JP2019059894A - Rubber vibration isolator composition and rubber vibration isolator product - Google Patents

Abstract

To provide a rubber composition capable of forming a rubber vibration isolator improved in the dynamic-to-static modulus ratio and the compression set compared to conventional EPDM based rubber vibration isolators.SOLUTION: A rubber vibration isolator composition contains (A) 100 pts.wt of a copolymer of ethylene, C3-20 α-olefin and nonconjugated polyene, and (B) 1-100 pts.wt of hydrophobic silica that is surface-treated with octylsilane.SELECTED DRAWING: None

Description

  The present invention relates to a composition for vibration-proof rubber containing an ethylene / α-olefin / non-conjugated polyene copolymer and a vibration-proof rubber product obtained by vulcanizing the composition.

  Ethylene-propylene-nonconjugated diene copolymer rubber (EPDM) is superior in heat resistance (including heat aging resistance), weather resistance, etc. to general-purpose diene rubbers because it has no unsaturated bond in the main chain. In the field of automotive parts and industrial parts, etc., they are used as anti-vibration rubbers for preventing vibration and noise.

  In the field of automobile parts, anti-vibration rubbers are used, for example, in engine mounts, muffler hangers and the like in order to absorb vibrations when the engine is driven and prevent noise. As such a vibration-proof rubber material, a rubber composition in which EPDM is mixed with a filler such as silica and carbon black is conventionally used (see, for example, Patent Documents 1 and 2).

  However, in recent years, the demand for vibration damping characteristics such as dynamic magnification and compression set has become increasingly high, and further improvement is desired.

Unexamined-Japanese-Patent No. 2004-161985 JP, 2006-348095, A

  An object of the present invention is to provide a rubber composition capable of producing a vibration-proof rubber having an improved dynamic magnification (vibration-proof property) and compression set (rubber elasticity) more than conventional EPDM-based vibration-proof rubbers. I assume.

  The present inventors have intensively studied to solve the above-mentioned problems, and as a result, by blending hydrophobic silica surface-treated with octylsilane into an ethylene / α-olefin / non-conjugated polyene copolymer, a dynamic magnification can be obtained. It has been found that a vibration-proof rubber having improved compression set and compression set can be obtained, and the present invention has been completed. That is, the present invention relates to, for example, the following [1] to [10].

  [1] Ethylene / α-olefin / non-conjugated polyene copolymer having a structural unit derived from ethylene (a1), α-olefin having 3 to 20 carbon atoms (a2), and non-conjugated polyene (a3) (A) 100 parts by weight, and 1 to 100 parts by weight of hydrophobic silica surface-treated with octylsilane (B).

[2] The composition according to item [1], wherein the copolymer (A) satisfies the following conditions (i) to (vii):
(I) The molar ratio [(a1) / (a2)] of the structural unit derived from ethylene (a1) and the structural unit derived from α-olefin (a2) is 40/60 to 99.9 / 0. Is 1;
(Ii) The weight fraction of the structural unit derived from the nonconjugated polyene (a3) is 0.07% by weight to 10% by weight in 100% by weight of the copolymer (A);
(Iii) Weight average molecular weight (Mw) of copolymer (A) and weight fraction of constituent unit derived from non-conjugated polyene (a3) (weight fraction of (a3) (% by weight)), non-conjugated The molecular weight of polyene (a3) (the molecular weight of (a3)) satisfies the following formula (1);
4.5 ≦ Mw × (a3) weight fraction / 100 / (a3) molecular weight ≦ 40 (1)
(Iv) Complex viscosity ^** ₍ ω _{= 0.1)} (Pa · sec) at a frequency ω = _0.1 rad / s obtained by linear viscoelasticity measurement (190 ° C.) using a rheometer, and a frequency ω = The ratio P (η ^* ₍ ω _{= 0.1)} / η ^* ₍ ω _{= 100)} ) to the complex viscosity ^** ₍ ω _{= 100)} (Pa · sec) at ₁₀₀ rad / s, the limiting viscosity [η], and The weight fraction of the constituent unit derived from the conjugated polyene (a3) (the weight fraction of (a3)) satisfies the following formula (2);
Weight fraction of P / ([η] ^2.9 ) ≦ (a 3) × 6 (2)
(V) The ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) (molecular weight distribution; Mw / Mn) measured by gel permeation chromatography (GPC) is in the range of 8 to 30;
(Vi) the number average molecular weight (Mn) is 30,000 or less;
(Vii) The chart obtained by GPC measurement shows two or more peaks, and the area of the peak appearing on the side of the smallest molecular weight is in the range of 1 to 20% of the total peak area.

  [3] The item [1] or the item [1], wherein the nonconjugated polyene (a3) contains two or more partial structures in total of a partial structure selected from the group consisting of the following general formulas (I) and (II) The composition for vibration-proof rubber as described in [2].

  [4] The composition for vibration-proof rubber according to any one of [1] to [3], wherein the nonconjugated polyene (a3) contains 5-vinyl-2-norbornene (VNB) .

  [5] The composition for vibration-proof rubber according to any one of [1] to [4], wherein the α-olefin (a1) is propylene.

  [6] The composition for vibration-proof rubber according to any one of [1] to [5], further containing zinc oxide (C).

  [7] The composition for vibration-proof rubber as described in [6], wherein the zinc oxide (C) is active zinc flower.

  [8] A vibration-proof rubber comprising the cross-linked body of the composition for vibration-proof rubber according to any one of Items [1] to [7].

  [9] A vibration-proof rubber product for automobile parts, which comprises the crosslinked body of the composition for vibration-proof rubber according to any one of items [1] to [7].

  [10] The anti-vibration rubber product for automobile parts according to [9], wherein the anti-vibration rubber product for automobile parts is an engine mount.

  ADVANTAGE OF THE INVENTION According to this invention, compared with the case where the conventional EPDM type | system | group rubber composition is used, the vibration-proof rubber in which dynamic magnification and compression set were improved is obtained.

It is the schematic of the continuous-polymerization apparatus used in the Example.

Hereinafter, the present invention will be described in detail.
[Composition for anti-vibration rubber]
The composition for vibration-proof rubber according to the present invention (hereinafter sometimes simply referred to as "the composition of the present invention" or "the rubber composition of the present invention") is ethylene / α-olefin / non-conjugated polyene copolymer 100 parts by weight of the combined (A) (hereinafter sometimes referred to simply as “copolymer (A)”), and hydrophobic silica (B) surface-treated with octylsilane (hereinafter referred to simply as “hydrophobic silica (B) may be referred to as "(B)" 1) to 100 parts by weight. The composition of the present invention preferably contains zinc oxide (C), and may further contain other components.

<Ethylene · α-olefin · nonconjugated polyene copolymer (A)>
The copolymer (A) used in the present invention has a structural unit derived from ethylene (a1), an α-olefin having 3 to 20 carbon atoms (a2), and a non-conjugated polyene (a3).

  Examples of the α-olefin (a2) include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-eicosene etc. are mentioned. Among these, α-olefins having 3 to 8 carbon atoms such as propylene, 1-butene, 1-hexene and 1-octene are preferable, and propylene is particularly preferable. Such an α-olefin is preferable because the cost of the raw material is relatively low, the obtained copolymer (A) exhibits excellent mechanical properties, and a molded article having rubber elasticity can be obtained.

  The above α-olefins (a2) may be used alone or in combination of two or more. That is, the copolymer (A) contains a structural unit derived from at least one α-olefin having 3 to 20 carbon atoms (a2), and 2 or more α having 3 to 20 carbon atoms -The structural unit derived from an olefin (a2) may be included.

  The non-conjugated polyene (a3) is not particularly limited as long as it is a compound having two or more non-conjugated unsaturated bonds, and for example, partial structures selected from the group consisting of the following general formulas (I) and (II) And compounds containing two or more in the molecule.

  Examples of the nonconjugated polyene (a3) include 5-vinyl-2-norbornene (VNB), norbornadiene, 1,4-hexadiene, dicyclopentadiene and the like. Among these, the non-conjugated polyene (a3) is a VNB because the availability is high, the reactivity with the peroxide is good at the time of crosslinking reaction after polymerization, and the heat resistance of the polymer composition is easily improved. It is preferable that the nonconjugated polyene (a3) is VNB. The nonconjugated polyene (a3) may be used alone or in combination of two or more.

  In addition to the structural units derived from the above (a1), (a2) and (a3), the above copolymer (A) further has a partial structure selected from the group consisting of the above general formulas (I) and (II) You may have the structural unit derived from nonconjugated polyene (a4) which contains only one in a molecule.

  As the non-conjugated polyene (a4), 5-ethylidene-2-norbornene (ENB), 5-methylene-2-norbornene, 5- (2-propenyl) -2-norbornene, 5- (3-butenyl) -2 -Norbornene, 5- (1-methyl-2-propenyl) -2-norbornene, 5- (4-pentenyl) -2-norbornene, 5- (1-methyl-3-butenyl) -2-norbornene, 5- ( 5-hexenyl) -2-norbornene, 5- (1-methyl-4-pentenyl) -2-norbornene, 5- (2,3-dimethyl-3-butenyl) -2-norbornene, 5- (2-ethyl-) 3-butenyl) -2-norbornene, 5- (6-heptenyl) -2-norbornene, 5- (3-methyl-5-hexenyl) -2-norbornene, 5- (3,4-dimethyl) 4-pentenyl) -2-norbornene, 5- (3-ethyl-4-pentenyl) -2-norbornene, 5- (7-octenyl) -2-norbornene, 5- (2-methyl-6-heptenyl) -2 -Norbornene, 5- (1,2-dimethyl-5-hexenyl) -2-norbornene, 5- (5-ethyl-5-hexenyl) -2-norbornene, 5- (1,2,3-trimethyl-4-) And pentenyl) -2-norbornene. Among these, ENB is preferable because of high availability, high reactivity with sulfur and vulcanization accelerator at the time of crosslinking reaction after polymerization, easy control of crosslinking rate, and easy to obtain good mechanical properties. . The nonconjugated polyene (a4) may be used alone or in combination of two or more.

  When the copolymer (A) contains a constitutional unit derived from the non-conjugated polyene (a4), the ratio is not particularly limited as long as the object of the present invention is not impaired. 20 wt%, preferably 0 to 8 wt%, more preferably 0.01 to 8 wt% or so (provided that the weight fraction of (a1), (a2), (a3), (a4)) The sum of the rates is 100% by weight).

The copolymer (A) preferably satisfies the following requirements (i) to (vii) (hereinafter, also referred to as requirements (i) to (vii), respectively).
(I) The molar ratio [(a1) / (a2)] of the structural unit derived from ethylene (a1) and the structural unit derived from α-olefin (a2) is 40/60 to 99.9 / 0. It is 1.
(Ii) The weight fraction of the structural unit derived from the nonconjugated polyene (a3) is 0.07% by weight to 10% by weight in 100% by weight of the copolymer (A).
(Iii) Weight average molecular weight (Mw) of copolymer (A) and weight fraction of constituent unit derived from non-conjugated polyene (a3) (weight fraction of (a3) (% by weight)), non-conjugated The molecular weight of polyene (a3) (molecular weight of (a3)) satisfies the following formula (1).
4.5 ≦ Mw × (a3) weight fraction / 100 / (a3) molecular weight ≦ 40 (1)

(Iv) Complex viscosity ^** ₍ ω _{= 0.1)} (Pa · sec) at a frequency ω = _0.1 rad / s obtained by linear viscoelasticity measurement (190 ° C.) using a rheometer, and a frequency ω = The ratio P (η ^* ₍ ω _{= 0.1)} / η ^* ₍ ω _{= 100)} ) to the complex viscosity ^** ₍ ω _{= 100)} (Pa · sec) at ₁₀₀ rad / s, the limiting viscosity [η], and The weight fraction of the structural unit derived from the conjugated polyene (a3) (the weight fraction of (a3)) satisfies the following formula (2).
Weight fraction of P / ([η] ^2.9 ) ≦ (a 3) × 6 (2)

(V) The ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) (molecular weight distribution; Mw / Mn) measured by gel permeation chromatography (GPC) is in the range of 8 to 30.
(Vi) The number average molecular weight (Mn) is 30,000 or less.
(Vii) The chart obtained by GPC measurement shows two or more peaks, and the area of the peak appearing on the side of the smallest molecular weight is in the range of 1 to 20% of the total peak area.

«Requirement (i)»
Requirement (i) specifies that the molar ratio of ethylene (a1) / α-olefin (a2) in the above-mentioned copolymer (A) satisfies 40/60 to 99.9 / 0.1. The molar ratio is preferably 50/50 to 90/10, more preferably 55/45 to 85/15, and still more preferably 55/45 to 78/22.

By using the copolymer (A) satisfying the requirement (i), a vibration-proof rubber excellent in rubber elasticity, mechanical strength and flexibility can be obtained. The amount of ethylene in the copolymer (A) (content of constituent unit derived from ethylene (a1)) and the amount of α-olefin (content of constituent unit derived from α-olefin (a2)) are ¹³ C- It can be determined by NMR.

«Requirement (ii)»
The requirement (ii) is that the weight fraction of the constituent unit derived from the non-conjugated polyene (a3) is 100% by weight of the above copolymer (A) (that is, 100% by weight in total of the weight fraction of all constituent units) , 0.07% by weight to 10% by weight. The weight fraction of the structural unit derived from this non-conjugated polyene (a3) is preferably 0.1% by weight to 8.0% by weight, more preferably 0.5% by weight to 5.0% by weight.

The copolymer (A) satisfying the requirement (ii) has sufficient hardness and is excellent in mechanical properties, and when crosslinked with a peroxide, exhibits a rapid crosslinking rate. The amount of nonconjugated polyene (a3) in the copolymer (A) (the content of the constitutional unit derived from the nonconjugated polyene (a3)) can be determined by ¹³ C-NMR.

<< requirement (iii) >>
Requirement (iii) is that, in the copolymer (A), the weight average molecular weight (Mw) of the copolymer (A) and the constituent unit derived from the nonconjugated polyene (a3) in the copolymer (A) It is specified that the weight fraction (weight fraction of (a3): weight%) and the molecular weight of the non-conjugated polyene (a3) (molecular weight of (a3)) satisfy the above-mentioned formula (1). It is preferable that the said Formula (1) of requirement (iii) is following formula (1 ').
4.5 ≦ Mw × (a3) weight fraction / 100 / (a3) molecular weight ≦ 35 (1 ′)

  When the copolymer (A) satisfies the requirement (iii), the content of the structural unit derived from the non-conjugated polyene (a3) is appropriate, exhibits sufficient crosslinking performance, and is excellent in crosslinking rate, It is possible to produce an anti-vibration rubber exhibiting excellent mechanical properties. In addition, the weight average molecular weight (Mw) of a copolymer (A) can be calculated | required as a numerical value of polystyrene conversion measured by gel permeation chromatography (GPC).

  In the above-mentioned copolymer (A), when “molecular weight of Mw × (a3) / 100 / (a3)” satisfies the above formula (1) or (1 ′), the degree of crosslinking becomes appropriate, and the machine It is possible to produce an anti-vibration rubber which is excellent in balance between physical properties and heat aging resistance. When the value of “weight fraction of Mw × (a3) / 100 / (a3) molecular weight” ”is too low, the crosslinkability may be insufficient and the crosslinking rate may be slow, and when the value is too high However, excessive crosslinking may occur to deteriorate mechanical properties.

«Requirements (iv)»
Requirement (iv) is the complex viscosity η ^* ₍ ω _{= 0.1} at frequency ω = 0.1 rad / s) obtained by linear viscoelasticity measurement (190 ° C.) of the above-mentioned copolymer (A) using a rheometer The ratio P (η ^* ₍ ω _{= 0.1)} / η ^* ₍ ω _{= 100) of} (Pa · sec) to the complex viscosity ^** ₍ ω _{= 100 )} (Pa · sec) at a frequency ω = 100 rad / s ), The intrinsic viscosity [η], and the weight fraction of the constituent unit derived from the nonconjugated polyene (a3) (weight fraction of (a3): wt%) satisfy the above formula (2) It is to identify. It is preferable that said Formula (2) of requirement (iv) is following formula (2 ').
P / ([η] ^2.9 ) ≦ (a3) weight fraction × 5.7 (2 ′)

Here, the ratio P (η ^* ₍ ω ₎ between the complex viscosity η ^* ₍ ω _{= 0.1)} at frequency ω = _0.1 rad / s and the complex viscosity ^** ₍ ω _{= 100)} at frequency ω = 100 rad / s _{= 0.1)} / η ^* ₍ ω _{= 100)} ) represents the frequency dependency of viscosity, and P / ([η] ^2.9 ) corresponding to the left side of equation (2) represents short chain branching, molecular weight, etc. Although there is an influence, it tends to show a high value when there are many long chain branches. Generally, in the ethylene / α-olefin / nonconjugated polyene copolymer, the longer the long-chain branching tends to be, the more the component unit derived from the nonconjugated polyene contains, but the copolymer (A) of the present invention It is believed that the above formula (2) can be satisfied by having less long chain branching than conventionally known ethylene / α-olefin / nonconjugated polyene copolymers.

In the present invention, the P value is a complex viscosity at 0.1 rad / s, which is obtained by measurement using a viscoelasticity measuring apparatus Ares (manufactured by Rheometric Scientific) under conditions of 190 ° C., strain 1.0% and frequency change. The ratio (η ^* ratio) is determined from the complex viscosity at 100 rad / s and the complex viscosity at 100 rad / s. The intrinsic viscosity [粘度] means a value measured in decalin at 135 ° C.

«Requirements (v)»
The requirement (v) is the ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the above-mentioned copolymer (A) measured by gel permeation chromatography (GPC) (molecular weight distribution; Mw / It is specified that Mn) is in the range of 8 to 30. The molecular weight distribution (Mw / Mn) is preferably in the range of 9 to 28, more preferably 10 to 26.

When the copolymer (A) satisfies the requirement (v), the low molecular weight component is contained in an appropriate amount, so that the processability becomes good.
In addition, the weight average molecular weight (Mw) and number average molecular weight of the said copolymer (A) can be calculated | required as a numerical value of polystyrene conversion measured by gel permeation chromatography (GPC).

«Requirements (vi)»
The requirement (vi) specifies that the number average molecular weight (Mn) of the copolymer (A) is 30,000 or less. The number average molecular weight (Mn) is preferably in the range of 3,000 to 26,000, more preferably 6,000 to 23,000.
When the copolymer (A) satisfies the requirement (vi), the low molecular weight component is contained in an appropriate amount, so that the processability becomes good.

<< Requirement (vii) >>
Requirement (vii) is that the chart obtained by the GPC measurement of the copolymer (A) shows two or more peaks, and the area of the peak appearing on the side with the smallest molecular weight is 20% or less of the entire peak area It is something which specifies something. The area of the peak appearing on the side with the lowest molecular weight is preferably 2 to 18%, more preferably 3 to 16%, relative to the total peak area.
When the copolymer (A) satisfies the requirement (vii), the molecular weight distribution of the copolymer (A) exhibits multimodality such as bimodality, and the high molecular weight component and the low molecular weight component The proper proportion is included, and the processability is good.

«Requirements (viii)»
The copolymer (A) is obtained by using 3D-GPC and obtained by using the number of long chain branches per 1000 carbon atoms (LCB _{1000 C} ) and the natural logarithm [Ln (Mw)] of weight average molecular weight (Mw). It is preferable to satisfy the following formula (3), and it is more preferable to satisfy the following formula (3 ′).
LCB _{1000 C} ≦ 1-0.07 × Ln (Mw) (3)
LCB _1000C ≦ 1-0.071 × Ln (Mw) (3 ′)
The upper limit value of the long chain branch content per unit carbon number of the copolymer (A) is specified by the above formula (3) or (3 ′).

  Such a copolymer (A) has a small proportion of long chain branching, and is excellent in the curing characteristics in the case of crosslinking using a peroxide, as well as obtaining a vibration-proof rubber excellent in heat aging resistance. Can.

Here, Mw and the number of long chain branches per 1000 carbon atoms (LCB _1000C ) can be determined by structural analysis using 3D-GPC. In the present specification, specifically, it was determined as follows.

  The absolute molecular weight distribution was determined using a 3D-high temperature GPC apparatus PL-GPC 220 (manufactured by Polymer Laboratories), and at the same time, the limiting viscosity was determined with a viscometer. The main measurement conditions are as follows.

Detector: Built-in differential refractometer / GPC device
Two-angle light scattering photometer PD2040 (manufactured by Precison Detectors)
Bridge-type viscometer PL-BV 400 (manufactured by Polymer Laboratories)
Column: TSKgel GMH _HR- H (S) HT x 2 + TSKgel GMH _HR- M (S) x 1
(Each one has an inner diameter of 7.8 mmφ × 300 mm in length)
Temperature: 140 ° C
Mobile phase: 1,2,4-Trichlorobenzene (containing 0.025% BHT)
Injection volume: 0.5mL
Sample concentration: ca 1.5 mg / mL
Sample filtration: filtration with a pore diameter of 1.0 μm sintered filter In the above, dn / dc value necessary for determination of absolute molecular weight is 0.053 of dn / dc value of standard polystyrene (molecular weight 190000) and differential refractometer per unit injection mass From the response strength, it was determined for each sample.

  The long chain branching parameter g'i for each eluted component was calculated from the following formula (v-1) from the relationship between the intrinsic viscosity obtained from the viscometer and the absolute molecular weight obtained from the light scattering photometer.

Here, the relation of [η] = KM ^v ; v = 0.725 was applied.
Moreover, each average value was computed from following formula (v-2), (v-3), (v-4) as g '. In addition, Trendline assumed to have only short chain branching was determined for each sample.

Furthermore, using g'w, the branch number BrNo per molecular chain, the number of long-chain branches LCB _1000C per 1000 carbons, and the degree of branch λ per unit molecular weight were calculated. Calculation of BrNo used the following formula (v-5) of Zimm-Stockmayer, and calculation of LCB _1000C and (lambda) used following formula (v-6) and (v-7). g is a long chain branching parameter determined from the radius of inertia Rg, and the following simple correlation is made with g 'determined from the limiting viscosity. In the formula, various values have been proposed according to the form of the molecule. Here, the calculation was performed assuming that ε = 1 (that is, g ′ = g).

λ = Br No / M (V-6)
LCB _{1000 C} = λ × 14000 (V-7)
Wherein (V-7), "14000" represents a molecular weight of 1000 pieces of methylene (CH ₂₎ units.

  The intrinsic viscosity [η] of the above copolymer (A) is preferably 0.1 to 5 dL / g, more preferably 0.5 to 5.0 dL / g, still more preferably 0.9 to 4.0 dL / g It is.

  The weight average molecular weight (Mw) of the above-mentioned copolymer (A) is preferably 10,000 to 600,000, more preferably 30,000 to 500,000, and still more preferably 50,000 to 400,000. is there.

  It is preferable that the above-mentioned copolymer (A) be satisfied in combination with the above-mentioned intrinsic viscosity [η] and weight average molecular weight (Mw).

  In the copolymer (A), as described above, the non-conjugated polyene (a3) preferably contains VNB, more preferably VNB. That is, in the formulas (1), (2) and the formula (4) described later, it is preferable that "weight fraction of (a3)" is "weight fraction of VNB" (% by weight).

  As described above, the copolymer (A) further includes, in addition to the structural units derived from the (a1), (a2) and (a3), structural units derived from the non-conjugated polyene (a4) It is also preferable to include a weight fraction of 0% by weight to 20% by weight (provided that the total of the weight fractions of (a1), (a2), (a3) and (a4) is 100% by weight). In this case, it is preferable to satisfy the following requirement (ix).

«Requirements (ix)»
Weight average molecular weight (Mw) of the above-mentioned copolymer (A), weight fraction of constituent units derived from non-conjugated polyene (a3) (weight fraction of (a3) (% by weight)), non-conjugated polyene (a) The weight fraction of the constituent unit derived from a4) (the weight fraction of (a4) (% by weight)), the molecular weight of the nonconjugated polyene (a3) (molecular weight of (a3)), and the nonconjugated polyene (a4) The molecular weight (molecular weight of (a4)) satisfies the following formula (4).
4.5 ≦ Mw × {(weight fraction of (a3) / 100 / molecular weight of (a3) + (weight fraction of (a4) / 100 / molecular weight of (a4))} ≦ 45 (4)

In Formula (4), the content of the nonconjugated diene (sum of (a3) and (a4)) in one copolymer molecule is specified.
When the copolymer (A) containing the structural unit derived from the above (a4) satisfies the formula (4), a vibration-proof rubber excellent in mechanical properties and heat aging resistance can be obtained.

  Not satisfying the requirement (ix), “Mw × {((weight fraction of (a3)) / 100 / molecular weight of (a3) + (weight fraction of (a4) / 100 / (a4)” in the formula (4) If the value of “molecular weight)} is too low, ie, the content of non-conjugated diene is too low, sufficient crosslinking may not be achieved and appropriate mechanical properties may not be obtained, and when the value is too high, ie When the content of conjugated diene is too large, crosslinking may be excessive to deteriorate mechanical properties, and heat aging resistance may be further deteriorated.

«Requirement (x)»
The copolymer (A) is not particularly limited, obtained by linear viscoelastic measurement using a rheometer (190 ° C.), the complex viscosity at the frequency ω = 0.01rad / s η ^* ₍ ω _{= 0.01)} (Pa · sec), complex viscosity ^{* *} ₍ ω _{= 10)} (Pa · sec) at frequency ω = 10 rad / s, and apparent iodine value derived from non-conjugated polyene (a3) It is preferable to satisfy the following formula (5).
Log {η ^* ₍ ω _{= 0.01)} } / Log {η ^* ₍ ω _{= 10)} } ≦ 0.0753 × {apparent iodine value derived from nonconjugated polyene (a3)} + 1.42 (5)

Here, the complex viscosity ^** ₍ ω _{= 0.01)} and the complex viscosity ^{* *} ₍ ω _{= 10)} are measured with the complex viscosity ^{* *} ₍ ω _{= 0.1)} and the complex viscosity ^{* *} ₍ ω _{= 100)} in requirement (iv) Other than the frequency can be obtained in the same manner. The apparent iodine value derived from the nonconjugated polyene (a3) can be determined by the following equation.
Apparent iodine number derived from (a3) = weight fraction of (a3) x molecular weight of 253.81 / (a3)

  In the above formula (5), the left side represents the shear rate dependence which is an index of the amount of long chain branching, and the right side represents the index of the content of the nonconjugated polyene (a3) not consumed as the long chain branch during polymerization. When the said copolymer (A) satisfy | fills the said Formula (5), since the grade of a long chain branch is not too high, it is preferable. On the other hand, when the above formula (5) is not satisfied, it can be seen that the proportion of the copolymerized non-conjugated polyene (a3) consumed for the formation of long chain branching is high.

  Furthermore, the copolymer (A) preferably contains a sufficient amount of a constituent unit derived from the non-conjugated polyene (a3), and the constituent unit derived from the non-conjugated polyene (a3) in the copolymer It is more preferable that the weight fraction (the weight fraction of (a3) (% by weight)) and the weight average molecular weight (Mw) of the copolymer satisfy the following formula (6).

6−0.45 × Ln (Mw) ≦ (a3) weight fraction ≦ 10 (6)
The copolymer (A) preferably has a number (n _a3 ) of constituent units derived from the non-conjugated polyene (a3) per weight average molecular weight (Mw) of preferably 6 or more, more preferably 6 The number is 40 or more, more preferably 7 or more and 39 or less, and particularly preferably 10 or more and 38 or less.

  Such a copolymer (A) contains a sufficient amount of a structural unit derived from a nonconjugated polyene (a3) such as VNB, and has a long chain branch content and is crosslinked using a peroxide. As well as being excellent in the curing characteristics in the case of performing the above, the formability is good, the balance of physical properties such as mechanical characteristics is excellent, and in particular, the heat aging resistance is excellent.

The copolymer (A) preferably has a number ( _na4 ) of structural units derived from the non-conjugated polyene (a4) per weight average molecular weight (Mw) of preferably 29 or less, more preferably 10 The following is more preferably less than one.

  In such a copolymer (A), the content of structural units derived from non-conjugated polyenes (a4) such as ENB is suppressed within a range that does not impair the object of the present invention, and post-crosslinking hardly occurs. Heat aging resistance.

Here, the number of structural units derived from the nonconjugated polyene (a3) per weight average molecular weight (Mw) of the copolymer (A) ( _na3 ) or the number of structural units derived from the nonconjugated polyene (a4) ( _Na4 ) is the molecular weight of the nonconjugated polyene (a3) or (a4), and the weight fraction of the structural unit derived from the nonconjugated polyene (a3) or (a4) in the copolymer ((a3) or (a3) From the weight fraction (weight%) of a4) and the weight average molecular weight (Mw) of the copolymer (A), it can be determined by the following formula.

( _Na3 ) = (Mw) × {(a3) weight fraction / 100} / molecular weight of non-conjugated polyene (a3) ( _na4 ) = (Mw) × {(a4) weight fraction / 100} / Molecular Weight of Non-Conjugated Polyene (a4) In the above-mentioned copolymer (A), the number (n _a3 ) of the respective constituent units derived from the non-conjugated polyenes (a3) and (a4) per weight average molecular weight (Mw) When all (n _a4 ) satisfy the above-mentioned range, the copolymer (A) has a small content of long-chain branching and is excellent in the curing characteristics in the case of crosslinking using a peroxide, and molding It is preferable because it is excellent in the physical property balance such as mechanical properties and the like, and it is difficult to cause post-crosslinking, and in particular, it is excellent in heat aging resistance.

<Preparation of Copolymer (A)>
The copolymer (A) is obtained by copolymerizing monomers consisting of ethylene (a1), α-olefin (a2), non-conjugated polyene (a3) and, if necessary, non-conjugated polyene (a4) Copolymer.

  The above copolymer (A) may be prepared by any method as long as the above requirements (i) to (vii) are satisfied, but it is obtained by copolymerizing monomers in the presence of a metallocene compound It is preferable that it is one which is obtained by copolymerization of monomers in the presence of a catalyst system containing a metallocene compound, more preferably copolymerization in the presence of a polymerization catalyst containing a specific metallocene compound. It is more preferable that the method is obtained by a method including the step (1) to be performed and the step (2) of adding an alcohol as a catalyst deactivator to deactivate the polymerization catalyst.

«Metallocene compounds»
The copolymer (A) is preferably obtained by copolymerizing monomers in the presence of a polymerization catalyst system containing at least one metallocene compound selected from compounds represented by the following general formula [A1]. Is desirable. When copolymerization of monomers is carried out using a polymerization catalyst system containing such a metallocene compound, long chain branching contained in the resulting copolymer is suppressed, and a copolymer (A) satisfying the above requirements is obtained. It can be easily prepared.

In formula [A1], R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁸ , R ⁹ and R ¹² each independently represent a hydrogen atom, a hydrocarbon group, a silicon-containing group or a hetero group other than a silicon-containing group An atom-containing group is shown, and two adjacent groups among R ^{1 to} R ⁴ may be bonded to each other to form a ring.

  The hydrocarbon group is preferably a hydrocarbon group having 1 to 20 carbon atoms, and specifically, an alkyl group having 1 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or 6 to 20 carbon atoms An aryl (aryl) group or a substituted aryl (aryl) group may, for example, be mentioned. For example, methyl group, ethyl group, n-propyl group, isopropyl group, allyl (allyl) group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, amyl group, n-pentyl group, neopentyl group , N-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decanyl group, 3-methylpentyl group, 1,1-diethylpropyl group, 1,1-dimethylbutyl group, 1- Methyl-1-propylbutyl group, 1,1-propylbutyl group, 1,1-dimethyl-2-methylpropyl group, 1-methyl-1-isopropyl-2-methylpropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl Group, cyclooctyl group, norbornyl group, adamantyl group, phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, xylyl group, isopropyl And phenyl group, t-butylphenyl group, naphthyl group, biphenyl group, terphenyl group, phenanthryl group, anthracenyl group, benzyl group and cumyl group, and oxygen-containing groups such as methoxy group, ethoxy group and phenoxy group, Nitrogen-containing groups such as nitro, cyano, N-methylamino, N, N-dimethylamino, N-phenylamino, boron-containing groups such as boranetriyl and diboranyl, sulfonyl and sulfenyl Those containing a sulfur-containing group are also mentioned as hydrocarbon groups.

  In the above-mentioned hydrocarbon group, a hydrogen atom may be substituted by a halogen atom, and examples thereof include trifluoromethyl group, trifluoromethylphenyl group, pentafluorophenyl group, chlorophenyl group and the like.

  Examples of silicon-containing groups include silyl groups, siloxy groups, hydrocarbon-substituted silyl groups, and hydrocarbon-substituted siloxy groups. For example, methylsilyl group, dimethylsilyl group, trimethylsilyl group, ethylsilyl group, diethylsilyl group, triethylsilyl group, diphenylmethylsilyl group, triphenylsilyl group, dimethylphenylsilyl group, dimethyl-t-butylsilyl group, dimethyl (pentafluorophenyl) Silyl group etc. can be mentioned.

R ⁶ and R ¹¹ are the same atom or the same group selected from hydrogen atom, hydrocarbon group, silicon-containing group and hetero atom-containing group other than silicon-containing group, and R ⁷ and R ¹⁰ are hydrogen atom, hydrocarbon R ⁶ and R ⁷ may be combined with each other to form a ring, R ¹⁰ and R ¹⁰ and R ⁷ may be bonded to each other to form a ring. R ¹¹ may be bonded to each other to form a ring. However, R ⁶ , R ⁷ , R ¹⁰ and R ¹¹ are not all hydrogen atoms.

R ¹³ and R ¹⁴ each independently represent an aryl group.
M ¹ represents a zirconium atom.
Y ¹ represents a carbon atom or a silicon atom.
Q represents a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a neutral conjugated or nonconjugated diene having 4 to 20 carbon atoms, an anionic ligand or a neutral ligand capable of coordinating with a lone electron pair J represents an integer of 1 to 4 and when j is an integer of 2 or more, a plurality of Qs may be the same or different.

  The halogen atom includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, preferably a chlorine atom.

  As a hydrocarbon group, a C1-C10 hydrocarbon group is preferable, and, specifically, a methyl group, an ethyl group, n-propyl group, isopropyl group, 2-methylpropyl group, 1,1-dimethylpropyl group , 2,2-dimethylpropyl group, 1,1-diethylpropyl group, 1-ethyl-1-methylpropyl group, 1,1,2,2-tetramethylpropyl group, sec-butyl group, t-butyl group, 1,1-dimethylbutyl, 1,1,3-trimethylbutyl, neopentyl, cyclohexylmethyl, cyclohexyl, 1-methyl-1-cyclohexyl, benzyl and the like, with preference given to methyl, ethyl And benzyl.

The neutral conjugated or nonconjugated diene having 4 to 20 carbon atoms is preferably a neutral conjugated or nonconjugated diene having 4 to 10 carbon atoms. Specific examples of the conjugated or nonconjugated diene neutral, s- cis - or s- trans eta ^{4-1,3-butadiene,} s- cis - or s- trans eta ^{4-1,4-diphenyl} - 1,3-butadiene, s- cis - or s- trans eta ^{4-3-methyl-1,3-pentadiene,} s- cis - or s- trans eta ^{4-1,4-dibenzyl-1,3} butadiene, s- cis - or s- trans eta ^{4-2,4-hexadiene,} s- cis - or s- trans eta ^{4-1,3-pentadiene,} s- cis - or s- trans eta ⁴ - 1,4-ditolyl-1,3-butadiene, s-cis- or s-trans-− ⁴ -1,4-bis (trimethylsilyl) -1,3-butadiene and the like can be mentioned.

  Specific examples of the anionic ligand include alkoxy groups such as methoxy, t-butoxy and phenoxy, carboxylate groups such as acetate and benzoate, and sulfonate groups such as mesylate and tosylate.

  Specific examples of the neutral ligand which can be coordinated by a lone electron pair include organophosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine and diphenylmethylphosphine, or tetrahydrofuran, diethyl ether, dioxane, 1,2- 1,2- Ethers such as dimethoxyethane are mentioned.

As the cyclopentadienyl group having substituents R ^{1 to} R ⁴ in the above formula [A1], unsubstituted cyclopentadienyl group wherein R ^{1 to} R ⁴ is a hydrogen atom, 3-t-butylcyclopentadienyl Group, 3-methylcyclopentadienyl group, 3-trimethylsilylcyclopentadienyl group, 3-phenylcyclopentadienyl group, 3-adamantylcyclopentadienyl group, 3-amyl cyclopentadienyl group, 3-cyclohexyl 3-substituted monosubstituted cyclopentadienyl group such as cyclopentadienyl group, 3-t-butyl-5-methylcyclopentadienyl group, 3-t-butyl-5-ethylcyclopentadienyl group, 3-phenyl -5-Methylcyclopentadienyl group, 3,5-di-t-butylcyclopentadienyl group, 3,5-dimethylcyclopentadienyl group And 3,5-disubstituted cyclopentadienyl groups such as 3-phenyl-5-methylcyclopentadienyl group, 3-trimethylsilyl-5-methylcyclopentadienyl group, etc. is not. The cyclopentadienyl group which is unsubstituted (R < ¹ > -R < ⁴ > is a hydrogen atom) is preferable from the viewpoint of the easiness of the synthesis | combination of a metallocene compound, manufacturing cost, and the copolymerization ability of nonconjugated polyene.

As the fluorenyl group having a substituent R ^{5 to} R ¹² in the formula [A1],
An unsubstituted fluorenyl group in which R ^{5 to} R ¹² are a hydrogen atom,
2-position monosubstituted fluorenyl group such as 2-methylfluorenyl group, 2-t-butylfluorenyl group, 2-phenylfluorenyl group, etc.
4-substituted monosubstituted fluorenyl group such as 4-methylfluorenyl group, 4-t-butylfluorenyl group, 4-phenylfluorenyl group, etc.
Or 2,7- or 3,6-disubstituted fluorenyl group such as 2,7-di-t-butylfluorenyl group, 3,6-di-t-butylfluorenyl group, etc.
2,3,6,7 position 4 such as 2,7-dimethyl-3,6-di-t-butylfluorenyl group and 2,7-diphenyl-3,6-di-t-butylfluorenyl group Substituted fluorenyl group,
Alternatively, R ⁶ and R ⁷ are bonded to each other to form a ring, and R ¹⁰ and R ¹¹ are bonded to each other to form a ring, as represented by the following general formulas [V-I] and [V-II] Although 2, 3, 6 and 7 4-substituted fluorenyl group etc. are mentioned, it is not this limitation.

In the formulas [V-I] and [V-II], R ⁵ , R ⁸ , R ⁹ and R ¹² are the same as the definition in the general formula [A1],
R ^a , R ^b , R ^c , R ^d , R ^e , R ^f , R ^g and R ^h each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and they are mutually bonded to adjacent substituents And may form a ring. Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, amyl group and n-pentyl group. Further, in the formula [V-I], R ^x and R ^y each independently represent a hydrocarbon group which may have a ^C 1 to ^C 3 unsaturated bond, and R ^x is R ^a or R ^c is a bond And R ^y may form a double bond in combination with carbon to which R ^e or R ^g is bonded, and R ^x and R ^y may form a double bond. It is preferable that both are a C1 or C2 saturated or unsaturated hydrocarbon group.

  Specifically, as a compound represented by the above general formula [V-I] or [V-II], an octamethyloctahydrodibenzofluorenyl group represented by the formula [V-III], a compound of the formula [V- A tetramethyldodecahydrodibenzofluorenyl group represented by formula IV, an octamethyltetrahydrodicyclopentafluorenyl group represented by formula [V-V], and a hexamethyl dihydrochloride represented by formula [V-VI] Examples thereof include a dicyclopentafluorenyl group and a b, h-dibenzofluorenyl group represented by the formula [V-VII].

The metallocene compounds represented by the above general formula [A1] containing any of these fluorenyl groups are all excellent in the copolymerization ability of non-conjugated polyenes, but when Y ¹ is a silicon atom, 2,7-position disubstituted fluorenyl group, Transition metals having a 3,6-position 2-substituted fluorenyl group, a 2,3,6,7-position 4-substituted fluorenyl group, and a 2,3,6,7-position 4-substituted fluorenyl group represented by the above general formula [V-I] The compounds are particularly good. When Y is a carbon atom, R ⁵ to R ^{12 each} represents a hydrogen atom, a unsubstituted fluorenyl group, a 3,6-disubstituted fluorenyl group, a 2,3,6,7-position 4-substituted fluorenyl group, the above general formula [V A metallocene compound having a 2,3,6,7-position 4-substituted fluorenyl group represented by -I] is particularly excellent.

In the present invention, in the metallocene compound represented by the above general formula [A1], when Y ¹ is a silicon atom and all of R ⁵ to R ¹² are hydrogen atoms, R ¹³ and R ¹⁴ are methyl. A group other than butyl, phenyl, silicon-substituted phenyl, cyclohexyl and benzyl;
When Y ¹ is a silicon atom, R ⁶ and R ¹¹ are both t-butyl, and R ⁵ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹² are not t-butyl, R ¹³ And R ¹⁴ is selected from a group other than benzyl group and silicon-substituted phenyl group;
When Y ¹ is a carbon atom and all of R ⁵ to R ¹² are hydrogen atoms, R ¹³ and R ^{14 each} represent a methyl group, an isopropyl group, a t-butyl group, an isobutyl group, a phenyl group or p-t-butylphenyl A group other than a group, pn-butylphenyl group, silicon-substituted phenyl group, 4-biphenyl group, p-tolyl group, naphthyl group, benzyl group, cyclopentyl group, cyclohexyl group and xylyl group;
Y ¹ is a carbon atom, and R ⁶ and R ¹¹ are common groups selected from a t-butyl group, a methyl group or a phenyl group, and R ⁵ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹² When they are different groups or atoms, R ¹³ and R ¹⁴ are selected from groups other than methyl group, phenyl group, p-t-butylphenyl group, p-n-butylphenyl group, silicon-substituted phenyl group, and benzyl group ;
A group in which Y ¹ is a carbon atom, R ⁶ is a dimethylamino group, a methoxy group or a methyl group, and R ⁵ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are different from R ⁶ or When it is an atom, R ¹³ and R ¹⁴ are selected from a group other than methyl and phenyl;
When Y ¹ is a carbon atom and the site composed of a fluorenyl group and R ^{5 to} R ¹² is b, h-dibenzofluorenyl or a, i-dibenzofluorenyl, R ¹³ and R ¹⁴ are It is preferable to select from groups other than a methyl group and a phenyl group.

  Specific examples of the metallocene compound represented by the above general formula [A1] are shown below, but the scope of the present invention is not particularly limited thereby.

Specific examples of the metallocene compound represented by the above general formula [A1] are
In the case where Y is a silicon atom,
Diphenylsilylene (cyclopentadienyl) (2,7-di-t-butylfluorenyl) zirconium dichloride,
Diphenylsilylene (cyclopentadienyl) (3,6-di-t-butylfluorenyl) zirconium dichloride,
Diphenylsilylene (cyclopentadienyl) (2,7-dimethyl-3,6-di-t-butylfluorenyl) zirconium dichloride;
Diphenylsilylene (cyclopentadienyl) (2,7-diphenyl-3,6-di-t-butylfluorenyl) zirconium dichloride;
Diphenylsilylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride,
Diphenylsilylene (cyclopentadienyl) (tetramethyldodecahydrodibenzofluorenyl) zirconium dichloride,
Diphenylsilylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride,
Diphenylsilylene (cyclopentadienyl) (hexamethyl dihydro dicyclopentafluorenyl) zirconium dichloride,
Diphenylsilylene (cyclopentadienyl) (b, h-dibenzofluorenyl) zirconium dichloride,
Di (p-tolyl) silylene (cyclopentadienyl) (fluorenyl) zirconium dichloride,
Di (p-tolyl) silylene (cyclopentadienyl) (2,7-di-t-butylfluorenyl) zirconium dichloride,
Di (p-tolyl) silylene (cyclopentadienyl) (3,6-di-t-butylfluorenyl) zirconium dichloride,
Di (p-tolyl) silylene (cyclopentadienyl) (2,7-dimethyl-3,6-di-t-butylfluorenyl) zirconium dichloride,
Di (p-tolyl) silylene (cyclopentadienyl) (2,7-diphenyl-3,6-di-t-butylfluorenyl) zirconium dichloride,
Di (p-tolyl) silylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride,
Di (p-tolyl) silylene (cyclopentadienyl) (tetramethyldodecahydrodibenzofluorenyl) zirconium dichloride,
Di (p-tolyl) silylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride,
Di (p-tolyl) silylene (cyclopentadienyl) (hexamethyldihydrodicyclopentafluorenyl) zirconium dichloride,
Di (p-tolyl) silylene (cyclopentadienyl) (b, h-dibenzofluorenyl) zirconium dichloride,
Di (m-tolyl) silylene (cyclopentadienyl) (fluorenyl) zirconium dichloride,
Di (m-tolyl) silylene (cyclopentadienyl) (2,7-di-t-butylfluorenyl) zirconium dichloride,
Di (m-tolyl) silylene (cyclopentadienyl) (3,6-di-t-butylfluorenyl) zirconium dichloride,
Di (m-tolyl) silylene (cyclopentadienyl) (2,7-dimethyl-3,6-di-t-butylfluorenyl) zirconium dichloride,
Di (m-tolyl) silylene (cyclopentadienyl) (2,7-diphenyl-3,6-di-t-butylfluorenyl) zirconium dichloride,
Di (m-tolyl) silylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride,
Di (m-tolyl) silylene (cyclopentadienyl) (tetramethyldodecahydrodibenzofluorenyl) zirconium dichloride,
Di (m-tolyl) silylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride,
Di (m-tolyl) silylene (cyclopentadienyl) (hexamethyldihydrodicyclopentafluorenyl) zirconium dichloride,
Examples include di (m-tolyl) silylene (cyclopentadienyl) (b, h-dibenzofluorenyl) zirconium dichloride and the like.

In the case where Y is a carbon atom,
Diphenylmethylene (cyclopentadienyl) (3,6-di-t-butylfluorenyl) zirconium dichloride,
Diphenylmethylene (cyclopentadienyl) (2,7-dimethyl-3,6-di-t-butylfluorenyl) zirconium dichloride;
Diphenylmethylene (cyclopentadienyl) (2,7-diphenyl-3,6-di-t-butylfluorenyl) zirconium dichloride;
Diphenylmethylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride,
Diphenylmethylene (cyclopentadienyl) (tetramethyl dodecahydrodibenzofluorenyl) zirconium dichloride,
Diphenylmethylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride,
Diphenylmethylene (cyclopentadienyl) (hexamethyldihydrodicyclopentafluorenyl) zirconium dichloride,
Diphenylmethylene (cyclopentadienyl) (b, h-dibenzofluorenyl) zirconium dichloride,
Di (p-tolyl) methylene (cyclopentadienyl) (2,7-di-t-butylfluorenyl) zirconium dichloride,
Di (p-tolyl) methylene (cyclopentadienyl) (3,6-di-t-butylfluorenyl) zirconium dichloride,
Di (p-tolyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-di-t-butylfluorenyl) zirconium dichloride,
Di (p-tolyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-di-t-butylfluorenyl) zirconium dichloride,
Di (p-tolyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride,
Di (p-tolyl) methylene (cyclopentadienyl) (tetramethyldodecahydrodibenzofluorenyl) zirconium dichloride,
Di (p-tolyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride,
Di (p-tolyl) methylene (cyclopentadienyl) (hexamethyldihydrodicyclopentafluorenyl) zirconium dichloride,
Di (p-tolyl) methylene (cyclopentadienyl) (b, h-dibenzofluorenyl) zirconium dichloride,
Di (m-tolyl) methylene (cyclopentadienyl) (fluorenyl) zirconium dichloride,
Di (m-tolyl) methylene (cyclopentadienyl) (2,7-di-t-butylfluorenyl) zirconium dichloride,
Di (m-tolyl) methylene (cyclopentadienyl) (3,6-di-t-butylfluorenyl) zirconium dichloride,
Di (m-tolyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-di-t-butylfluorenyl) zirconium dichloride,
Di (m-tolyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-di-t-butylfluorenyl) zirconium dichloride,
Di (m-tolyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride,
Di (m-tolyl) methylene (cyclopentadienyl) (tetramethyldodecahydrodibenzofluorenyl) zirconium dichloride,
Di (m-tolyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride,
Di (m-tolyl) methylene (cyclopentadienyl) (hexamethyldihydrodicyclopentafluorenyl) zirconium dichloride,
Di (m-tolyl) methylene (cyclopentadienyl) (b, h-dibenzofluorenyl) zirconium dichloride,
Di (p-t-butylphenyl) methylene (cyclopentadienyl) (3,6-di-t-butylfluorenyl) zirconium dichloride,
Di (p-t-butylphenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-di-t-butylfluorenyl) zirconium dichloride,
Di (p-t-butylphenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-di-t-butylfluorenyl) zirconium dichloride,
Di (p-t-butylphenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride,
Di (p-t-butylphenyl) methylene (cyclopentadienyl) (tetramethyldodecahydrodibenzofluorenyl) zirconium dichloride,
Di (p-t-butylphenyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride,
Di (p-t-butylphenyl) methylene (cyclopentadienyl) (hexamethyldihydrodicyclopentafluorenyl) zirconium dichloride,
Di (p-t-butylphenyl) methylene (cyclopentadienyl) (b, h-dibenzofluorenyl) zirconium dichloride,
Di (4-biphenyl) methylene (cyclopentadienyl) (2,7-di-t-butylfluorenyl) zirconium dichloride,
Di (4-biphenyl) methylene (cyclopentadienyl) (3,6-di-t-butylfluorenyl) zirconium dichloride,
Di (4-biphenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-di-t-butylfluorenyl) zirconium dichloride,
Di (4-biphenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-di-t-butylfluorenyl) zirconium dichloride,
Di (4-biphenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride,
Di (4-biphenyl) methylene (cyclopentadienyl) (tetramethyldodecahydrodibenzofluorenyl) zirconium dichloride,
Di (4-biphenyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride,
Di (4-biphenyl) methylene (cyclopentadienyl) (hexamethyldihydrodicyclopentafluorenyl) zirconium dichloride,
Di (4-biphenyl) methylene (cyclopentadienyl) (b, h-dibenzofluorenyl) zirconium dichloride,
Di (p-chlorophenyl) methylene (cyclopentadienyl) (fluorenyl) zirconium dichloride,
Di (p-chlorophenyl) methylene (cyclopentadienyl) (2,7-di-t-butylfluorenyl) zirconium dichloride,
Di (p-chlorophenyl) methylene (cyclopentadienyl) (3,6-di-t-butylfluorenyl) zirconium dichloride,
Di (p-chlorophenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-di-t-butylfluorenyl) zirconium dichloride,
Di (p-chlorophenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-di-t-butylfluorenyl) zirconium dichloride,
Di (p-chlorophenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride,
Di (p-chlorophenyl) methylene (cyclopentadienyl) (tetramethyldodecahydrodibenzofluorenyl) zirconium dichloride,
Di (p-chlorophenyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride,
Di (p-chlorophenyl) methylene (cyclopentadienyl) (hexamethyldihydrodicyclopentafluorenyl) zirconium dichloride,
Di (p-chlorophenyl) methylene (cyclopentadienyl) (b, h-dibenzofluorenyl) zirconium dichloride,
Di (m-chlorophenyl) methylene (cyclopentadienyl) (fluorenyl) zirconium dichloride,
Di (m-chlorophenyl) methylene (cyclopentadienyl) (2,7-di-t-butylfluorenyl) zirconium dichloride,
Di (m-chlorophenyl) methylene (cyclopentadienyl) (3,6-di-t-butylfluorenyl) zirconium dichloride,
Di (m-chlorophenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-di-t-butylfluorenyl) zirconium dichloride,
Di (m-chlorophenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-di-t-butylfluorenyl) zirconium dichloride,
Di (m-chlorophenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride,
Di (m-chlorophenyl) methylene (cyclopentadienyl) (tetramethyldodecahydrodibenzofluorenyl) zirconium dichloride,
Di (m-chlorophenyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride,
Di (m-chlorophenyl) methylene (cyclopentadienyl) (hexamethyldihydrodicyclopentafluorenyl) zirconium dichloride,
Di (m-chlorophenyl) methylene (cyclopentadienyl) (b, h-dibenzofluorenyl) zirconium dichloride,
Di (m-trifluoromethylphenyl) methylene (cyclopentadienyl) (fluorenyl) zirconium dichloride,
Di (m-trifluoromethylphenyl) methylene (cyclopentadienyl) (2,7-di-t-butylfluorenyl) zirconium dichloride,
Di (m-trifluoromethylphenyl) methylene (cyclopentadienyl) (3,6-di-t-butylfluorenyl) zirconium dichloride,
Di (m-trifluoromethylphenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-di-t-butylfluorenyl) zirconium dichloride,
Di (m-trifluoromethylphenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-di-t-butylfluorenyl) zirconium dichloride,
Di (m-trifluoromethylphenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride,
Di (m-trifluoromethylphenyl) methylene (cyclopentadienyl) (tetramethyldodecahydrodibenzofluorenyl) zirconium dichloride,
Di (m-trifluoromethylphenyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride,
Di (m-trifluoromethylphenyl) methylene (cyclopentadienyl) (hexamethyldihydrodicyclopentafluorenyl) zirconium dichloride,
Di (m-trifluoromethylphenyl) methylene (cyclopentadienyl) (b, h-dibenzofluorenyl) zirconium dichloride,
Di (2-naphthyl) methylene (cyclopentadienyl) (2,7-di-t-butylfluorenyl) zirconium dichloride,
Di (2-naphthyl) methylene (cyclopentadienyl) (3,6-di-t-butylfluorenyl) zirconium dichloride,
Di (2-naphthyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-di-t-butylfluorenyl) zirconium dichloride,
Di (2-naphthyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-di-t-butylfluorenyl) zirconium dichloride,
Di (2-naphthyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride,
Di (2-naphthyl) methylene (cyclopentadienyl) (tetramethyldodecahydrodibenzofluorenyl) zirconium dichloride,
Di (2-naphthyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride,
Di (2-naphthyl) methylene (cyclopentadienyl) (hexamethyldihydrodicyclopentafluorenyl) zirconium dichloride,
Di (2-naphthyl) methylene (cyclopentadienyl) (b, h-dibenzofluorenyl) zirconium dichloride and the like can be mentioned.

  Examples of structural formulas of these metallocene compounds include di (p-tolyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride (the following (A)), and di (p-chlorophenyl): The structural formula of the (methylene) (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride (the following (B)) is shown below.

  The above metallocene compounds may be used alone or in combination of two or more.

  The metallocene compound represented by the above-mentioned formula [A1] which can be suitably used for preparation of the above-mentioned copolymer (A) can be manufactured by arbitrary methods, without being limited in particular. For example, J. Organomet. Chem. , 63, 509 (1996), WO 2005/100410, WO 2006/123759, WO 01/27124, JP-A 2004-168744, JP-A 2004-175759, JP-A 2000-212194, etc. It can manufacture based on the method as described in these.

«Catalysts containing metallocene compounds»
Examples of the polymerization catalyst that can be suitably used for the production of the above-mentioned copolymer (A) include those containing the aforementioned metallocene compound [A1] and capable of copolymerizing monomers.

Preferably,
(A) A metallocene compound represented by the above general formula [A1],
(B) (b-1) at least one selected from organic metal compounds, (b-2) organic aluminum oxy compounds, and (b-3) compounds which react with the metallocene compound (a) to form an ion pair Compounds of the formula (hereinafter also referred to as "ionized ionic compounds"),
If necessary,
(C) A polymerization catalyst composed of a particulate carrier can be mentioned. Each component will be specifically described below.

<< Compound (b) >>
The compound (b) is at least one compound selected from (b-1) organometallic compounds, (b-2) organoaluminum oxy compounds and (b-3) ionizing ionic compounds, preferably at least one compound It contains the organometallic compound (b-1).

(B-1) Organometallic Compound Examples of the organometallic compound (b-1) include organic compounds of Groups 1, 2 and 12, and 13 of the periodic table such as the following General Formulas [VII] to [IX]. Metal compounds are used.

(B-1a) _{^{formula: R a m Al (OR b}} ) n H p X q ... [VII]
(In the formula [VII], R ^a and R ^b may be the same or different, each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and X represents a halogen atom, m is 0 <m ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, q is a number of 0 ≦ q <3, and m + n + p + q = 3) Compound.

  Such compounds include trialkylaluminums such as trimethylaluminum, triethylaluminum, triisobutylaluminum, tri n-octylaluminum, tricycloalkylaluminum, isobutylaluminum dichloride, diethylaluminum chloride, ethylaluminum dichloride, ethylaluminum sesquichloride, methyl Aluminum dichloride, dimethylaluminum chloride and diisobutylaluminum hydride can be exemplified.

(B-1b) General formula: M ² AlR ^a ₄ ... [VIII]
(In the formula [VIII], M ² represents Li, Na or K, and R ^a is a hydrocarbon group having 1 to 15, preferably 1 to 4 carbon atoms). Complex alkylated with Group 1 metal and aluminum.

As such a compound, LiAl (C ₂ H ₅ ) ₄ , LiAl (C ₇ H ₁₅ ) _{4 and the} like can be exemplified.

(B-1c) General formula: R ^a R ^b M ³ ... [IX]
(In formula [IX], R ^a and R ^b may be the same or different, and represent a hydrocarbon group having 1 to 15, preferably 1 to 4 carbon atoms, and M ³ represents Mg, Zn or A dialkyl compound having a metal of Group 2 or Group 12 of the periodic table represented by the formula Cd).

  Among the above organic metal compounds (b-1), organic aluminum compounds such as triethylaluminum, triisobutylaluminum and tri n-octylaluminum are preferable. Moreover, such an organometallic compound (b-1) may be used individually by 1 type, and may be used in combination of 2 or more types.

(B-2) Organoaluminum oxy compound The organoaluminum oxy compound (b-2) may be a conventionally known aluminoxane, or a benzene insoluble organic compound as exemplified in JP-A-2-78687. It may be an aluminum oxy compound.

A conventionally known aluminoxane can be produced, for example, by the following method, and is usually obtained as a solution of a hydrocarbon solvent.
(1) Compounds containing adsorbed water or salts containing crystal water, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, cerous chloride hydrate, etc. A method in which an organoaluminum compound such as trialkylaluminum is added to a hydrocarbon medium suspension in the above to cause adsorbed water or crystal water to react with the organoaluminum compound.
(2) A method in which water, ice or water vapor is allowed to directly act on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran.
(3) A method of reacting an organotin oxide such as dimethyltin oxide or dibutyltin oxide with an organoaluminum compound such as trialkylaluminum in a medium such as decane, benzene or toluene.

  The aluminoxane may contain a small amount of an organic metal component. Alternatively, the solvent or unreacted organoaluminum compound may be distilled off from the recovered solution of the aluminoxane, and then redissolved in the solvent or suspended in the poor solvent of the aluminoxane.

  As an organic aluminum compound used when preparing an aluminoxane, the organic aluminum compound similar to what was illustrated as an organic aluminum compound which belongs to said (b-1a) can be mentioned.

  Among these, trialkylaluminum and tricycloalkylaluminum are preferable, and among them, trimethylaluminum and triisobutylaluminum are particularly preferable.

  The organoaluminum compounds as described above are used singly or in combination of two or more.

  Further, in the benzene-insoluble organoaluminum oxy compound which is one aspect of the organoaluminum oxy compound (b-2) used in the present invention, the Al component dissolved in benzene at 60 ° C. is 100% by weight of benzene in terms of Al atom. Usually, one having 10% by weight or less, preferably 5% by weight or less, particularly preferably 2% by weight or less, that is, one insoluble or poorly soluble in benzene is preferred.

  As the organoaluminum oxy compound (b-2) used in the present invention, an organoaluminum oxy compound containing boron represented by the following general formula [X] can also be mentioned.

In formula [X], R ¹ represents a hydrocarbon group having 1 to 10 carbon atoms, R ^{2 to} R ⁵ may be the same as or different from each other, and a hydrogen atom, a halogen atom, or 1 carbon atom -10 hydrocarbon groups are shown.

The organoaluminum oxy compound containing boron represented by the above general formula [X] is
General formula: R ¹ -B (OH) ₂ ... [XI]
(In formula [XI], R ¹ represents the same group as R ¹ in the general formula [X].)
And an alkyl boronic acid represented by
The reaction can be carried out by reacting an organoaluminum compound in an inert solvent under an inert gas atmosphere at a temperature of −80 ° C. to room temperature for 1 minute to 24 hours.

  As the alkylboronic acid represented by the above general formula [XI], methylboronic acid, ethylboronic acid, isopropylboronic acid, n-propylboronic acid, n-butylboronic acid, isobutylboronic acid, n-hexylboronic acid, cyclohexylboronic acid And phenylboronic acid, 3,5-difluorophenylboronic acid, pentafluorophenylboronic acid, 3,5-bis (trifluoromethyl) phenylboronic acid and the like.

  Among these, methylboronic acid, n-butylboronic acid, isobutylboronic acid, 3,5-difluorophenylboronic acid and pentafluorophenylboronic acid are preferable. These are used singly or in combination of two or more.

  As the organoaluminum compound to be reacted with such an alkylboronic acid, the same organoaluminum compounds as exemplified as the organoaluminum compound belonging to the above (b-1a) can be mentioned. Among these, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum, triethylaluminum and triisobutylaluminum are particularly preferable.

  The organoaluminum oxy compounds (b-2) as described above are used singly or in combination of two or more.

(B-3) Ionizing Ionizable Compound Examples of the ionizing ionic compound (b-3) include: JP-A Nos. 1-501950, 1-502036, 3-179005 and 3-179005. Examples thereof include Lewis acids, ionic compounds, borane compounds and carborane compounds described in, for example, 179006, JP-A-3-207703, JP-A-3-207704 and USP 5321106. Furthermore, heteropoly compounds and isopoly compounds can also be mentioned. Such ionizing ionic compounds (b-3) may be used alone or in combination of two or more.

Specifically, examples of the Lewis acid include compounds represented by BR ₃ (R is a phenyl group which may have a substituent such as fluorine, a methyl group or a trifluoromethyl group, or fluorine). For example, trifluoroboron, triphenylboron, tris (4-fluorophenyl) boron, tris (3,5-difluorophenyl) boron, tris (4-fluoromethylphenyl) boron, tris (pentafluorophenyl) boron, tris ( p-Tolyl) boron, tris (o-tolyl) boron, tris (3,5-dimethylphenyl) boron and the like can be mentioned.
As an ionic compound, the compound represented, for example by the following general formula [XII] is mentioned.

In the formula [XII], as R ¹⁺ , H ⁺ , a carbonium cation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptitrilienyl cation, a ferrocenium cation having a transition metal, and the like can be mentioned. R ^{2 to} R ⁵ may be the same as or different from each other, and are an organic group, preferably an aryl group or a substituted aryl group.

  Specific examples of the carbonium cation include trisubstituted carbonium cations such as triphenyl carbonium cation, tri (methyl phenyl) carbonium cation and tri (dimethyl phenyl) carbonium cation.

Specific examples of the ammonium cation include trialkyl ammonium cations such as trimethyl ammonium cation, triethyl ammonium cation, tripropyl ammonium cation, tributyl ammonium cation and tri (n-butyl) ammonium cation;
N, N-dialkylanilinium cations such as N, N-dimethylanilinium cations, N, N-diethylanilinium cations, N, N, 2,4,6-pentamethylanilinium cations;
And dialkyl ammonium cations such as di (isopropyl) ammonium cation and dicyclohexyl ammonium cation.

  Specific examples of the phosphonium cation include triaryl phosphonium cations such as triphenyl phosphonium cation, tri (methyl phenyl) phosphonium cation and tri (dimethyl phenyl) phosphonium cation.

As R ^<1+> , a carbonium cation, an ammonium cation, etc. are preferable, and a triphenyl carbonium cation, a N, N- dimethylanilinium cation, and a N, N-diethylanilinium cation are particularly preferable.

  Moreover, a trialkyl substituted ammonium salt, a N, N- dialkyl anilinium salt, a dialkyl ammonium salt, a triaryl phosphonium salt etc. can also be mentioned as an ionic compound.

  Specific examples of the trialkyl-substituted ammonium salt include, for example, triethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, tri (n-butyl) ammonium tetra (phenyl) boron, trimethylammonium tetra (p-tolyl) Boron, trimethylammonium tetra (o-tolyl) boron, tri (n-butyl) ammonium tetra (pentafluorophenyl) boron, tripropylammonium tetra (o, p-dimethylphenyl) boron, tri (n-butyl) ammonium tetra (t) N, N-dimethylphenyl) boron, tri (n-butyl) ammonium tetra (p-trifluoromethylphenyl) boron, tri (n-butyl) ammonium tetra (3,5-ditrifluoromethylphene) Le) boron, tri (n- butyl) ammonium tetra (o-tolyl) and boron and the like.

  Specific examples of the N, N-dialkylanilinium salt include, for example, N, N-dimethylanilinium tetra (phenyl) boron, N, N-diethylanilinium tetra (phenyl) boron, N, N, 2,4,6 -Pentamethylanilinium tetra (phenyl) boron etc. are mentioned.

  Specific examples of the dialkyl ammonium salt include di (1-propyl) ammonium tetra (pentafluorophenyl) boron and dicyclohexylammonium tetra (phenyl) boron.

  Furthermore, as an ionic compound, triphenylcarbenium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, ferrocenium tetra (pentafluorophenyl) borate, triphenylcarbenium pentaphenyl Cyclopentadienyl complexes, N, N-diethylanilinium pentaphenylcyclopentadienyl complexes, boron compounds represented by the following formula [XIII] or [XIV], and the like can also be mentioned. In the following formulas, Et represents an ethyl group.

Specifically as a borane compound, for example, decaborane;
Bis [tri (n-butyl) ammonium] nonaborate, bis [tri (n-butyl) ammonium] decaborate, bis [tri (n-butyl) ammonium] undecaborate, bis [tri (n-butyl) ammonium] dodecaborate And salts of anions such as bis [tri (n-butyl) ammonium] decachlorodecaborate and bis [tri (n-butyl) ammonium] dodecachlorododecaborate;
Of metal borane anions such as tri (n-butyl) ammonium bis (dodecahydride dodecaborate) cobaltate (III), bis [tri (n-butyl) ammonium] bis (dodecahydrate dodecaborate) nickelate (III) Salt etc. are mentioned.

Specifically as a carborane compound, for example, 4-carbanonaborane, 1,3-dicarbanonaborane, 6,9-dicarbadecaborane, dodecahydride-1-phenyl-1,3-dicarbanonaborane, dodecahydride -1-methyl-1,3-dicarbanonaborane, undecahydride-1,3-dimethyl-1,3-dicarbanonaborane, 7,8-dicarbaundecaborane, 2,7-dicarbaundecaborane Undecahydride-7,8-dimethyl-7,8-dicarbaundecaborane, dodecahydride-11-methyl-2,7-dicarbaundecaborane, tri (n-butyl) ammonium 1-carbadecaborate, tri (N-butyl) ammonium-1-carbundecaborate, tri (n-butyl) ammonium-1-cal Dodecaborate, tri (n-butyl) ammonium-1-trimethylsilyl-1-carbadecaborate, tri (n-butyl) ammonium bromo-1-carbadodecaborate, tri (n-butyl) ammonium-6-carbadecaborate, Tri (n-butyl) ammonium-7-carbaundecaborate, tri (n-butyl) ammonium-7,8-dicarbaundecaborate, tri (n-butyl) ammonium-2,9-dicarbaundecaborate, tri (N-butyl) ammonium dodecahydride-8-methyl-7,9-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-8-ethyl-7,9-dicarbaundecaborate, tri (n-butyl) ammonium Butyl) ammonium undecahydride-8-butyl-7 , 9-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-8-allyl-7,9-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-9-trimethylsilyl-7,8 Salts of anions such as dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-4,6-dibromo-7-carbaundecaborate;
Tri (n-butyl) ammonium bis (nonahydride-1,3-dicarbanonaborate) cobalt acid salt (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) Ferrite (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) cobaltate (III), tri (n-butyl) ammonium bis (undecahydride-7) , 8-Dicarbaundecaborate) nickelate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) cuprate (III), tri (n-butyl) Ammonium bis (undecahydride-7,8-dicarbaundecaborate) aborate (III), tri (n-butyl) ammonium Bis (nonahydride-7,8-dimethyl-7,8-dicarbaundecaborate) ferrate (III), tri (n-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dical) Boundecaborate) chromate (III), tri (n-butyl) ammonium bis (tribromooctahydride-7,8-dicarbaundecaborate) cobaltate (III), tris [tri (n-butyl) ammonium ] Bis (undecahydride-7-carbundecaborate) chromate (III), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carbundecaborate) manganate (IV) Bis (tri (n-butyl) ammonium) bis (undecahydride-7-carbundecaborate) cobalt acid (III), such as bis [tri (n- butyl) ammonium] bis (carborane borate) salt of a metal carborane anions such as nickel salt (IV).

  The heteropoly compound is composed of an atom selected from silicon, phosphorus, titanium, germanium, arsenic and tin, and one or more atoms selected from vanadium, niobium, molybdenum and tungsten. Specifically, phosphorus vanadic acid, germano vanadic acid, arsenic vanadic acid, phosphoniobic acid, germano niobic acid, silicono molybdic acid, phosphomolybdic acid, titanium molybdic acid, germano molybdic acid, arsenic molybdic acid, tin molybdic acid, phosphorus Tungstic acid, germanotungstic acid, tin tungstic acid, linmolybdovanadic acid, lintungstovanadic acid, germanotungstovanadic acid, linmolybd tangstovanadic acid, germano molybd tungstovanadic acid, linmolybd tungstic acid , Linmolybdo niobic acid, and salts of these acids, such as metals of group 1 or 2 of the periodic table, specifically lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium Etc Salts, and organic salts such as triphenylethyl salts can be used, not limited thereto.

  Among the ionizing ionic compounds (b-3), the above-mentioned ionic compounds are preferable, among which triphenylcarbenium tetrakis (pentafluorophenyl) borate and N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate are preferred. More preferable.

  In the present invention, as a polymerization catalyst, a metallocene compound (a) represented by the above general formula [A1], an organic metal compound (b-1) such as triisobutylaluminum, an organic aluminum oxy compound (b-) such as methylaluminoxane 2) and the use of a metallocene catalyst containing an ionizing ionic compound (b-3) such as triphenylcarbenium tetrakis (pentafluorophenyl) borate, the polymerization activity of the copolymer (A) is very high. Can be shown.

(C) Particulate carrier In the present invention, the (c) particulate carrier which is optionally used is an inorganic compound or an organic compound, and is a granular or particulate solid.

  As the inorganic compound, a porous oxide, an inorganic halide, a clay, a clay mineral or an ion exchange layered compound is preferable. Specific examples thereof include those described in WO 2015/122495.

  The clay, clay mineral, and ion exchange layered compound used in the present invention may be used as it is, or may be used after processing such as ball milling and sieving. In addition, water may be newly added and adsorbed, or may be used after being subjected to heat dehydration treatment. Furthermore, they may be used alone or in combination of two or more.

  Among these, preferred are clays or clay minerals, and particularly preferred are montmorillonite, vermiculite, hectorite, teniolite and synthetic mica.

  As the organic compound, granular or particulate solid having a particle size in the range of 10 to 300 μm can be mentioned. Specifically, (co) polymers produced from an α-olefin having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene, 4-methyl-1-pentene as a main component, or vinylcyclohexane, styrene The (co) polymers produced by using as a main component and their modified products can be exemplified.

  The metallocene catalyst used in the present invention is at least one selected from a metallocene compound (a), an organometallic compound (b-1), an organoaluminum oxy compound (b-2) and an ionizing ionic compound (b-3) A specific organic compound component (d) can also be included, if necessary, together with a species compound (b) and, if necessary, a carrier (c).

(D) Organic Compound Component In the present invention, the organic compound component (d) is used for the purpose of improving the polymerization performance and the physical properties of the produced polymer as required. Examples of such organic compounds include alcohols, phenolic compounds, carboxylic acids, phosphorus compounds and sulfonates, but not limited thereto.

<< Method and conditions for producing copolymer (A) >>
The above-mentioned copolymer (A) comprises ethylene (a1), α-olefin having 3 to 20 carbon atoms (a2), non-conjugated polyene (a3) and, if necessary, non-conjugated polyene (a4) Can be produced by copolymerizing the following monomers.

When such a monomer is copolymerized, the usage method and addition order of each component which comprise the polymerization catalyst mentioned above are chosen arbitrarily, but methods like following (1)-(5) are illustrated.
(1) A method of independently adding a metallocene compound (a) to a polymerization vessel.
(2) A method in which the metallocene compound (a) and the compound (b) are added to the polymerizer in any order.
(3) A method of adding a catalyst component having a metallocene compound (a) supported on a carrier (c) and a compound (b) in any order to a polymerizer.
(4) A method in which the catalyst component supporting the compound (b) on the carrier (c) and the metallocene compound (a) are added to the polymerization vessel in an arbitrary order.
(5) A method of adding a catalyst component having a metallocene compound (a) and a compound (b) supported on a carrier (c) to a polymerizer.

  In each of the methods (2) to (5), at least two of the metallocene compound (a), the compound (b) and the carrier (c) may be contacted in advance.

  In each of the methods (4) and (5) in which the compound (b) is supported, the compound (b) not supported may be added in an arbitrary order, as necessary. In this case, the compound (b) may be the same as or different from the compound (b) carried on the carrier (c).

  The solid catalyst component having the metallocene compound (a) supported on the carrier (c) and the solid catalyst component having the metallocene compound (a) and the compound (b) supported on the carrier (c) is olefin prepolymerization The catalyst component may further be supported on the prepolymerized solid catalyst component.

  The copolymer (A) can be suitably obtained by copolymerizing monomers in the presence of a polymerization catalyst as described above.

The metallocene compound (a) is usually 10 ^-12 to 10 ^-2 mol, preferably 10 ^-10 to 10 ^-8 mol, per liter of the reaction volume when the polymerization of olefin is carried out using the polymerization catalyst as described above. It is used in such an amount that

  In the compound (b-1), the molar ratio [(b-1) / M] of the compound (b-1) to all transition metal atoms (M) in the metallocene compound (a) is usually 0.01 to 0.01. It is used in an amount of 50,000, preferably 0.05 to 10,000. In the compound (b-2), the molar ratio [(b-2) / M] of the aluminum atom in the compound (b-2) to the total transition metal (M) in the metallocene compound (a) is usually 10 It is used in an amount of about 50000, preferably 20 to 10,000. In the compound (b-3), the molar ratio [(b-3) / M] of the compound (b-3) to the transition metal atom (M) in the metallocene compound (a) is usually 1 to 20, preferably Is used in an amount of 1 to 15.

  In the present invention, the method for producing the copolymer (A) can be carried out in any of liquid phase polymerization methods such as solution (solution) polymerization and suspension polymerization, or gas phase polymerization methods, and is not particularly limited. It is preferable to have the process of obtaining the following polymerization reaction liquid.

In the step of obtaining a polymerization reaction solution, an aliphatic hydrocarbon is used as a polymerization solvent, and the above metallocene catalyst, preferably, R ¹³ and R ¹⁴ bonded to Y ¹ in the general formula [A1] is a phenyl group or , An alkyl group or a phenyl group substituted by a halogen group, and R ⁷ and R ^{10 each} have an alkyl substituent-containing transition metal compound in the presence of a polymerization catalyst containing ethylene (a1) and 3 to 20 carbon atoms The step of obtaining a polymerization reaction liquid of the copolymer (A) by copolymerizing a monomer consisting of the α-olefin (a2) of the above, a nonconjugated polyene (a3) and optionally a nonconjugated polyene (a4) .

  Examples of the polymerization solvent include aliphatic hydrocarbons and aromatic hydrocarbons. Specifically, aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane and kerosene, alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclopentane, benzene, toluene and xylene And aromatic hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane, and the like, and they can be used singly or in combination of two or more. Also, olefin itself can be used as a solvent. Among these, hexane is preferable from the viewpoint of separation with the copolymer (A) to be obtained and purification.

  The polymerization temperature is usually in the range of -50 to + 200 ° C, preferably in the range of 0 to + 150 ° C, more preferably in the range of +70 to + 110 ° C, although depending on the ultimate molecular weight of the metallocene catalyst system used and the polymerization activity It is desirable from the viewpoint of catalyst activity, copolymerizability and productivity that it is (+ 70 ° C. or higher).

  The polymerization pressure is usually atmospheric pressure to 10 MPa gauge pressure, preferably 1.1 to 5 MPa gauge pressure, more preferably 1.2 to 2.0 MPa gauge pressure, and the polymerization reaction is batchwise or semicontinuous. And any continuous method. Furthermore, it is also possible to divide the polymerization into two or more stages under different reaction conditions. In the present invention, among these, it is preferable to adopt a method of continuously supplying monomers to the reactor to carry out copolymerization.

  The reaction time (average residence time when copolymerization is carried out continuously) varies depending on the conditions such as catalyst concentration and polymerization temperature, but it is usually 0.5 minutes to 5 hours, preferably 5 minutes to 3 hours And more preferably 10 minutes to 2 hours.

  The molecular weight of the resulting copolymer (A) can also be adjusted by the presence of hydrogen in the polymerization system or by changing the polymerization temperature. Furthermore, it can also be adjusted by the amount of compound (b) used. Specifically, triisobutylaluminum, methylaluminoxane, diethyl zinc and the like can be mentioned. When hydrogen is added, its amount is suitably about 0.001 to 100 NL per kg of olefin.

  Further, the molar ratio of ethylene (a1) to the above α-olefin (a2) (ethylene (a1) / α-olefin (a2)) is preferably 40/60 to 99.9 / 0.1, It is preferably 50/50 to 90/10, more preferably 55/45 to 85/15, and most preferably 55/45 to 78/22.

  The preparation amount of the non-conjugated polyene (a3) is usually 0. 1% with respect to 100% by weight of the total (total monomer preparation amount) of ethylene (a1), α-olefin (a2) and non-conjugated polyene (a3). It is 07 to 10% by weight, preferably 0.1 to 8.0% by weight, and more preferably 0.5 to 5.0% by weight.

In the present invention, it is preferable to include the step (2) of deactivating the polymerization catalyst by adding a catalyst deactivator after the step (1) of performing copolymerization in the presence of the polymerization catalyst.
As the catalyst deactivator, alcohols can be used, methanol or ethanol is preferable, and ethanol is particularly preferable.

  In the step (2), the catalyst deactivator is preferably 0.05 to 3.0 mol times, more preferably 0.06 to 2.5 mol times the organic metal compound (b-1), More preferably, when added in an amount of 0.08 to 2.0 mol times, a catalyst denatured agent such as ethanol is slightly generated as a catalyst denatured to polymerize low molecular weight components moderately, resulting in appropriate molecular weight distribution. The copolymer (A) can be obtained in a wide range. On the other hand, when the addition amount of the catalyst deactivator is too large, the deterioration catalyst is hardly generated and the polymerization of the low molecular weight component is hardly performed, so that the molecular weight distribution of the obtained copolymer (A) tends to be narrow. is there. In addition, when the catalyst deactivator is not added or the addition amount is too small, a large amount of a deterioration catalyst is generated to polymerize a large amount of low molecular weight components, so the content of the low molecular weight components of the obtained copolymer (A) Tend to be too much.

<Hydrophobic silica (B)>
The hydrophobic silica (B) used in the present invention is one which has been surface-treated with octylsilane. By using such hydrophobic silica (B), it is possible to improve the dynamic magnification and compression set of the resulting vibration-proof rubber.

The average particle diameter of the hydrophobic silica (B) is preferably 1 to 50 nm, more preferably 2 to 45 nm, and still more preferably 5 to 40 nm. When the average particle size is in the above range, the dispersibility of the hydrophobic silica (B) in the composition is excellent. Further, the specific surface area of the hydrophobic silica (B) (BED method) is preferably 50 m ² / g or more, more preferably 100 to 400 m ² / g.

  As the silica before the surface treatment, those produced by a known method can be used, but those produced by a dry method or a high temperature hydrolysis method are preferable. Moreover, it does not specifically limit as a method of surface treatment by octylsilane, A well-known method is applicable.

The octyl silane, octyl group (C 8 _H 17 _-) is not particularly limited as long as it is a silane compound containing, for example, n- octyltriethoxysilane, etc. n- octyl dimethyl chlorosilane and the like.

  As a commercial item of the said hydrophobic silica (B), R805 of Aerosil series made from EVONIK, TG-C243, TG-C390, TG-3130 of CAB-O-SIL series made by Cabot, etc. are mentioned, for example .

  The content of the hydrophobic silica (B) in the composition of the present invention is 1 to 100 parts by weight, preferably 5 to 60 parts by weight, more preferably 10 to 50 parts by weight with respect to 100 parts by weight of the above-mentioned copolymer Range. When the content of the hydrophobic silica (B) is in the above range, the effect of improving the dynamic magnification and the compression set is excellent.

<Zinc oxide (C)>
As zinc oxide (C) which can be used in the present invention, for example, those commercially available under the names of zinc flower, active zinc flower, complex zinc flower, surface treated zinc flower, complex activated zinc flower and the like can be mentioned. Be Among these, active zinc flower is preferable because it exhibits a high activation effect.

The specific surface area of the zinc oxide (C) is preferably in the range of 1 to 100 m ² / g, in particular in the range of 10 to 80 m ² / g in the case of the active zinc white is preferable. In addition, the average particle diameter of zinc oxide (C) is preferably in the range of 0.01 to 100 μm, and particularly in the case of active zinc flower, in the range of 0.05 to 20 μm. When the specific surface area and the average particle size are in the above ranges, a high activation effect is exhibited.

  Such zinc oxide (C) acts as a vulcanization accelerator at the time of molding, and when a fatty acid is present, it forms a complex therewith to enhance the activity of the vulcanization accelerator and improve the vulcanization rate. Zinc oxide (C) also acts as a bulking agent. Zinc oxide (C) may be used alone or in combination of two or more.

  The content of zinc oxide (C) in the composition of the present invention is preferably 0.2 to 15 parts by weight, preferably 0.5 to 10 parts by weight, further 100 parts by weight of the copolymer (A). Preferably, it is in the range of 1 to 8 parts by weight. When the content of zinc oxide (C) is in the above range, a vibration-proof rubber excellent in vibration-proof characteristics is obtained.

<Other ingredients>
The composition of the present invention is not limited to the components (A) to (C) as long as the object of the present invention is not impaired, rubber additives known per se, such as organic peroxides, α, β- Metal salts of unsaturated organic acids, carbon black, softeners, antioxidants, crosslinking aids, crosslinking accelerators, fillers, processing aids, activators, antioxidants, foaming agents, plasticizers, tackifiers, etc. Can be blended appropriately.

«Organic peroxides»
When the composition of the present invention contains an organic peroxide as a crosslinking agent, as the organic peroxide, conventionally known organic peroxides usually used in crosslinking of rubber can be used. .

In particular,
Dicumyl peroxide, di-t-butyl peroxide, di-t-butylperoxy-3,3,5-trimethylcyclohexane, t-butylcumyl peroxide, di-t-amyl peroxide, 2,5-dimethyl-2,5 -Di (t-butylperoxy) hexyne-3,2,5-dimethyl-2,5-di (benzoylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, α , Alkyl peroxides such as α'-bis (t-butylperoxy-m-isopropyl) benzene and t-butyl hydroperoxide;
t-Butylperoxyacetate, t-butylperoxyisobutyrate, t-butylperoxypivalate, t-butylperoxymaleic acid, t-butylperoxyneodecanoate, t-butylperoxybenzoate, di-t-butylperoxyphthalate Peroxyesters such as;
And ketone peroxides such as dicyclohexanone peroxide. These can be used alone or in combination of two or more. Among these, organic peroxides having a one-minute half-life temperature of 130 to 200 ° C. are preferable. For example, dicumyl peroxide, di-t-butyl peroxide, di-t-butylperoxy-3,3,5-trimethyl Preferred are cyclohexane, t-butylcumyl peroxide, di-t-amyl peroxide and t-butyl hydroperoxide.

  The organic peroxide is 100 parts by weight of the above copolymer (A) in the composition of the present invention from the viewpoint of prevention of adverse effects due to excessive decomposition products and cost, as well as obtaining desired physical properties by sufficient crosslinking. It is preferably used in an amount of 1 to 10 parts by weight, more preferably 2 to 8 parts by weight, based on part.

«Metal salt of α, β- unsaturated organic acid»
When the composition of the present invention contains a metal salt of an α, β-unsaturated organic acid, the dynamic fatigue resistance and the abrasion resistance of the composition can be improved in a well-balanced manner.

  As metal salts of α, β-unsaturated organic acids, for example, acrylic acid, methacrylic acid, maleic acid, fumaric acid, ethacrylic acid, vinyl-acrylic acid, itaconic acid, methylitaconic acid, aconitic acid, methylaconic acid, Metal salts of acids such as crotonic acid, alpha-methyl crotonic acid, cinnamic acid and 2,4-dihydroxy cinnamic acid. These salts can be zinc, cadmium, calcium, magnesium, sodium or aluminum salts, but in particular zinc salts. Preferred metal salts of α, β-unsaturated organic acids are zinc diacrylate and zinc dimethacrylate, particularly preferably zinc dimethacrylate. The metal salts of α, β-unsaturated organic acids can be used alone or in combination of two or more.

  The metal salt of the α, β-unsaturated organic acid is preferably 5 to 30 parts by weight, more preferably 5 to 25 parts by weight, particularly preferably 7 to 25 parts by weight with respect to 100 parts by weight of the copolymer rubber (A). It is used in the range of 20 parts by weight.

«Carbon black»
When the composition of the present invention contains a specific amount of carbon black, it is possible to improve the processability of the composition and to obtain a rubber composition having improved mechanical properties such as tensile strength, tear strength and abrasion resistance. it can.

  As carbon black, for example, Asahi # 55 G, Asahi # 60 G (all, Asahi Carbon Co., Ltd. product), Siest (SRF, GPF, FEF, MAF, HAF, ISAF, SAF, SAF, FT, MT, G-SO, etc.) A known material such as (manufactured by Tokai Carbon Co., Ltd.) can be used. These can be used alone or in combination. Moreover, what was surface-treated by the silane coupling agent etc. can also be used.

  The carbon black is preferably in the range of 0.1 to 100 parts by weight, more preferably 0.5 to 50 parts by weight, and particularly preferably 1 to 20 parts by weight with respect to 100 parts by weight of the copolymer rubber (A). Used in If the compounding amount of carbon black is in the above range, a rubber composition excellent in dynamic magnification (dynamic elastic modulus / static elastic modulus), processability, mechanical properties and the like can be obtained.

«Softeners»
As the softener, known softeners used in general rubber compositions can be used. Specifically, petroleum-based softeners such as process oil, lubricating oil, liquid paraffin, petroleum asphalt, vaseline; coal tar-based softeners such as coal tar and coal tar pitch; castor oil, linseed oil, rapeseed oil, soybean oil Fatty oil-based softeners such as coconut oil; tall oil; sub (factice); waxes such as beeswax, carnauba wax, lanolin, etc .: ricinoleic acid, palmitic acid, stearic acid, barium stearate, calcium stearate, zinc laurate, etc. Fatty acids and fatty acid salts; and synthetic polymers such as petroleum resins, atactic polypropylene and coumarone indene resins. Among them, petroleum-based softeners are preferable, process oils are more preferable, paraffin-based process oils, naphthene-based process oils, aroma-based process oils and the like are more preferable, and paraffin-based process oils are particularly preferable. These softeners can be used alone or in combination of two or more.

  The softening agent is preferably used in an amount of 20 to 150 parts by weight, more preferably 20 to 80 parts by weight, and particularly preferably 20 to 70 parts by weight with respect to 100 parts by weight of the copolymer rubber (A). When the amount of the softener (E) is within the above range, it is possible to obtain a rubber composition which has low tack and is excellent in processability, heat aging resistance, mechanical properties and the like.

«Anti-aging agent»
As an antiaging agent, the well-known antiaging agent used for a general rubber composition can be used. Specifically, sulfur based antioxidants, phenol based antioxidants, amine based antioxidants and the like can be mentioned.

  In the present invention, although the anti-aging agent may be used alone, it is preferable to use a combination of two or more in view of maintaining heat aging resistance for a long time under high temperature.

  In the present invention, the sulfur-based antioxidant is preferably 0.2 to 10 parts by weight, more preferably 0.2 to 8 parts by weight, particularly preferably 0.2 to 10 parts by weight, per 100 parts by weight of the copolymer (A). It can be used in the range of 2 to 6 parts by weight. It is preferable to use a sulfur-based anti-aging agent in the above-mentioned range because the effect of improving the heat aging resistance is large, and furthermore, the crosslinking of the composition of the present invention is not inhibited.

  The phenolic antioxidant is preferably 0.2 to 5 parts by weight, more preferably 0.5 to 4 parts by weight, particularly preferably 0.5 to 3 parts by weight, per 100 parts by weight of the copolymer (A). It can be used in the range of parts. It is preferable to use a phenolic anti-aging agent in the above range because the effect of improving the heat aging resistance is large, and furthermore, the crosslinking of the composition of the present invention is not inhibited.

  The amine-based antioxidant is preferably 0.05 to 5 parts by weight, more preferably 0.1 to 4 parts by weight, particularly preferably 0.2 to 3 parts by weight per 100 parts by weight of the copolymer (A). Used in the range of parts. It is preferable to use an amine-based anti-aging agent in the above-mentioned range because the effect of improving the heat aging resistance is large, and furthermore, the crosslinking of the composition of the present invention is not inhibited.

«Crosslinking aids»
Specific examples of the crosslinking assistant include: sulfur; quinone dioxime compounds such as p-quinone dioxime; methacrylate compounds such as polyethylene glycol dimethacrylate; allyl compounds such as diallyl phthalate and triallyl cyanurate; maleimide And divinylbenzene and the like. Such a coagent is preferably used in an amount of 0.5 to 2 moles, more preferably about equimole, to 1 mole of the organic peroxide used.

«Fillers»
Examples of fillers include silica, finely divided silicic acid, activated calcium carbonate, light calcium carbonate, ground calcium carbonate, talc, clay and the like. These fillers may be used alone or in combination of two or more. Such a filler is preferably used in an amount of 1 to 500 parts by weight, more preferably 1 to 400 parts by weight, still more preferably 1 to 300 parts by weight, per 100 parts by weight of the copolymer rubber (A). . When the compounding amount of the filler is within the above range, mechanical properties such as tensile strength, tear strength and abrasion resistance of the rubber can be improved.

«Processing aids»
As a processing aid, those generally blended with rubber as a processing aid can be widely used. Specifically, ricinoleic acid, stearic acid, palmitic acid, lauric acid, barium stearate, zinc stearate, calcium stearate, zinc laurate or esters, etc. may be mentioned. These processing aids may be used alone or in combination of two or more. The processing aid can be suitably blended in an amount of preferably 30 parts by weight or less, more preferably 25 parts by weight or less, still more preferably 20 parts by weight or less, per 100 parts by weight of the copolymer rubber (A) . It is excellent in processability, such as kneading | mixing processability, extrusion processability, injection moldability, as the compounding quantity of a processing aid is in the said range.

«Activator»
Examples of the activator include glycols such as polyethylene glycol and diethylene glycol; and amines such as di-n-butylamine and triethanolamine. These active agents may be used alone or in combination of two or more. The amount of the activator is preferably 0.2 to 15 parts by weight, preferably 0.3 to 10 parts by weight, more preferably 0.5 to 8 parts by weight, per 100 parts by weight of the copolymer rubber (A). Can be appropriately blended.

<Preparation of composition for vibration proof rubber>
The composition of the present invention can be prepared by combining the above-mentioned components sequentially or simultaneously by known methods.

  In order to produce a cross-linked product from the composition of the present invention, an uncrosslinked rubber composition is prepared once, and then the rubber composition is molded into the intended shape, as well as crosslinking of known rubber compositions. Then, crosslinking may be performed. Preparation, molding and crosslinking of the rubber composition may be carried out separately or continuously.

  The crosslinkable rubber composition of the present invention is preferably 80 to 190 ° C., more preferably 80 to 190 ° C., for example, by internal mixers (closed mixers) such as Banbury mixers, kneaders and intermixes. After kneading at a temperature of 80 to 170 ° C., preferably for 2 to 20 minutes, more preferably 3 to 10 minutes, using rolls or a kneader such as an open roll, 3 to 30 at a roll temperature of 40 to 80 ° C. After kneading for a minute, it can be prepared by extruding / dividing the kneaded material. When the kneading temperature in the internal mixers is low, a vulcanization accelerator or the like may be simultaneously kneaded.

[Anti-vibration rubber and its manufacturing method]
The vibration-proof rubber of the present invention comprises a crosslinked product of the composition of the present invention. Moreover, the manufacturing method of the vibration-proof rubber of this invention includes the process of bridge | crosslinking the composition of this invention.

  The cross-linking is formed into the intended shape by simultaneously molding the uncrosslinked rubber composition of the present invention by various forming methods using an extruder, calender roll, press, injection molding machine, transfer molding machine, etc. Alternatively, the molded product can be introduced into the crosslinking tank and heated at a temperature of 100 to 270 ° C. for 1 to 40 minutes, or irradiated with radiation such as light, γ-ray or electron beam. Moreover, it can also bridge | crosslink at normal temperature.

  Such crosslinking step may use a mold or may perform crosslinking without using a mold. When a mold is not used, the steps of molding and crosslinking are usually carried out continuously. As a heating method in the crosslinking tank, a method using a heating tank such as hot air, glass bead fluidized bed, UHF (ultrahigh frequency electromagnetic wave), steam, LCM (hot molten salt tank), etc. may be mentioned.

  The anti-vibration rubber of the present invention can be suitably used for an anti-vibration rubber product for automobile parts, more specifically for an engine mount.

  Hereinafter, the present invention will be more specifically described based on examples, but the present invention is not limited to these examples. In addition, the evaluation method of each physical property in a following example and a comparative example is as follows.

<Composition of Ethylene / α-Olefin / Non-conjugated Polyene Copolymer>
The weight fraction (% by weight) of each constituent unit of the ethylene / α-olefin / nonconjugated polyene copolymer was determined by the measurement value by ¹³ C-NMR. The measurement value is measured using an ECX400P nuclear magnetic resonance apparatus (manufactured by JEOL) at a measurement temperature of 120 ° C., a measurement solvent: ortho-dichlorobenzene / deuterated benzene = 4/1, and the number of integrations: 8,000. It was obtained by measuring the ¹³ C-NMR spectrum of the polymer.

<Iodine value>
The iodine value of the ethylene / α-olefin / nonconjugated polyene copolymer rubber was determined by a titration method. Specifically, it was measured by the following method.

  Dissolve 0.5 g of ethylene / α-olefin / non-conjugated polyene copolymer rubber in 60 ml of carbon tetrachloride, add a small amount of Wiss reagent and 20% potassium iodide solution, and add 0.1 mol / L sodium thiosulfate solution. I decided. A starch indicator was added near the end point, and while stirring well, it was adjusted to the point where the light purple color disappeared, and the g number of iodine was calculated as the amount of consumed halogen per 100 g of sample.

<Intrinsic viscosity>
The intrinsic viscosity [η] was measured at a temperature of 135 ° C. and a measurement solvent of decalin using a fully automatic limiting viscometer manufactured by Rigosha Co., Ltd.

<Weight Average Molecular Weight (Mw), Number Average Molecular Weight (Mn), Molecular Weight Distribution (Mw / Mn)>
The weight average molecular weight (Mw), the number average molecular weight (Mn), and the molecular weight distribution (Mw / Mn) are polystyrene equivalent values measured by gel permeation chromatography (GPC). The measuring device and conditions are as follows. In addition, the molecular weight was calculated based on a conversion method by preparing a calibration curve using commercially available monodispersed polystyrene.

Equipment: Gel permeation chromatography Alliance GP 2000 (manufactured by Waters),
Analyzer: Empower 2 (manufactured by Waters),
Column: TSKgel GMH6-HTx2 + TSKgel GMH6-HTLx2 (7.5 mm ID x 30 cm, manufactured by Tosoh Corporation),
Column temperature: 140 ° C,
Mobile phase: o-dichlorobenzene (containing 0.025% BHT),
Detector: Differential refractometer (RI), flow rate: 1.0 mL / min,
Injection volume: 400 μL,
Sampling time interval: 1s,
Column calibration: monodispersed polystyrene (made by Tosoh Corporation),
Molecular weight conversion: Calibration method taking into consideration old method EPR conversion / viscosity.

<Low molecular weight component>
When the chart obtained by the above GPC measurement shows two or more peaks, the ratio (%) of the area of the peak appearing on the side of the smallest molecular weight to the entire peak area is that the molecular weight is 2000 or less It was the content of low molecular weight components. In addition, when the chart obtained by GPC measurement showed only one peak, the content of the low molecular weight component was set to 0%.

<Complex viscosity ^{* *} >
As a rheometer, using a viscoelasticity measuring apparatus Ares (manufactured by Rheometric Scientific), complex viscosity ^** ₍ ω _{= 0.01)} at a frequency ω = 0.01 rad / s under conditions of 190 ° C. and strain 1.0%. Complex viscosity ^** ₍ ω _{= 0.1)} at frequency ω _{= 0.1} rad / s, complex viscosity ^** ₍ ω _{= 10) at} frequency ω = ₁₀ rad / s and complex viscosity η ^* at frequency ω = 100 rad / s ₍ ω _{= 100)} (in all units, Pa · sec) was measured. Also, from the results obtained, the P value (η ^* ₍ ω _{= 0.1)} / ^{* *} ₍ ω) which is the ratio (η ^* ratio) of the complex viscosity of η ^* ₍ ω _{= 0.1)} and η ^* ₍ ω _{= 100) = 100)} ) was calculated.

<Number of long chain branches per 1000 carbon atoms (LCB _1000c )>
It measured by the method mentioned above.

<Evaluation of physical properties of unvulcanized rubber>
(1) Mooney viscosity (ML (1 + 4) 125 ° C.)
The Mooney viscosity (ML (1 + 4) 125 ° C.) at 125 ° C. was measured under the condition of 125 ° C. using a Mooney viscometer (Model SMV 202 manufactured by Shimadzu Corporation) in accordance with JIS K6300.

(2) Vulcanization induction time Using the uncrosslinked rubber compound in the examples and comparative examples, a vulcanizing measuring apparatus: MDR 2000 (manufactured by ALPHA TECHNOLOGIES) under the measuring conditions of a temperature of 170 ° C. and a time of 20 minutes. The induction time (TS1) was measured as follows.

  The torque change obtained under conditions of constant temperature and constant shear rate was measured. The time taken for the torque to increase by 1 point (1 dNm) from the minimum torque value was taken as the vulcanization induction time (TS1; minutes).

(3) Vulcanization rate Using the uncrosslinked rubber composition in the examples and comparative examples, a measurement apparatus: MDR 2000 (manufactured by ALPHA TECHNOLOGIES), the vulcanization rate under the measurement conditions of a temperature of 170 ° C. and a time of 20 minutes. (TC90) was measured as follows.

  The torque change obtained under conditions of constant temperature and constant shear rate was measured. The time to reach 90% of the difference between the maximum value and the minimum value of the torque was taken as the vulcanization speed (TC 90; minutes).

Physical properties of vulcanized rubber
(1) Hardness test (Duro-A hardness)
According to JIS K 6253, measurement of sheet hardness (type A durometer, HA) was carried out by stacking flat portions to a thickness of about 12 mm using six 2 mm vulcanized rubber sheets having a smooth surface. However, test pieces containing foreign matter, bubbles, and flaws were not used. In addition, the dimensions of the measurement surface of the test piece were such that the tip of the needle could be measured at a position at least 12 mm away from the end of the test piece.

(2) Tensile Test The vulcanized rubber sheets obtained in Examples and Comparative Examples were punched out to prepare No. 3 dumbbell test pieces described in JIS K 6251 (2001). Using this test piece, a tensile test is carried out under the conditions of a measuring temperature of 25 ° C. and a tensile speed of 500 mm / min according to the method specified in the same JIS K 6251, 25% modulus (M ₂₅ ), 50% modulus (M ₅₀ ) 100% modulus (M ₁₀₀ ), 200% modulus (M ₂₀₀ ), 300% modulus (M ₃₀₀ ), tensile stress at break (T _B ) and tensile elongation at break (E _B ) were measured.

<Crosslink density>
The crosslinking density ν was calculated from the Flory-Rehner equation (a) using the following equilibrium swelling. V _R in the formula (a) was determined by extracting the crosslinked 2 mm sheet with toluene under the condition of 37 ° C. × 72 h.

<Compression set>
A specimen for measurement of compression set (CS) was obtained by vulcanizing a straight cylindrical specimen having a thickness of 12.7 mm and a diameter of 29 mm at 170 ° C. for 15 minutes. The compression set of the obtained test piece after being treated at 160 ° C. for 70 hours was measured according to JIS K6262 (1997).

<Dynamic characteristics>
A test piece for measurement of dynamic characteristics was obtained by vulcanizing a straight cylindrical test piece having a thickness of 12.7 mm and a diameter of 29 mm at 170 ° C. for 15 minutes. First, using a static spring tester (Instron "dual column bench type universal testing system 5969", load cell 50 kN), the test temperature is 23 ° C, the test speed is 5 mm / mim, and the condition of the compression strain 3 mm is static. The spring constant (Ks) (N / mm) was measured. Subsequently, using a test piece used in the static spring test, using a dynamic spring tester ("servo pulser EHF-EM020K1-20-1A" manufactured by Shimadzu Corporation, load cell 1 kN), test temperature 23 ° C, average deflection 1 Under 25 mm, dynamic spring constants (Kd) (N / mm) and tan δ were measured at 15 Hz (flexure amplitude ± 0.5 mm) and 100 Hz (flexure amplitude ± 0.05 mm). Furthermore, the dynamic magnification (Kd / Ks) was calculated from the calculated static spring constant (N / mm) and dynamic spring constant (N / mm).

Production Example 1
The ethylene-propylene-VNB copolymer (A-1) was produced as follows using the continuous polymerization apparatus shown in FIG.

In a polymerization reactor C having a volume of 300 liters, 58.3 L / hr of the hexane solvent dehydrated and purified from the tube 6, 4.5 mmol / hr of triisobutylaluminum (TiBA) from the tube 7, (C ₆ H ₅ ) ₃ CB (C ₆ H ₅ ) 0.150 mmol / hr of C ₆ F ₅ ) ₄ and 0.030 mmol / hr of di (p-tolyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride were continuously fed at 0.150 mmol / hr. . At the same time, 6.6 kg / hr of ethylene, 9.3 kg / hr of propylene, 18 kg / hr of hydrogen, and 340 g / hr of VNB were continuously fed into the polymerization reactor C from tubes 2, 3, 4, and 5, respectively. Then, copolymerization was performed under the conditions of a polymerization temperature of 87 ° C., a total pressure of 1.6 MPaG, and a residence time of 1.0 hour.

  The solution of the ethylene-propylene-VNB copolymer produced in the polymerization reactor C is continuously discharged at a flow rate of 88.0 L / hr through the pipe 8 to raise the temperature to 170 ° C. (pressure: 4.1 MPaG To the phase separator D). At this time, ethanol as a polymerization inhibitor was continuously introduced into the tube 8 in a quantity of 0.1 mol times the amount of TiBA in the liquid component withdrawn from the polymerization reactor C.

  In phase separator D, a solution of ethylene-propylene-VNB copolymer is divided into a concentrated phase (lower phase part) containing most ethylene-propylene-VNB copolymer and a dilute phase (upper phase part) containing a small amount of polymer And separated.

  The concentrated phase separated is introduced at 85.4 liters / hr into the heat exchanger K through the pipe 11 and further into the hopper E, where the solvent is evaporated off, and the ethylene / propylene / VNB copolymer Was obtained in an amount of 7.8 kg / hr.

  The physical properties of the obtained ethylene-propylene-VNB copolymer (A-1) were evaluated as described above. The results are shown in Table 1. In addition, the molecular weight distribution of the obtained copolymer (A-1) showed bimodality.

Example 1
As a first step, 100 parts by weight of the ethylene-propylene-VNB copolymer (A-1) obtained in Production Example 1 is masticated for 1 minute using a BB-4 type Banbury mixer (manufactured by Kobe Steel). Next, 30 parts by weight of hydrophobic silica (Aerosil R805, manufactured by EVONIK) surface-treated with octylsilane, 5 parts by weight of activated zinc flower (META-Z 102, manufactured by Inoue Lime Industry Co., Ltd.), carbon black Add 5 parts by weight of Sheist G-SO, Tokai Carbon Co., Ltd., 50 parts by weight of paraffinic process oil (Diana Process PW-380, Idemitsu Kosan Co., Ltd.) and 1 part by weight of stearic acid, Knead for 2 minutes. Thereafter, the ram was raised and cleaned, and kneading was further carried out for 1 minute, and the mixture was discharged at about 150 ° C. to obtain a first stage composition.

  Next, as a second step, the composition obtained in the first step is a 6 inch roll (manufactured by Nippon Roll Co., Ltd., the surface temperature of the front roll is 50 ° C., the surface temperature of the rear roll is 50 ° C., the front roll 16 rpm, rotation speed of the rear roll 18 rpm), 4 parts by weight of dicumyl peroxide (DCP-40C, manufactured by Kayaku Akzo Co., Ltd.) is added thereto, and the mixture is kneaded for 10 minutes to obtain an uncrosslinked rubber compound I got Unvulcanized rubber physical properties were evaluated using this rubber compound.

  The kneaded product was divided into sheets and pressed at 170 ° C. for 10 minutes using a 100-ton press molding machine to prepare a 2 mm-thick vulcanized rubber sheet. Using this, the evaluation of the physical properties of the vulcanized rubber, the crosslink density, the compression set and the dynamic magnification were measured. The results are shown in Table 2.

[Comparative Examples 1 and 2]
An uncrosslinked rubber compound, as in Example 1, except that the type and amount of each compounded in the first and second steps are as shown in Table 2 in Example 1. A crosslinked rubber sheet and a vulcanized rubber sheet were obtained and evaluated. The results are shown in Table 2.

1) to 7) in Table 2 are as follows.
1) Hydrophobic silica (Aerosil R 805, manufactured by EVONIK)
2) Hydrophilic silica (Aerosil 200, manufactured by EVONIK)
3) Active zinc flower (Meta-Z 102, manufactured by Inoue Lime Industry Co., Ltd.)
4) Carbon black (Siest G-SO, manufactured by Tokai Carbon Co., Ltd.)
5) Stearic acid (bead stearic acid, made by NOF Corporation)
6) Paraffinic process oil (Diana Process PW-380, manufactured by Idemitsu Kosan Co., Ltd.)
7) Dicumyl peroxide (DCP-40C, manufactured by Kayaku Akzo)
By using hydrophobic silica surface-treated with the above-mentioned specific silane compound, the reason why the vibration resistance and rubber elasticity are significantly improved is unknown.
(1) Improved compatibility between silica and EPDM by hydrophobization of the silica surface
(2) Improving the dispersibility due to the decrease in cohesive force due to the reduction of silanol groups on the silica surface,
(3) It is considered that there is binding or dissociation due to hydrophobic interaction between hydrophobic groups of the surface treated silane (as the reason for the increase of tan δ).

C polymerization reactor D phase separator E hopper F pump G heat exchanger H heat exchanger I heat exchanger J heat exchanger K heat exchanger

Claims (10)

  Ethylene-alpha-olefin nonconjugated polyene copolymer (A) which has a structural unit derived from ethylene (a1), C3-C20 alpha-olefin (a2), and nonconjugated polyene (a3) A composition for vibration-proof rubber, comprising 100 parts by weight and 1 to 100 parts by weight of hydrophobic silica (B) surface-treated with octylsilane. The composition according to claim 1, wherein the copolymer (A) satisfies the following conditions (i) to (vii):
(I) The molar ratio [(a1) / (a2)] of the structural unit derived from ethylene (a1) and the structural unit derived from α-olefin (a2) is 40/60 to 99.9 / 0. Is 1;
(Ii) The weight fraction of the structural unit derived from the nonconjugated polyene (a3) is 0.07% by weight to 10% by weight in 100% by weight of the copolymer (A);
(Iii) Weight average molecular weight (Mw) of copolymer (A) and weight fraction of constituent unit derived from non-conjugated polyene (a3) (weight fraction of (a3) (% by weight)), non-conjugated The molecular weight of polyene (a3) (the molecular weight of (a3)) satisfies the following formula (1);
4.5 ≦ Mw × (a3) weight fraction / 100 / (a3) molecular weight ≦ 40 (1)
(Iv) Complex viscosity ^** ₍ ω _{= 0.1)} (Pa · sec) at a frequency ω = _0.1 rad / s obtained by linear viscoelasticity measurement (190 ° C.) using a rheometer, and a frequency ω = The ratio P (η ^* ₍ ω _{= 0.1)} / η ^* ₍ ω _{= 100)} ) to the complex viscosity ^** ₍ ω _{= 100)} (Pa · sec) at ₁₀₀ rad / s, the limiting viscosity [η], and The weight fraction of the constituent unit derived from the conjugated polyene (a3) (the weight fraction of (a3)) satisfies the following formula (2);
Weight fraction of P / ([η] ^2.9 ) ≦ (a 3) × 6 (2)
(V) The ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) (molecular weight distribution; Mw / Mn) measured by gel permeation chromatography (GPC) is in the range of 8 to 30;
(Vi) the number average molecular weight (Mn) is 30,000 or less;
(Vii) The chart obtained by GPC measurement shows two or more peaks, and the area of the peak appearing on the side of the smallest molecular weight is in the range of 1 to 20% of the total peak area. The non-conjugated polyene (a3) according to claim 1 or 2, wherein a total of two or more partial structures selected from the group consisting of the following general formulas (I) and (II) in the molecule. Antivibration rubber composition.

  The composition for vibration-proof rubber according to any one of claims 1 to 3, wherein the non-conjugated polyene (a3) contains 5-vinyl-2-norbornene (VNB).   The composition for vibration-proof rubber according to any one of claims 1 to 4, wherein the α-olefin (a1) is propylene.   Furthermore, a zinc oxide (C) is contained, The composition for vibration-proof rubber as described in any one of the Claims 1-5 characterized by the above-mentioned.   The composition for vibration-proof rubber according to claim 6, wherein the zinc oxide (C) is active zinc flower.   The vibration-proof rubber which consists of a crosslinked body of the composition for vibration-proof rubbers as described in any one of Claims 1-7.   The vibration-proof rubber product for motor vehicle parts containing the crosslinked body of the composition for vibration-proof rubber as described in any one of Claims 1-7.   The anti-vibration rubber product for automobile parts according to claim 9, wherein the anti-vibration rubber product for automobile parts is an engine mount.

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