbon atoms, specifically, methylamine, ethylamine, propylamine, butylamine, cyclohexylamine, methylethylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, dicyclohexylamine. Alkylamines such as methylethylamine; alkenylamines such as vinylamine, propenylamine, cyclohexenylamine, divinylamine, dipropenylamine, dicyclohexenylamine; arylalkylamines such as phenylamine, phenylethylamine, phenylpropylamine; And arylamines such as naphthylamine.

  Examples of ethers include aliphatic single ether compounds such as methyl ether, ethyl ether, propyl ether, isopropyl ether, butyl ether, isobutyl ether, n-amyl ether, and isoamyl ether; methyl ethyl ether, methyl propyl ether, methyl isopropyl ether, Aliphatic hybrid ether compounds such as methyl-n-amyl ether, methyl isoamyl ether, ethyl propyl ether, ethyl isopropyl ether, ethyl butyl ether, ethyl isobutyl ether, ethyl-n-amyl ether, ethyl isoamyl ether; vinyl ether, allyl ether, methyl Aliphatic unsaturated ether compounds such as vinyl ether, methyl allyl ether, ethyl vinyl ether, ethyl allyl ether; anisole Aromatic ether compounds such as phenetol, phenyl ether, benzyl ether, phenyl benzyl ether, α-naphthyl ether, β-naphthyl ether, and cyclic ether compounds such as ethylene oxide, propylene oxide, trimethylene oxide, tetrahydrofuran, tetrahydropyran, and dioxane. Can be mentioned.

  Examples of phosphines include phosphines having 1 to 20 carbon atoms. Specifically, monohydrocarbon substituted phosphines such as methylphosphine, ethylphosphine, propylphosphine, butylphosphine, hexylphosphine, cyclohexylphosphine, octylphosphine; dimethylphosphine, diethylphosphine, dipropylphosphine, dibutylphosphine, dihexylphosphine, dicyclohexyl Dihydrocarbon-substituted phosphines such as phosphine and dioctylphosphine; alkylphosphines such as trihydrocarbon-substituted phosphines such as trimethylphosphine, triethylphosphine, tripropylphosphine, tributylphosphine, trihexylphosphine, tricyclohexylphosphine, and trioctylphosphine; vinyl Such as phosphine, propenyl phosphine, cyclohexenyl phosphine, etc. Dialkenyl phosphine in which two alkenyls are substituted with alkenyl phosphine or phosphine hydrogen atom; Trialkenyl phosphine in which alkenyl is substituted with three alkenyl hydrogen atoms; Aryl alkyl phosphine such as benzyl phosphine, phenylethyl phosphine, phenylpropyl phosphine; Diarylalkylphosphine or aryldialkylphosphine having three hydrogen atoms substituted with aryl or alkenyl; phenylphosphine, tolylphosphine, dimethylphenylphosphine, trimethylphenylphosphine, ethylphenylphosphine, propylphenylphosphine, biphenylphosphine, naphthylphosphine, methylnaphthyl Phosphine, Anthracenylphosphine, Phenanthonylphosphine; And an aryl phosphines such as tri (alkylaryl) phosphines a hydrogen atom alkylaryl has three substituents phosphine; a hydrogen atom fin alkylaryl two substituted di (alkylaryl) phosphines. Examples of the thioethers include the aforementioned sulfides.

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, a germanium-containing group, a tin-containing group, -O CO -, - S - , - SO 2 -, - Se -, - NR -, - PR -, - P (O) R -, - BR- Or -AlR-, wherein R 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.
Among such crosslinking groups, at least one is preferably a crosslinking group composed of a hydrocarbon group having 1 or more carbon atoms. As such a crosslinking group, for example, the general formula (a)

(D is a group 14 element in the periodic table, for example, carbon, silicon, germanium and tin. R ^{9 and} R ¹⁰ are each a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and they are the same as each other. However, they may be different from each other and may be bonded to each other to form a ring structure.
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 tetramethyldisilylene group, a diphenyldisilylene group, and the like. Among these, an ethylene group, an isopropylidene group, and a dimethylsilylene group are preferable.

  Specific examples of the transition metal compound represented by the general formula [II] include (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) (3-methylcyclopentadienyl) (3'-methyl Cyclopentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-isopropylidene) (3-methylcyclopentadienyl) (3′-methylcyclopentadienyl) zirconium dichloride, (1 , 2′-dimethylsilylene) (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'-isopropyl Pyridene) (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 dichloride , (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-dimethylcyclopentadienyl) (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 -Dimethylcyclopentadienyl) (3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) (3-methyl-5-ethylcyclohexane) Pentadienyl) (3′-methyl-5′-ethylcyclopentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) (3-methyl-5-ethylcyclopenta) Dienyl) (3′-methyl-5′-ethylcyclopentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) (3-methyl-5-isopropylcyclopentadiene) Enyl) (3′-methyl-5′-isopropylcyclopentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) ( , 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-isopropylcyclopentadienyl) (3′-methyl-5′-isopropylcyclopentadienyl) zirconium dichloride, (1 , 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'-ethylcyclo Pentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-ethylene) (3-methyl-5-isopropylcyclopentadienyl) (3′-methyl-5′-isopropylcyclopentadiene) Enyl) 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-phenylcyclopentadiene) ) (3'-methyl-5'-phenylcyclopentadienyl) 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-isopropylcyclopentadienyl) (3′-methyl-5′-isopropylcyclopentadienyl) zirconium dichloride, (1 , 2′-dimethylsilylene) (2,1′-methylene) (3-methyl-5-n-butylcyclopentadienyl) (3′-methyl-5′-n-butylcyclopentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-methylene) (3-methyl-5-phenylcyclopentadienyl) (3′-methyl-5′-phenylcyclopentadienyl) zirconium dichloride, (1 , 2′-ethylene) (2,1′-methylene) (3-methyl-5-isopropylcyclopentadienyl) (3′-methyl-5′-isopropylcyclopentadienyl) ) Zirconium dichloride, (1,2'-ethylene) (2,1'-isopropylidene) (3-methyl-5-isopropylcyclopentadienyl) (3'-methyl-5'-isopropylcyclopentadienyl) Zirconium dichloride, (1,2′-methylene) (2,1′-methylene) (3-methyl-5-isopropylcyclopentadienyl) (3′-methyl-5′-isopropylcyclopentadienyl) zirconium dichloride, (1,2′-methylene) (2,1′-isopropylidene) (3-methyl-5-isopropylcyclopentadienyl) (3′-methyl-5′-isopropylcyclopentadienyl) zirconium dichloride and the like In which zirconium in the compound is substituted with titanium or hafnium, and represented by the general formula (II) described later Mention may be made of the compound. Moreover, the analogous compound of the metal element of another group may be sufficient. A transition metal compound belonging to Group 4 of the periodic table is preferred, and a zirconium compound is particularly preferred.
Among the transition metal compounds represented by the general formula [II], the compounds represented by the general formula [II-a] are preferable.

In the general formula [II-a], M represents a metal element of Groups 3 to 10 of the periodic table, and A ^1a and A ^2a are each represented by the general formula (a) in the general formula (I). Represents a bridging group, preferably CH ₂ , CH ₂ CH ₂ , (CH ₃ ) ₂ C, (CH ₃ ) ₂ C (CH ₃ ) ₂ C, (CH ₃ ) ₂ Si and (C ₆ H ₅ ) ₂ Si . A ^1a and A ^2a may be the same as or different from each other. R ^{14 to} R ²³ 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. Examples of the halogen atom, the hydrocarbon group having 1 to 20 carbon atoms, and the silicon-containing group are the same as those described in the above general formula [II]. Examples of the halogen-containing hydrocarbon group having 1 to 20 carbon atoms include p-fluorophenyl group, 3,5-difluorophenyl group, 3,4,5-trifluorophenyl group, pentafluorophenyl group, 3,5-bis ( (Trifluoro) phenyl group, fluorobutyl group and the like. Examples of the heteroatom-containing group include C1-C20 heteroatom-containing groups. Specifically, nitrogen-containing groups such as dimethylamino group, diethylamino group, and diphenylamino group; phenylsulfide group, methylsulfide group, and the like Sulfur-containing groups of: phosphorus-containing groups such as dimethylphosphino groups and diphenylphosphino groups; oxygen-containing groups such as methoxy groups, ethoxy groups, and phenoxy groups. Among these, as R ¹⁴ and R ¹⁵ , groups containing heteroatoms such as halogen, oxygen, silicon and the like are preferable because of high polymerization activity. R ^{16 to} R ²³ are preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. X and Y are the same as those in the general formula [II]. q represents an integer of 1 to 5 and represents [(M valence) -2], and r represents an integer of 0 to 3.

  Of the transition metal compounds represented by the general formula [II-a], when both indenyl groups are the same, the transition metal compound of Group 4 of the periodic table is (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-ethylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) bis (3-isopropylindenyl) Zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) bis (3-trimethylsilylmethylin) Nyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) bis (3-butylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethyl Silylene) bis (4-methylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) bis (4,7-dimethylindenyl) zirconium dichloride, (1,2'- Dimethylsilylene) (2,1′-dimethylsilylene) bis (5,6-dimethylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (3-ethoxymethylindene Nyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilyl) Emissions) bis (3-ethoxy-ethyl) zirconium dichloride,

(1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (3-methoxymethylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis ( 3-methoxyethylindenyl) zirconium dichloride, (1,2′-phenylmethylsilylene) (2,1′-phenylmethylsilylene) bis (indenyl) zirconium dichloride, (1,2′-phenylmethylsilylene) (2, 1'-phenylmethylsilylene) bis (3-methylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-isopropylidene) bis (indenyl) zirconium dichloride, (1,2'-dimethyl Silylene) (2,1′-isopropylidene) bis (3-methylindenyl) Zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-isopropylidene) bis (3-isopropylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-isopropylidene) Bis (3-n-butylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-isopropylidene) bis (3-trimethylsilylmethylindenyl) zirconium dichloride, (1,2'-dimethyl Silylene) (2,1′-isopropylidene) bis (3-trimethylsilylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-isopropylidene) bis (3-phenylindenyl) zirconium dichloride , (1,2'-dimethylsilylene) (2,1'- Styrene) (indenyl) zirconium dichloride,

(1,2'-dimethylsilylene) (2,1'-methylene) bis (3-methylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-methylene) bis (3-isopropyl Indenyl) zirconium 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′-di) Enylsilylene) (2,1′-methylene) bis (3-methylindenyl) zirconium dichloride, (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 and the like, and those obtained by substituting zirconium in these compounds with titanium or hafnium, are not limited thereto. Further, it may be a compound similar to a metal element other than Group 4. A transition metal compound belonging to Group 4 of the periodic table is preferred, and a zirconium compound is particularly preferred.

On the other hand, among the transition metal compounds represented by the above general formula [II-a], when R ¹⁵ is a hydrogen atom and R ¹⁴ is not a hydrogen atom, the transition metal compound of Group 4 of the periodic table is (1 , 2′-dimethylsilylene) (2,1′-dimethylsilylene) (indenyl) (3-trimethylsilylmethylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) (indenyl) ) (3-methylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) (indenyl) (3-trimethylsilylindenyl) zirconium dichloride (1,2'-dimethylsilylene) (2,1′-dimethylsilylene) (indenyl) (3-phenylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) ) (2,1′-dimethylsilylene) (indenyl) (3-benzylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) (indenyl) (3-neopentyl) Indenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) (indenyl) (3-phenethylindenyl) zirconium dichloride, (1,2′-ethylene) (2,1 ′ -Ethylene) (indenyl) (3-trimethylsilylmethylindenyl) zirconium dichloride, (1,2'-ethylene) (2,1'-ethylene) (indenyl) (3-methylindenyl) zirconium dichloride, (1,2 '-Ethylene) (2,1'-Ethylene) (indenyl) (3-trimethylsilylindenyl) zirconi Umdichloride, (1,2'-ethylene) (2,1'-ethylene) (indenyl) (3-phenylindenyl) zirconium dichloride, (1,2'-ethylene) (2,1'-ethylene) (indenyl ) (3-benzylindenyl) zirconium dichloride, (1,2'-ethylene) (2,1'-ethylene) (indenyl) (3-neopentylindenyl) zirconium dichloride, (1,2'-ethylene) ( Examples include 2,1′-ethylene) (indenyl) (3-phenethylindenyl) zirconium dichloride, and those obtained by substituting zirconium in these compounds with titanium or hafnium, but are not limited thereto. Further, it may be a compound similar to a metal element other than Group 4. A transition metal compound belonging to Group 4 of the periodic table is preferred, and a zirconium compound is particularly preferred.

  As a compound capable of reacting with the transition metal compound (B) constituting the catalyst used in the present invention to form an ionic complex, a high purity terminal unsaturated olefin polymer having a relatively low molecular weight can be obtained, and A borate compound is preferable in terms of high catalyst activity. Examples of borate compounds include triethylammonium tetraphenylborate, tri-n-butylammonium tetraphenylborate, trimethylammonium tetraphenylborate, tetraethylammonium tetraphenylborate, and methyl (tri-n-butyl) ammonium tetraphenylborate. , Benzyl (tri-n-butyl) ammonium tetraphenylborate, dimethyldiphenylammonium tetraphenylborate, triphenyl (methyl) ammonium tetraphenylborate, trimethylanilinium tetraphenylborate, methylpyridinium tetraphenylborate, tetra Benzylpyridinium phenylborate, methyl tetraphenylborate (2-cyanopyridinium), tetrakis (pentafluorophenyl) borate trie Ruammonium, tetrakis (pentafluorophenyl) borate tri-n-butylammonium, tetrakis (pentafluorophenyl) borate triphenylammonium, tetrakis (pentafluorophenyl) borate tetra-n-butylammonium, tetrakis (pentafluorophenyl) ) Tetraethylammonium borate, benzyl (tri-n-butyl) ammonium tetrakis (pentafluorophenyl) borate, methyldiphenylammonium tetrakis (pentafluorophenyl) borate, triphenyl (methyl) ammonium tetrakis (pentafluorophenyl) borate , Tetrakis (pentafluorophenyl) methylanilinium borate, tetrakis (pentafluorophenyl) dimethylanilinium borate, tetra Scan (pentafluorophenyl) borate trimethyl anilinium,

Methyl pyridinium tetrakis (pentafluorophenyl) borate, benzylpyridinium tetrakis (pentafluorophenyl) borate, methyl tetrakis (pentafluorophenyl) borate (2-cyanopyridinium), benzyl tetrakis (pentafluorophenyl) borate (2- Cyanopyridinium), methyl tetrakis (pentafluorophenyl) borate (4-cyanopyridinium), triphenylphosphonium tetrakis (pentafluorophenyl) borate, tetrakis [bis (3,5-ditrifluoromethyl) phenyl] dimethylaniline borate Nitrogen, ferrocenium tetraphenylborate, silver tetraphenylborate, trityl tetraphenylborate, tetraphenylporphyrin manganese tetraphenylborate, tetrakis Ntafluorophenyl) triphenylcarbenium borate, methylanilinium tetrakis (perfluorophenyl) borate, ferrocenium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) boric acid (1,1′-dimethylferrocete) Nium), tetrakis (pentafluorophenyl) borate decamethylferrocenium, tetrakis (pentafluorophenyl) silver borate, tetrakis (pentafluorophenyl) trityl borate, tetrakis (pentafluorophenyl) lithium borate, tetrakis (penta Fluorophenyl) sodium borate, tetrakis (pentafluorophenyl) borate tetraphenylporphyrin manganese, silver tetrafluoroborate and the like. These can be used individually by 1 type or in combination of 2 or more types. When the molar ratio of hydrogen and transition metal compound (hydrogen / transition metal compound) described later is 0, dimethylanilinium tetrakis (pentafluorophenyl) borate, triphenylcarbenium tetrakis (pentafluorophenyl) borate, and tetrakis (Perfluorophenyl) methylanilinium borate and the like are preferable.

The catalyst used in the production method of the present invention may use an organoaluminum compound as the component (C) in addition to the components (A) and (B).
As the organoaluminum compound of component (C), trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trinormal hexylaluminum, trinormaloctylaluminum, dimethylaluminum chloride, diethylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride. Dimethylaluminum fluoride, diisobutylaluminum hydride, diethylaluminum hydride and ethylaluminum sesquichloride. These organoaluminum compounds may be used alone or in combination of two or more.
Among these, in the present invention, trialkylaluminum such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trinormalhexylaluminum and trinormaloctylaluminum is preferable, and triisobutylaluminum, trinormalhexylaluminum and trimethylaluminum Normal octyl aluminum is more preferred.

The amount of component (A) used is usually 0.1 × 10 ^{−6 to} 1.5 × 10 ⁻⁵ mol / L, preferably 0.15 × 10 ^{−6 to} 1.3 × 10 ⁻⁵ mol / L, More preferably, it is 0.2 × 10 ^{−6 to} 1.2 × 10 ⁻⁵ mol / L, and particularly preferably 0.3 × 10 ^{−6 to} 1.0 × 10 ⁻⁵ mol / L. When the amount of component (A) used is 0.1 × 10 ⁻⁶ mol / L or more, the catalytic activity is sufficiently expressed, and when it is 1.5 × 10 ⁻⁵ mol / L or less, the heat of polymerization is easy. Can be removed.
The use ratio (A) / (B) of the component (A) and the component (B) is preferably 10/1 to 1/100, more preferably 2/1 to 1/10 in terms of molar ratio. When (A) / (B) is in the range of 10/1 to 1/100, an effect as a catalyst can be obtained and the catalyst cost per unit mass polymer can be suppressed. Moreover, there is no fear that a large amount of boron exists in the target terminal unsaturated olefin polymer.
The use ratio (A) / (C) of the component (A) and the component (C) is preferably 1/1 to 1/10000, more preferably 1/5 to 1/2000, and further preferably 1 in terms of molar ratio. / 10 to 1/1000. By using the component (C), the polymerization activity per transition metal can be improved. When (A) / (C) is in the range of 1/1 to 1/10000, the balance between the effect of addition of component (C) and economy is good, and the intended terminal unsaturated olefin polymer There is no fear that a large amount of aluminum is present inside.
In the production method of the present invention, the preliminary contact may be performed using the above-described component (A) and component (B), or component (A), component (B) and component (C). The preliminary contact can be performed by bringing the component (A) into contact with, for example, the component (B). However, the method is not particularly limited, and a known method can be used. Such preliminary contact is effective in reducing the catalyst cost, such as improving the catalytic activity and reducing the proportion of the (B) component used as the cocatalyst.

The poly α-olefin according to the present invention can be obtained by performing a polymerization reaction in the presence of the catalyst. The molar ratio of hydrogen to transition metal compound (hydrogen / transition metal compound) is preferably in the range of 0 to 5000. In order to enhance terminal vinylidene selectivity and catalytic activity, the polymerization reaction is preferably performed in the presence of a trace amount of hydrogen.
Usually, hydrogen functions as a chain transfer agent, and it is known that polymer chain ends have a saturated structure. It also has a function of reactivating the dormant to increase the catalytic activity. Although the influence of a trace amount of hydrogen on the catalyst performance is unclear, it has been found that by using hydrogen within a specific range, terminal vinylidene selectivity is high and high activity is achieved. When hydrogen / transition metal is 0, as described above, (B) compounds capable of reacting with the transition metal compound to form an ionic complex include tetrakis (perfluorophenyl) methylanilinium borate, tetrakis. (Pentafluorophenyl) dimethylanilinium borate and tetrakis (pentafluorophenyl) borate triphenylcarbenium are preferred.
The molar ratio of hydrogen to transition metal compound (hydrogen / transition metal compound) is preferably 200 to 4500, more preferably 300 to 4000, and most preferably 400 to 3000. When this molar ratio is 5,000 or less, the production of polyolefin-based polymerizability having extremely low terminal unsaturation is suppressed, and the target terminal-modified poly α-olefin can be obtained.
Although there is no restriction | limiting in particular about the polymerization method at the time of manufacturing a modified poly alpha olefin, Solution polymerization and bulk polymerization are preferable. In addition, either a batch method or a continuous polymerization method can be applied. Solvents used for solution polymerization include saturated hydrocarbon solvents such as hexane, heptane, butane, octane and isobutane, alicyclic hydrocarbon solvents such as cyclohexane and methylcyclohexane, and aromatic hydrocarbons such as benzene, toluene and xylene. And system solvents.

The intrinsic viscosity [η], molecular weight distribution (Mw / Mn), mesopentad fraction [mmmm] and melting point (Tm) in the poly α-olefin according to the present invention can be controlled by the following methods.
The intrinsic viscosity [η] can be controlled by changing general polymerization conditions. In order to increase the intrinsic viscosity, it is made by any one or more of the following factors: decrease in polymerization temperature, increase in olefin monomer concentration due to increase in polymerization pressure, decrease in transition metal catalyst amount, etc. The respective control factors are set in reverse to the above.
The molecular weight distribution (Mw / Mn) is usually almost determined by the catalyst used, and Mw / Mn is in the range of about 1.5 to 2.5. In order to control the molecular weight distribution, polymerization may be performed in multiple stages, and the molecular weight generated in each stage may be changed.
The mesopentad fraction [mmmm] can be controlled by selecting a catalyst and selecting polymerization conditions. A polymer having a low mesopentad fraction can be produced using a highly symmetrical catalyst having a ligand having the same substituent species and substitution position, as in the catalyst described in Example 1 described later. When the substituent species and the substitution position are different, or when only one ligand has a substituent, a polymer with higher stereoregularity can be produced. Furthermore, when the ligand does not have a substituent other than a crosslinking group, a polymer having the highest stereoregularity can be produced.
Moreover, polymerization temperature and olefin monomer concentration are mentioned as factors of polymerization conditions. The mesopentad fraction can be increased by decreasing the polymerization temperature and increasing the olefin monomer concentration by increasing the polymerization pressure.
The melting point (Tm) is the mesopentad fraction [mmmm]
1.76 [mmmm] -25.0 ≦ Tm ≦ 1.76 [mmmm] +5.0
The mesopentad fraction is the governing factor of the melting point. Therefore, the melting point can be controlled by generally controlling the mesopentad fraction. In addition, when a catalyst having a different substituent type and substitution position or only one of the ligands has a substituent, a heterogeneous bond such as 2,1-insertion or 1,3-insertion must be generated. Furthermore, since the stereoregularity can be changed by multistage polymerization and the stereoregularity distribution can be expanded, the melting point can be controlled with the same stereoregularity by these control factors.

The following (I) or (II) is mentioned as a residue produced | generated by reaction with the said poly (alpha) -olefin and the silicon compound which has Si-H group.
(I) Silicon compound residue represented by general formula [I]

In the general formula [I], R ¹ represents a monovalent hydrocarbon group having 1 to 12 carbon atoms, and examples thereof include a methyl group, an ethyl group, and an isopropyl group. When R ¹ is a plurality, the plurality of R ¹ may be the same or different. L represents a hydrolyzable group selected from a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amide group, an acid amide group, and an aminooxy group. Examples of the halogen atom include a chlorine atom, a fluorine atom, a bromine atom and an iodine atom. Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, and an isopropoxy group. Examples of the acyloxy group include an acetoxy group and a benzoyloxy group. When there are a plurality of L, the plurality of L may be the same or different. a is 0, 1 or 2, and 0 or 1 is preferred. -Si is a bonding site with the poly α-olefin.
The silicon compound residue represented by the general formula [I] is a residue of the silicon compound (III) represented by the general formula [III].

(In the formula, R ¹ , L and a are the same as above.)
Examples of the silicon compound represented by the general formula [III] include halogenated silanes (trichlorosilane, methyldichlorosilane, dimethylchlorosilane, etc.), alkoxysilanes (trimethoxysilane, triethoxysilane, triisopropoxysilane, trinormal) Hexylsilane, tri-normal octylsilane, methyldimethoxysilane, ethyldiethoxysilane, phenyldimethoxysilane, phenyldiethoxysilane and bis (methylethylketoxymate) methylsilane), acyloxysilanes (triacetoxysilane and methyldiacetoxysilane) , Ketoximate silanes (tris (acetoxymate) silane, bis (dimethyl ketoximate), methyl silane and bis (cyclohexyl ketoximate) methyl silane Etc.), and the like. Of these, alkoxysilanes are particularly preferable.

(II) Polysiloxane residue satisfying the following (a) to (c)
(a) It has the structure of the siloxane terminal (A unit) represented by general formula (A), the siloxane main chain (B unit) represented by general formula (B), or both.
(b) The polysiloxane molecular main chain has a siloxane repeating unit (C unit) represented by the general formula (C).

(In the formula, R ^{2 to} R ⁶ each independently represent an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms. * -Si represents a bonding site with a poly α-olefin.)
(c) The number of A units is 0 to 2 / molecule, the number of B units is 0 to 10 / molecule, and A unit and B unit are not 0 at the same time. The total of A unit, B unit and C unit is 5 to 1500 per molecule, preferably 5 to 200, more preferably 10 to 150, and the polysiloxane terminal other than the bonding site with poly α-olefin is R ⁷ or OR ⁸ (R ⁷ and R ⁸ each independently represents an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms).
Examples of the unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms represented by R ^{2 to} R ⁸ include a methyl group, an ethyl group, an isopropyl group, and a phenyl group. Examples of the substituted monovalent hydrocarbon group having 1 to 12 carbon atoms include those in which these groups are substituted with a hydrogen atom, an alkoxy group, an amino group, or the like.
Here, the A unit is a group corresponding to the terminal of the reacted siloxane molecule, and the unit B is a group present in the main chain of the reacted siloxane molecule. The number of the A unit, the B unit, and the C unit is an integer. However, when the polysiloxane residue that satisfies the above (a) to (c) has a molecular weight distribution, the numbers of the A unit, the B unit, and the C unit are expressed as average values, and thus are positive numbers. The same applies to the following D unit and E unit.

The polysiloxane residue (II) is a residue derived from polysiloxane (IV) that satisfies the following (d) to (f).
As this polysiloxane (IV), one terminal hydridopolydimethylsiloxane, molecular chain both ends trimethylsiloxy group-blocked methylhydrogenpolysiloxane, molecular chain both ends trimethylsiloxy group-blocked dimethylsiloxane / methylhydrogensiloxane copolymer, molecule Silanol group-blocked methylhydrogenpolysiloxane with both ends of chain chain, Silanol group-blocked dimethylsiloxane / methylhydrogensiloxane copolymer with chain ends, dimethylhydrogensiloxy group-blocked dimethylpolysiloxane with molecular chain ends, and dimethylhydrosiloxane with molecular chain ends Examples include gensiloxy group-blocked methylhydrogenpolysiloxane and dimethylhydrogensiloxy group-blocked dimethylsiloxane / methylhydrogensiloxane copolymer. It is.
The polysiloxane residue is appropriately selected according to the purpose of use of the terminal-modified poly α-olefin. When the terminal-modified poly-α-olefin is used for the purpose of imparting lubricity and abrasion resistance to the resin, a single-terminal hydridopolydimethylsiloxane residue is preferable, and in addition, melting characteristics, flexibility and impact resistance are further improved. In the case of imparting mechanical properties such as gas permeability to the resin, a polysiloxane residue having 2 to 10 hydride bond residues is preferable. Moreover, when using terminal modified poly (alpha) -olefin for the process of an inorganic filler, the polysiloxane residue containing an alkoxy group is preferable.

The method for producing a terminal-modified poly α-olefin of the present invention comprises a poly α-olefin that satisfies the following (4) to (7) in the presence of a catalyst containing a transition metal compound, and the following (III) and (IV): One or more silicon compounds selected from the group consisting of hydrosilylation reaction.
(4) It is obtained by polymerization of one or more α-olefins having 3 to 28 carbon atoms, or copolymerization of ethylene with one or more selected from α-olefins having 3 to 28 carbon atoms.
(5) Mesopentad fraction [mmmm] is in the range of 30 to 80 mol%.
(6) It has 0.5 to 1.0 vinylidene group as a terminal unsaturated group per molecule.
(7) The intrinsic viscosity [η] measured at 135 ° C. in decalin is in the range of 0.01 to 2.5 dl / g.
(III) A silicon compound represented by the general formula [III].

(Wherein R ¹ is a monovalent hydrocarbon group having 1 to 12 carbon atoms, and L is selected from a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amide group, an acid amide group, and an aminooxy group. A hydrolyzable group, a being 0, 1 or 2)
(IV) Polysiloxane satisfying the following (d) to (f)
(d) It has the structure of the siloxane terminal (D unit) represented by general formula (D), the siloxane main chain (E unit) represented by general formula (E), or both.
(e) The polysiloxane molecular main chain has a siloxane repeating unit (C unit) represented by the general formula (C).

(In the formula, R ^{2 to} R ⁶ each independently represents an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms.)
(f) The number of D units is 0 to 2 / molecule, the number of E units is 0 to 10 / molecule, and the D unit and the E unit are not 0 at the same time. The total of D unit, E unit and C unit is 5 to 1500 per molecule, preferably 5 to 200, more preferably 10 to 150, and the polysiloxane terminal is R ⁷ or OR ⁸ (R ⁷ and R ^{7 8} each independently represents an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms.

The above (4), (5) and (7) are the same as (1), (2) and (3) described in the above-mentioned terminal-modified poly α-olefin.
In said (6), the number of terminal vinylidene groups is calculated | required by the measurement of < ¹ > H-NMR according to a conventional method. Based on the vinylidene group appearing in δ 4.8 to 4.6 (2H) obtained from ¹ H-NMR measurement, the content (C) (mol%) of the vinylidene group is calculated by a conventional method. Further, from the number average molecular weight (Mn) and monomer molecular weight (M) determined by gel permeation chromatography (GPC), the number of vinylidene groups per molecule is calculated according to the following formula.
Terminal vinylidene groups per molecule (pieces) = (Mn / M) × (C / 100)
The number average molecular weight (Mn) was determined by the Universal Calibration method using the constants K and α of the Mark-Houwink-Sakurada formula in order to convert the polystyrene-equivalent molecular weight into the molecular weight of the corresponding polymer. Specifically, it was determined by the method described in “Size Exclusion Chromatography” by Sadao Mori, P67-69, 1992, Kyoritsu Shuppan. K and α are “" Polymer Handbook "John Wiley & Sons, Inc. "It is described in. Moreover, it can determine by a usual method from the relationship of the intrinsic viscosity with respect to the newly calculated absolute molecular weight.
In the poly α-olefin used in the present invention, the number of vinylidene groups per molecule is preferably 0.6 to 1.0, more preferably 0.7 to 1.0, and most preferably 0.8 to 1.0. 1.0. When the number of terminal vinylidene groups per molecule is 0.5 or more, modification of the terminal of the poly α-olefin can be easily performed.

The production method of the polyα-olefin used in the production method of the terminal-modified polyα-olefin of the present invention is as described in the terminal-modified polyα-olefin.
The poly α-olefin used in the method for producing a terminal-modified poly α-olefin of the present invention is a propylene homopolymer, or at least one mass selected from propylene homopolymer or 90% by mass of propylene, ethylene and an α-olefin having 4 to 28 carbon atoms. % (%) Or less copolymer (propylene polymer), in addition to the above (4) to (7), it is preferable to satisfy (8) described in the terminal-modified poly α-olefin. It is more preferable that (9) to (12) are satisfied. In addition, the poly α-olefin used in the production method of the present invention is 1-butene homopolymer, or 1-butene 90% by mass or more, and one or more selected from ethylene, propylene, and an α-olefin having 5 to 28 carbon atoms. In the case of a copolymer with 1% by mass (1-butene polymer), in addition to the above (4) to (7), (13) and (14) described in the terminal-modified poly α-olefin are satisfied. It is preferable.

The silicon compound (III) and polysiloxane (IV) used in the method for producing a terminal-modified polyα-olefin of the present invention are as exemplified in the above-mentioned silicon compound residue. Silicon compound (III) and polysiloxane (IV) can be used singly or in combination of two or more.
The amount of the silicon compound and polysiloxane used is such that the number of terminal unsaturated groups of the poly α-olefin is usually 0.01 to 1 per Si—H bond of the silicon compound (III) and / or polysiloxane (IV). The amount is about 5, preferably 0.05 to 3.

In the hydrosilylation reaction, a transition metal complex catalyst is used. The catalyst is preferably a transition metal complex of Groups 8 to 10 of the periodic table, and examples thereof include a platinum complex, a rhodium complex, a cobalt complex, a palladium complex, and a nickel complex. In the present invention, platinum complexes such as chloroplatinic acid and platinum olefin complexes are preferred.
The usage-amount of a catalyst is about 0.1-1000 mass ppm normally as a metal unit with respect to poly alpha olefin, Preferably it is 1-500 mass ppm, Most preferably, it is 20-200 mass ppm.
The hydrosilylation reaction may be performed in a molten state or in a solution state (hereinafter may be referred to as “melting reaction” and “solution reaction”, respectively). In the case of a melt reaction, the reaction temperature needs to be equal to or higher than the melting temperature of the poly α-olefin, and is usually about 50 to 150 ° C, preferably 60 to 140 ° C. In the case of a solution reaction, the reaction temperature is usually about −30 to 150 ° C., preferably 30 to 140 ° C. The reaction time is about 1 minute to 20 hours. The hydrosilylation reaction is usually performed at normal pressure, but may be performed under pressure.

A typical processing apparatus (for example, an extruder, a batch mixer, a hot press, etc.) can be used for the said melting reaction. The reaction may be carried out batchwise or continuously. This melting reaction is carried out in the poly α-olefin melt phase. In this case, the poly α-olefin, the silicon compound, and the transition metal complex as a catalyst may be mixed before the reaction or may be sequentially added to the reactor.
In the solution reaction, the reaction apparatus is not particularly limited. For example, a tank type reaction group having a batch type or continuous type stirring apparatus can be used. Examples of the reaction solvent used in the solution reaction include hydrocarbon solvents, ethers, and the like. Examples of the hydrocarbon solvent include saturated aliphatic hydrocarbons such as hexane, heptane, octane and decane, saturated alicyclic hydrocarbons such as cyclohexane and methylcyclohexane, and aromatic hydrocarbons such as benzene, toluene and xylene. It is done. The solvent is preferably a hydrocarbon solvent, more preferably a saturated aliphatic hydrocarbon and a saturated alicyclic hydrocarbon.
The amount of the solvent used is not particularly limited as long as it is a state in which the poly α-olefin and the silicon compound are dissolved, but usually the total concentration of the poly α-olefin and the silicon compound is 5 to 50 mass. %, Preferably 10 to 40% by mass.

The present invention also provides a composition containing the terminal-modified poly α-olefin and one or more selected from other resins and inorganic fillers.
Examples of the other resins include polyolefin, polysiloxane, petroleum resin, polystyrene, and condensation polymers (polyamide, polyester, etc.). Examples of polyolefins include polyethylene (high density polyethylene (HDPE) and high pressure method low density polyethylene (LDPE), etc.), ethylene / α-olefin copolymers (ethylene / propylene copolymers and ethylene / propylene / diene copolymers, etc.). Polyolefin rubber, ethylene / butene copolymer, linear low density polyethylene (L-LDPE) such as ethylene / hexene copolymer and ethylene / octene copolymer), ethylene / polar monomer copolymer (ethylene / Vinyl acetate copolymer and saponified product thereof, ethylene / acrylic acid copolymer, ethylene / methyl methacrylate copolymer and ethylene / glycidyl methacrylate copolymer), polypropylene (isotactic polypropylene, syndiotactic polypropylene, Tactic polypropylene and low-medium isotactic polypropylene having a stereoregularity [mmmm] of 30 to 85 mol%, etc.), propylene copolymer (copolymerized polypropylene using ethylene, butene, hexene, octene, etc. as copolymerization components) , Polybutenes (such as isotactic polybutene and low-medium isotactic polybutene having a stereoregularity [mmmm] of 30 to 90%) and higher poly α-olefins derived from α-olefins having 16 to 28 carbon atoms. It is done. These can be used individually by 1 type or in combination of 2 or more types. In the present invention, polypropylene and polybutene are preferred.

As inorganic fillers, silica, alumina, glass, quartz, kaolin, mica, talc, clay, hydrated alumina, wollastonite, iron powder, potassium titanate, titanium oxide, zinc oxide, silicon carbide, silicon nitride, calcium carbonate , Carbon black, barium sulfate, and boron compounds. In the present invention, silica, alumina, glass, quartz, kaolin, mica, talc and clay are preferred.
The composition of the present invention may contain various resin additives such as antioxidants, ultraviolet absorbers and antifogging agents, catalysts such as silanol condensation reaction catalysts, process oils and the like.

The composition of the present invention includes (1) a combination of a resin and a terminal-modified poly α-olefin, (2) a combination of an inorganic filler and a terminal-modified poly α-olefin, and (3) a resin, an inorganic filler, and a terminal-modified poly. There are combinations with α-olefins. In the case of the above (1), the amount of the terminal-modified poly-α-olefin is usually about 0.1 to 50 parts by mass, preferably 0.5 to 40 parts by mass with respect to 100 parts by mass of the resin. If the amount of the terminal-modified poly α-olefin is 0.1 parts by mass or more, a modification effect is obtained, and if it is 50 parts by mass or less, deterioration of physical properties of the resin component is suppressed.
In the case of the above (2), the amount of the terminal-modified poly α-olefin is usually about 0.01 to 5000 parts by mass, preferably 0.1 to 1000 parts by mass with respect to 100 parts by mass of the inorganic filler. If the amount of the terminal-modified poly α-olefin is 0.01 or more, a modification effect can be obtained, and if it is 5000 parts by mass or less, the terminal-modified poly α-olefin not involved in the surface treatment may be excessive. Therefore, the physical properties are good. When terminal-modified poly α-olefin is used for the inorganic filler surface treatment, the amount of terminal-modified poly α-olefin is preferably 0.05 to 10 parts by mass with respect to 100 parts by mass of the inorganic filler. Moreover, in the case of a masterbatch, it is preferable that the compounding quantity of terminal modified poly alpha-olefin shall be 5-400 mass parts with respect to 100 mass parts of inorganic fillers.
In the case of (3) above, a mixture of terminal-modified poly α-olefin and an inorganic filler (mixture of inorganic filler 100 parts by mass and terminal-modified poly α-olefin 0.01 to 5000 parts by mass) with respect to 100 parts by mass of the resin. It is good to mix 0.5-100 mass parts. When the blending amount is 0.5 parts by mass or more, the effects of the terminal-modified poly α-olefin and the inorganic filler are sufficiently exhibited, and when the blending amount is 100 parts by mass or less, there is no fear that the mechanical properties are lowered.

As the inorganic filler, a surface-treated one can also be used. The surface treatment includes a wet method and a dry method. The wet method is a method in which surface treatment is performed by slurrying with a dilute solution of terminally modified poly-α-olefin or by direct immersion. The wet method is a method that can uniformly treat the surface of the inorganic filler, and can perform treatment with high accuracy.
The dry method is a method in which the terminal-modified poly α-olefin itself or a solution thereof is uniformly dispersed in an inorganic filler that is stirred at high speed with a stirrer. The dry method is an industrially effective method because a large amount of filler can be processed in a short time, although there is a problem that uniform processing is difficult.

  Examples of the industrially useful method having excellent workability for adding the terminal-modified poly α-olefin of the present invention to an organic material such as a polymer include an integral blend method and a master batch method. The integral blend method is a method in which terminal-modified poly α-olefin is added when an inorganic filler and a polymer are mixed. The masterbatch method is a method for producing a composite material by mixing a small amount of organic material with a terminal-modified poly α-olefin to form a masterbatch.

The terminal poly α-olefin of the present invention has the following effects (I) to (III) depending on the type of terminal.
(I) A composition of a poly α-olefin having a polydimethylsiloxane chain added to the terminal and a polyolefin or a composition of polyolefin / polydimethylsiloxane is excellent in bleed resistance, mold releasability and melt flow during molding. The molded product has good surface lubricity, impact resistance, flexibility and stress relaxation, and has improved flammability, resulting in good flame retardancy and non-drip properties, and good gas permeability. is there.
(II) Since the inorganic filler treated with the poly α-olefin having an alkoxy group at the terminal is excellent in dispersibility and interfacial adhesion, the mechanical strength can be improved by adding this inorganic filler to the resin. Further, bending strength, compressive strength, tensile strength and tear strength are improved, and the surface appearance of the molded body is also improved.
(III) A modified poly α-olefin having an alkoxy group and a crosslinked product formed by the reaction of the modified poly α-olefin with a polyfunctional siloxane having a plurality of alkoxy groups and silanol groups are used as an adhesive, a sealant, and a potting agent. It is suitable as a component.

  When the above (I) to (III) are accompanied by a silanol condensation reaction, a silanol condensation reaction catalyst can be used. Specific examples of the silanol condensation catalyst include titanic acid esters (tetrabutyl titanate, tetrapropyl titanate, etc.), tin carboxylates (dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, tin octylate and tin naphthenate). Etc.), organoaluminum compounds (such as aluminum trisacetylacetonate, aluminum trisethylacetoacetate and diisopropoxyaluminum ethylacetoacetate), chelate compounds (such as zirconium tetraacetylacetonate and titanium tetraacetylacetonate), amines Compound (Butylamine, Octylamine, Laurylamine, Dibutylamine, Monoethanolamine, Diethanolamine, Triethanolamine, Diethylenetriamine, Liethylenetetramine, oleylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2,4,6-tris (dimethylaminomethyl) phenol, morpholine, N-methylmorpholine, 2- Ethyl-4-methylimidazole and 1,8-diazabicyclo [5.4.0] undecene-7 (DBU), etc.), salts of these amine compounds with carboxylic acids, etc., excess polyamines and polybasic acids. Low molecular weight polyamide resin (reaction product of excess polyamine and epoxy compound, etc.) obtained and silane coupling agent having amino group (γ-aminopropyltrimethoxysilane and N- (β-aminoethyl) aminopropylmethyldi Metoki Silane) and the like. These silanol condensation catalysts may be used individually by 1 type, and may use 2 or more types together.

  The amount of the silanol condensation catalyst used is usually about 0.1 to 20 parts by mass, preferably 0.3 to 10 parts by mass with respect to 100 parts by mass of the terminal-modified poly α-olefin. When the amount of the silanol condensation catalyst used is 0.1 parts by mass or more, the silanol condensation reaction is promoted. On the other hand, when the amount is 10 parts by mass or less, the local progress of the silanol condensation reaction is suppressed. Foaming is suppressed. For this reason, the uniformity of the reaction is maintained. In addition, even when curing is involved, the pot life is not too short and is moderate, so workability is ensured.

EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
Production Example 1 (Production of propylene homopolymer)
(1) Synthesis of complex:
(a) Synthesis of (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) -bis (indene) Under a nitrogen stream, 50 ml of THF (tetrahydrofuran) and 2.5 g (41 mmol) of Mg were placed in a 1 L three-necked flask. ) Was added. To this, 0.1 ml of 1,2-dibromoethane was added and stirred to activate Mg. After stirring for 30 minutes, the solvent was extracted and 50 ml of THF was newly added. A solution of 2-bromoindene (5.0 g, 25.6 mmol) in THF (200 ml) was added dropwise thereto over 2 hours. After completion of the dropwise addition, the mixture was stirred at room temperature for 2 hours, cooled to −78 ° C., and a solution of 3.1 ml (25.6 mmol) of dichlorodimethylsilane in THF (100 ml) was added dropwise over 1 hour. After stirring for 15 hours, the solvent was distilled off. The residue was extracted with 200 ml of hexane, and then the solvent was distilled off to obtain 6.6 g (24.2 mmol) of 2-chloromethylsilylindene (yield 94%). Under a nitrogen stream, 400 ml of THF and 8 g of 2-chloromethylsilylindene were added to a 1 L three-necked flask and cooled to -78 ° C. 38.5 ml (38.5 mmol) of a THF solution (1.0 mol / L) of LiN (trimethylsilyl) ₂ was added dropwise thereto. After stirring at room temperature for 15 hours, the solvent was distilled off and extracted with 300 ml of hexane. The solvent was distilled off to obtain 2.2 g (6.4 mmol) of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (indene) (yield 33.4%).
The results of measurement by ¹ H-NMR (90 MHz, THF-d ₈ ) are as follows.
δ: -0.69,0.73 (12H, _{dimethylsilylene), 3.66 (4H, -CH 2} -), 7.17 (8H, Ar-H)

(b) Synthesis of (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride (1,2'-dimethylsilylene) (2, Lithium salt of 1′-dimethylsilylene) -bis (indene) (3.0 g, 6.97 mmol) was dissolved in 50 ml of THF 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 was dried to remove the solvent, and 3.04 g (5.88 mmol) of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylmethylindene) was obtained. Obtained (yield 84%).
Next, 3.04 g (5.88 mmol) of (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) -bis (3-trimethylsilylmethylindene) obtained above in a Schlenk bottle under a nitrogen stream. And 50 ml of ether. The solution was cooled to −78 ° C., and a hexane solution of n-BuLi (1.54 mol / L, 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 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 preliminarily cooled to -78 ° C 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 obtained residue was recrystallized from dichloromethane to obtain 0.9 g of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride (1. 33 mmol) 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)

(2) Polymerization of propylene:
To a heat-dried stainless steel autoclave with an internal volume of 1.4 L, 0.4 L of dry heptane and 10 ml of a toluene solution of 20 mmol of methylaluminoxane were added and stirred for 10 minutes while controlling at 50 ° C. Furthermore, 20 micromol of heptane slurry of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride of the transition metal compound complex prepared in (1) above. 5 ml was charged.
Next, the temperature was raised to 90 ° C. while stirring, and propylene gas was introduced to a total pressure of 0.1 MPa. During the polymerization reaction, propylene gas was supplied by a pressure regulator so that the pressure became constant, and polymerization was performed for 120 minutes, followed by cooling, unreacted propylene was removed by depressurization, and the contents were taken out. The contents were put into a large amount of methanol containing 5% by volume of 12 mol / L hydrochloric acid and deashed and washed. Polypropylene was recovered by a decantation method, and further washed with methanol three times to recover polypropylene. After air drying, 75.3 g of polypropylene was obtained by further drying under reduced pressure at 80 ° C. for 8 hours.
About the obtained polypropylene, the physical property was measured by the following method.

(1) Intrinsic viscosity [η]
The intrinsic viscosity [η] was calculated by measuring the reduced viscosity (η _SP / c) with a Ubbelohde viscometer in decalin at 135 ° C. and using the following general formula (Haggins formula).
η _SP / c = [η] + K [η] ² c
η _SP / c (dl / g): Reduced viscosity [η] (dl / g): Intrinsic viscosity c (g / dl): Polymer concentration K = 0.35 (Haggins constant)
(2) Measurement of molecular weight The weight average molecular weight (Mw) and the number average molecular weight (Mn) were measured by the following gel permeation chromatography (GPC) apparatus, and the molecular weight distribution (Mw / Mn) was determined. The weight average molecular weight (Mw) and number average molecular weight (Mn) were determined by the Universal Calibration method using the constants K and α of the Mark-Houwink-Sakurada formula in order to convert the polystyrene equivalent molecular weight into the molecular weight of the corresponding polymer. . Specifically, it was determined by the method described in “Size Exclusion Chromatography” by Sadao Mori, P67-69, 1992, Kyoritsu Shuppan. K and α are “" Polymer Handbook "John Wiley & Sons, Inc. "It is described in.
GPC measuring device Detector: RI detector for liquid chromatography Waters 150C
Column: TOSO GMHHR-H (S) HT
Measurement conditions Solvent: 1,2,4-trichlorobenzene Measurement temperature: 145 ° C
Flow rate: 1.0 ml / min Sample concentration: 0.3% by mass
(3) Terminal vinylidene group content per molecule Calculated by the method described above.
(4) Stereoregularity Measured by the method described above.
(5) Melting point (Tm)
It calculated | required by the DSC measurement mentioned above.

The intrinsic viscosity [η] was 0.11 dl / g, the weight average molecular weight (Mw) was 9720, and the molecular weight distribution (Mw / Mn) was 1.89. Further, from ¹ H-NMR, the terminal was only a vinylidene unsaturated structure, and the number of terminal vinylidene groups determined from these was 0.99 / molecule.
The stereoregularity and melting point were as follows.
[Mmmm] = 32.5 mol%
[Rmrm] = 3.2 mol%
[Rrrr] / {1- [mmmm]} = 0.035
[Mm] [rr] / [mr] [mr] = 1.10
Melting point (Tm) = 52 ° C.

Production Example 2 (Production of propylene homopolymer)
In a heat-dried stainless steel autoclave with an internal volume of 1.4 L, 0.4 L of dry heptane, 1 ml of heptane solution of 0.5 mmol of triisobutylaluminum, and 1.5 μmol of heptane slurry of methylanilinium tetrakis (perfluorophenyl) borate 2 ml was added and stirred for 10 minutes while controlling at 50 ° C. Furthermore, 0.5 micron of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride of the transition metal compound complex prepared in Production Example 1 (1). 2 ml of molar heptane slurry was charged.
Next, the temperature was raised to 70 ° C. while stirring, and propylene gas was introduced up to 0.8 MPa in total pressure.
During the polymerization reaction, propylene gas was supplied by a pressure regulator so as to keep the pressure constant, and polymerization was performed for 120 minutes. Thereafter, cooling was performed, unreacted propylene was removed by depressurization, and the contents were taken out. The contents were air-dried and further dried under reduced pressure at 80 ° C. for 8 hours to obtain 123 g of polypropylene.
About the obtained polypropylene, the physical property was measured by said method. The evaluation results are as follows.

[Mmmm] = 43.6 mol%
[Rmrm] = 3.0 mol%
[Rrrr] / {1- [mmmm]} = 0.037
[Mm] [rr] / [mr] [mr] = 1.37
Melting point (Tm) = 71 ° C.
Weight molecular weight (Mw) = 116000
Intrinsic viscosity [η] = 0.85 dl / g
Molecular weight distribution (Mw / Mn) = 2.08
Terminal vinylidene group = 1.0 / molecule

Example 1
In a 200 ml eggplant-shaped flask equipped with a stirrer, 20 g of the polypropylene obtained in Production Example 1 and 100 ml of cyclohexane as a solvent were added and dissolved while stirring. 11.1 g of methyl hydridosiloxane-dimethylsiloxane copolymer (manufactured by Gelest Inc., HMS-071) was added thereto, and the mixture was stirred uniformly, and then a xylene solution of divinyltetramethyldisiloxane / platinum complex (2. 0.05 ml) (containing 1 to 2.4% by mass of platinum) was added and reacted at 40 ° C. for 5 hours. After completion of the reaction, the solvent was removed by distillation under reduced pressure, acetone washing was sufficiently performed, and the solid component was dried to obtain 27.6 g of modified polypropylene.
As a result of GPC measurement, the weight average molecular weight (Mw) was 49980, and the molecular weight distribution (Mw / Mn) was 4.6. In order to evaluate the terminal vinylidene of the modified polypropylene, an infrared absorption spectrum was measured. As a result, there was no absorption at 888 cm ⁻¹ and the terminal vinylidene disappeared. Along with the increase in the molecular weight, it became clear that the siloxane chain was bonded to the terminal vinylidene terminal of polypropylene by a hydrosilation reaction.

Example 2
In Example 1, 1 g of methyldimethoxysilane was used as the silicon compound and reacted in the same manner. After completion of the reaction, the solvent and unreacted silicon compound were removed by distillation under reduced pressure. As a result, 20.4 g of modified polypropylene was obtained.
As in Example 1, there was no terminal vinylidene unsaturated group in the modified polypropylene, and the weight average molecular weight (Mw) was 11,200.

Example 3
In a 200 ml eggplant flask equipped with a stirrer, 20 g of the polypropylene obtained in Production Example 2 and 100 ml of cyclohexane as a solvent were added and dissolved while stirring. 10.2 g of methyl hydridosiloxane-dimethylsiloxane copolymer (manufactured by Gelest Inc., HMS-071) was added thereto and stirred uniformly, and then a xylene solution of divinyltetramethyldisiloxane / platinum complex (2. 0.05 ml) (containing 1 to 2.4% by mass of platinum) was added and reacted at 40 ° C. for 5 hours. After completion of the reaction, the solvent was removed by distillation under reduced pressure, acetone washing was sufficiently performed, and the solid component was dried to obtain 29.5 g of modified polypropylene.

  The terminal-modified poly α-olefin of the present invention can be subjected to a surface treatment in a solution or an emulsion state in addition to the surface treatment of the filler in a molten state. In addition, the poly α-olefin of the present invention is useful for various uses, for example, a modifier, a surface treatment agent for inorganic materials, an inorganic filler treatment agent, and the like.

Claims (11)

The terminal which has the residue produced | generated by reaction of this poly (alpha) -olefin and the silicon compound which has Si-H group in the terminal of the poly (alpha) -olefin which satisfies the following (1)-(3) Modified poly α-olefin.
(1) It is obtained by polymerization of one or more α-olefins having 3 to 28 carbon atoms or copolymerization of ethylene with one or more selected from α-olefins having 3 to 28 carbon atoms.
(2) Mesopentad fraction [mmmm] is in the range of 30 to 80 mol%.
(3) The intrinsic viscosity [η] measured at 135 ° C. in decalin is in the range of 0.01 to 2.5 dl / g. The residue produced by the reaction with the silicon compound having Si-H is the following (I) or (II)
The terminal-modified polyα-olefin according to claim 1.
(I) A silicon compound residue represented by the general formula [I].

(In the formula, R ¹ is a monovalent hydrocarbon group having 1 to 12 carbon atoms, and L is selected from a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amide group, an acid amide group, and an aminooxy group. A hydrolyzable group, when there are a plurality of R ¹ or L, the plurality of R ¹ and the plurality of L may be the same or different, a is 0, 1 or 2. -Si is poly α -A binding site with an olefin.
(II) Polysiloxane residue satisfying the following (a) to (c)
(a) It has the structure of the siloxane terminal (A unit) represented by general formula (A), the siloxane main chain (B unit) represented by general formula (B), or both.
(b) The polysiloxane molecular main chain has a siloxane repeating unit (C unit) represented by the general formula (C).

(In the formula, R ^{2 to} R ⁶ each independently represent an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms. * -Si represents a bonding site with a poly α-olefin.)
(c) The number of A units is 0 to 2 / molecule, the number of B units is 0 to 10 / molecule, and A unit and B unit are not 0 at the same time. The total of the A unit, B unit and C unit is 5 to 1500 per molecule, and the polysiloxane terminal other than the bonding site with the poly α-olefin is R ⁷ or OR ⁸ (R ⁷ and R ⁸ are each independently Represents an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms.).   The poly α-olefin is a propylene homopolymer or a copolymer of 90% by mass or more of propylene and one or more selected from ethylene and an α-olefin having 4 to 28 carbon atoms and 10% by mass or less. The terminal-modified poly α-olefin as described.   The poly α-olefin is a 1-butene homopolymer or a copolymer of 90% by mass or more of 1-butene and one or more types selected from ethylene, propylene and an α-olefin having 5 to 28 carbon atoms. The terminal-modified poly α-olefin according to claim 1 or 2. The number of carbon atoms in the presence of a catalyst containing poly (α-olefin) containing (A) a transition metal compound represented by the general formula [II] and (B) a compound capable of reacting with the transition metal compound to form an ionic complex. 5. The polymer according to claim 1, wherein the polymer is obtained by polymerization of one or more α-olefins having 3 to 28, or copolymerization of ethylene with one or more α-olefins having 3 to 28 carbon atoms. Terminal-modified polyalphaolefin.

[In the formula, M represents a metal element of Groups 3 to 10 of the periodic table, and E ¹ and E ² represent a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, and a heterocyclopenta, respectively. A ligand selected from a dienyl group, a substituted heterocyclopentadienyl group, an amide group, a phosphine group, a hydrocarbon group and a silicon-containing group is formed, and a crosslinked structure is formed through A ¹ and A ^2. ing. E ¹ and E ² may be the same or different from each other, and at least one of E ¹ and E ² is a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group or a substituted indenyl group. is there. X represents a σ-bonding ligand, and when there are a plurality of Xs, the plurality of Xs may be the same or different, and may be cross-linked with other X, E ¹ , 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. 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, a silicon-containing group, germanium containing group, a tin-containing group, -O -, - CO -, - S -, - SO 2 -, - Se -, - NR -, - PR -, - P (O) R -, - BR- or -AlR R 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 presence of a catalyst containing a transition metal compound, a polyα-olefin satisfying the following (4) to (7) and one or more silicon compounds selected from the following (III) and (IV) are subjected to a hydrosilylation reaction: The method for producing a terminally modified poly-α-olefin according to any one of claims 1 to 5.
(4) It is obtained by polymerization of one or more α-olefins having 3 to 28 carbon atoms, or copolymerization of ethylene with one or more selected from α-olefins having 3 to 28 carbon atoms.
(5) Mesopentad fraction [mmmm] is in the range of 30 to 80 mol%.
(6) It has 0.5 to 1.0 vinylidene group as a terminal unsaturated group per molecule.
(7) The intrinsic viscosity [η] measured at 135 ° C. in decalin is in the range of 0.01 to 2.5 dl / g.
(III) A silicon compound represented by the general formula [III].

(Wherein R ¹ is a monovalent hydrocarbon group having 1 to 12 carbon atoms, and L is selected from a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amide group, an acid amide group, and an aminooxy group. A hydrolyzable group, when there are a plurality of R ¹ or L, the plurality of R ¹ and the plurality of L may be the same or different, a is 0, 1 or 2)
(IV) Polysiloxane satisfying the following (d) to (f)
(d) It has the structure of the siloxane terminal (D unit) represented by general formula (D), the siloxane main chain (E unit) represented by general formula (E), or both.
(e) The polysiloxane molecular main chain has a siloxane repeating unit (C unit) represented by the general formula (C).

(In the formula, R ^{2 to} R ⁶ each independently represents an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms.)
(f) The number of D units is 0 to 2 / molecule, the number of E units is 0 to 10 / molecule, and the D unit and the E unit are not 0 at the same time. The total number of D units, E units and C units is 5 to 1500 per molecule, and the polysiloxane terminal is R ⁷ or OR ⁸ (R ⁷ and R ⁸ are each independently an unsubstituted or substituted carbon number of 1 to 12 represents a monovalent hydrocarbon group.). The number of carbon atoms in the presence of a catalyst containing poly (α-olefin) containing (A) a transition metal compound represented by the general formula [II] and (B) a compound capable of reacting with the transition metal compound to form an ionic complex. The terminal-modified polyα- according to claim 6, which is obtained by polymerization of one or more α-olefins having 3 to 28, or copolymerization of ethylene with one or more α-olefins having 3 to 28 carbon atoms. Production method of olefin.

[In the formula, M represents a metal element of Groups 3 to 10 of the periodic table, and E ¹ and E ² represent a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, and a heterocyclopenta, respectively. A ligand selected from a dienyl group, a substituted heterocyclopentadienyl group, an amide group, a phosphine group, a hydrocarbon group and a silicon-containing group is formed, and a crosslinked structure is formed through A ¹ and A ^2. ing. E ¹ and E ² may be the same or different from each other, and at least one of E ¹ and E ² is a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group or a substituted indenyl group. is there. X represents a σ-bonding ligand, and when there are a plurality of Xs, the plurality of Xs may be the same or different, and may be cross-linked with other X, E ¹ , 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. 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, a silicon-containing group, germanium containing group, a tin-containing group, -O -, - CO -, - S -, - SO 2 -, - Se -, - NR -, - PR -, - P (O) R -, - BR- or -AlR R 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. ] The poly α-olefin is a propylene homopolymer or a copolymer of 90% by mass or more of propylene and 10% by mass or less of ethylene and an α-olefin having 4 to 28 carbon atoms, and a differential scanning calorimeter (DSC) The method for producing a terminal-modified polyα-olefin according to claim 6 or 7, wherein the observed melting point (Tm, unit: ° C) and [mmmm] satisfy the relationship of the following formula [IV].
1.76 [mmmm] -25.0 ≦ Tm ≦ 1.76 [mmmm] +5.0 [IV]   The method for producing a terminally modified poly-α-olefin according to any one of claims 6 to 8, wherein the hydrosilylation reaction is performed in a molten state at a reaction temperature of 50 to 150 ° C.   The method for producing a terminally modified poly-α-olefin according to any one of claims 6 to 8, wherein the hydrosilylation reaction is performed in a solution state at a reaction temperature in the range of -30 to 150 ° C.   The composition containing 1 or more types chosen from the terminal modified poly alpha olefin in any one of Claims 1-5, and other resin and an inorganic filler.