JPH10259221A - Thermoplastic elastomer and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a thermoplastic elastomer having excellent rubber characteristics, low strain properties, durability and processability in a wide temperature range, by including specific two kinds of block units in a prescribed ratio and making a number-average molecular weight in a specified range. SOLUTION: This cyclic diene-based thermoplastic elastomer comprises two or more block units (block A) partially or totally composed of a cyclic conjugated diene monomer (derivative) of formula I and formula II ((n) is 1-4) and one or more of block units (block B) composed of a straight-chain conjugated diene monomer (a monomer consisting essentially of the diene monomer) and having 15-55wt.% of the vinyl bond content as a molecule structural unit constituting a polymer chain and has the weight ratio of the component A/B of 3/97 to 50/50 and the number average molecular weight (GPC method calculated as polystyrene) adjusted to 50,000 to 500,000.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel cyclic conjugated diene having at least two cyclic conjugated diene blocks having a specific structure and at least one linear conjugated diene block such as 1,3-butadiene or isoprene. The present invention relates to a thermoplastic elastomer, a partially hydrogenated cyclic diene thermoplastic elastomer thereof, and a method for producing these. More specifically, among cyclic diene-based block copolymers, a cyclic diene having a specific structure excellent in mechanical strength, compression set, dynamic hysteresis, heat aging resistance, weather resistance, rebound resilience, etc., especially at room temperature and high temperature. The present invention relates to a thermoplastic elastomer, a partially hydrogenated thermoplastic elastomer, and a method for producing the same.

[0002]

2. Description of the Related Art Numerous proposals have been made for conjugated diene polymers, mainly as elastomers, thermoplastic elastomers and special transparent resins for improving the impact resistance of tires, belts and resins. Widely used for adhesives, films, containers and the like. As a typical conjugated diene polymer,
Polybutadiene, polyisoprene, butadiene-isoprene copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, α-methylstyrene-butadiene copolymer, α-methylstyrene-isoprene copolymer, acrylonitrile-butadiene copolymer Polymers, acrylonitrile-isoprene copolymers, butadiene-methyl methacrylate copolymers, isoprene-methyl methacrylate copolymers, hydrogenated polymers thereof, and the like are known.

On the other hand, as a molecular structural unit constituting a polymer chain, a polymer block (constrained phase) having a glass transition temperature (Tg) higher than room temperature is provided at both ends, and a polymer block (Tg) having a Tg lower than room temperature is interposed therebetween. A block copolymer comprising a rubber phase), for example, a styrene-butadiene (or isoprene) -styrene block copolymer and a hydrogenated polymer thereof are used as thermoplastic elastomers in many applications such as modifying adhesives and resins. Widely used for In addition, polystyrene, polyolefin, polyphenylene ether, styrene-butadiene diblock copolymer, hydrogenated product thereof, etc. were blended with the styrene-butadiene (or isoprene) -styrene block copolymer and hydrogenated polymer thereof. The block copolymer composition is styrene-
The butadiene (or isoprene) -styrene block copolymer and its hydrogenated polymer are widely used to improve various physical properties such as heat resistance, fluidity, and adhesive properties.

However, with recent advances in industrial technology, the market requirements for polymer materials have become increasingly higher, and higher heat resistance (heat aging resistance) and mechanical properties (tensile strength / tensile elongation) have been required.・ High-temperature tensile strength, high-temperature tensile elongation, etc.) ・ The development of a thermoplastic elastomer having excellent compression set and dynamic hysteresis closer to vulcanized rubber has been strongly desired. One of the powerful means to solve this problem is to copolymerize not only monomers with relatively small steric hindrance such as butadiene and isoprene, but also monomers with large steric hindrance, that is, cyclic monomers. Research activities to improve the structure of the polymer chain of the conjugated diene polymer by further hydrogenating it as necessary to obtain a polymer material with advanced thermal and mechanical properties It is becoming popular.

However, not only is it difficult to homopolymerize or copolymerize cyclic conjugated diene monomers, but also for the purpose of remarkably exhibiting characteristics caused by introducing the cyclic conjugated diene monomers into the polymer chain. Attempts to block copolymerize cyclic conjugated diene monomers have also been studied, but a cyclic diene-based block copolymer expressing sufficient physical properties has not yet been obtained, and this solution has been strongly desired. . U.S. Pat. No. 4,020,251 discloses that 1,3-cyclohexadiene / butadiene-based triblock copolymer is charged with 1,3-cyclohexadiene and butadiene in the presence of THF and TMEDA, and dilithium is used as an initiator. Although a method of polymerizing is disclosed, the molecular weight of the obtained triblock copolymer is 4 to 4 in number average molecular weight.
Although there is a description of 58,000, the molecular weight distribution is broad (1.
86 to 2.35), the description of tensile strength, which is a representative of thermoplastic elastomer physical properties, is only described as "low", and a complete triblock is not obtained.

Japanese Patent Application Laid-Open No. Hei 7-247405 discloses a mixture of a cyclohexadiene-butadiene-cyclohexadientine block polymer and a diblock copolymer. Block body not obtained. Moreover, the microstructure of the butadiene portion also has a high vinyl bond content of 54 to 63%,
The mechanical strength is not satisfactory (150 kgf / cm ² or less at room temperature).

Further, Japanese Patent Application Laid-Open No. 7-258318 discloses a high molecular weight cyclohexadiene-conjugated diene-cyclohexadi entry block polymer in the detailed description of the invention, but a triblock useful as an elastomer. The above examples of the evaluation of the polymerization and physical properties of the block polymer, and the evaluation of other elastomer physical properties and hard segments /
There is no disclosure or suggestion of the microstructure of the soft component that is important for microphase separation of the soft segment. In addition, since these polymerization catalysts are obtained by isolating and purifying a reaction product of TMEDA / n-BuLi = 1/4 as a polymerization initiator, 1,2 (vinyl) bonds in the microstructure of the butadiene portion are not affected. It has the disadvantage that the mechanical strength, elongation, heat resistance and compression set are not sufficient. Comparison of the structure and physical properties of the polymer obtained when using these complexes will be described in detail in Comparative Examples.

[0008] Further, in the re-published patents WO95 / 21217 and WO95 / 21202, TMEDA /
Using a complex of n-BuLi = 1/4 (mol ratio) as a polymerization initiator, cyclohexadiene-butadiene-cyclohexadientine block polymer is polymerized, and the butadiene portion is completely hydrogenated to have a narrow molecular weight distribution (Mw / Mn).
≦ 1.1) Triblock polymers are disclosed,
There is no disclosure or suggestion about the microstructure of the butadiene portion, and there is no description of the hydrogenation rate of the cyclohexadiene portion or the glass transition temperature of the hard segment. This is also shown in Comparative Examples, but due to the nature of the polymerization initiator, the butadiene portion has a high microstructure, and thus has the disadvantage that the mechanical strength, elongation, and compression set useful for thermoplastic elastomers deteriorate.

[0009]

SUMMARY OF THE INVENTION The present invention provides a novel cyclic diene block copolymer having a molecular weight, a molecular weight distribution,
As a molecular structure unit constituting a polymer chain, a part or all of which is a cyclic conjugated diene monomer or a microstructure of a hydrogenation site and a hydrogenation rate / hard / soft ratio / soft segment in a specific range. Ultra high performance having at least two blocks composed of derivatives thereof and at least one block composed of a linear conjugated diene monomer or a monomer mainly composed of a linear conjugated diene monomer The present invention provides a cyclic diene-based thermoplastic elastomer, a partially hydrogenated cyclic diene-based thermoplastic elastomer, and methods for producing these.

[0010]

Means for Solving the Problems The present inventors have diligently studied the relationship between the primary structure / higher order structure and physical properties of the cyclic conjugated diene-based block copolymers reported so far in order to solve the above problems. As a result, the cyclic conjugated diene-based block copolymer having a specific structure, which could not be obtained by the conventional method, was found to be excellent as a thermoplastic elastomer. This thermoplastic elastomer was confirmed to be a high-performance thermoplastic elastomer having excellent rubber properties, low distortion, durability and processability in the widest temperature range among conventional thermoplastic elastomers, In addition, the present invention was completed by establishing the manufacturing method.

That is, the present invention is as follows. [1] (a) A block unit in which a part or the whole of a molecular structural unit constituting a polymer chain is composed of a cyclic conjugated diene monomer represented by the following general formulas (1) and (2) or a derivative thereof. A block unit (B block) composed of at least two (A blocks) and a monomer mainly composed of a linear conjugated diene monomer or a linear conjugated diene monomer
Has at least one, the number average molecular weight in terms of polystyrene by GPC method is 50,000 to 500,000,
A / B weight ratio in the range of 3/97 to 50/50,
And a cyclic diene-based thermoplastic elastomer, wherein the amount of vinyl bonds in the linear conjugated diene monomer unit constituting the B block is 15 to 55%.

[0012]

Embedded image (However, n is a value selected from an integer from 1 to 4.)

[0013]

Embedded image (However, n is a value selected from an integer from 1 to 4.)

[2] (a) Part or all of the molecular structural units constituting the polymer chain is composed of a cyclic conjugated diene monomer represented by the following general formulas (1) and (2) or a derivative thereof. Block unit (A block) is at least 2
And at least one block unit (B block) composed of a linear conjugated diene monomer or a monomer mainly composed of a linear conjugated diene monomer, and converted to polystyrene by GPC. Average molecular weight of 50,000-50
0000 and the weight ratio of A / B is 3/97 to 50/5
0 and the amount of vinyl bonds in the B block is 2
5 to 55%, the hydrogenation rate of unsaturated double bonds (A hydrogenation rate) in the monomer constituting the A block is 50% or less, and the hydrogenation rate in the monomer constituting the B block is 50% or less. A partially hydrogenated cyclic diene-based thermoplastic elastomer having a hydrogenation ratio (B hydrogenation ratio) of unsaturated double bonds of 90% or more.

[0015]

Embedded image (However, n is a value selected from an integer from 1 to 4.)

[0016]

Embedded image (However, n is a value selected from an integer from 1 to 4.)

[3] The partially hydrogenated cyclic diene-based thermoplastic elastomer according to [2], wherein the A hydrogenation rate is preferably 25% or less and the B hydrogenation rate is 95% or more. [4] Preferably, the hydrogenation rate of A is 25% or less, the hydrogenation rate of B is 95% or more, and the amount of 1,2-vinyl bond in the B block is 30 to 50%. The partially hydrogenated cyclic diene-based thermoplastic elastomer according to the item [2], which is characterized in that: [5] Preferably, a part or all of the monomers constituting the A block is 1,3-cyclohexadiene, a 1,3-cyclohexadiene derivative, or a cyclic conjugated diene monomer having a 6-membered ring structure in the molecule thereof And the monomer constituting the B block is 1,3-butadiene and / or isoprene, or a monomer mainly composed of 1,3-butadiene and / or isoprene [1] to
[4] The cyclic diene-based thermoplastic elastomer or the partially hydrogenated cyclic diene-based thermoplastic elastomer according to any one of the above items. [6] Preferably, the glass transition temperature of the hard segment determined from the G ″ peak temperature by a viscoelasticity measurement method is 130.
The cyclic diene-based thermoplastic elastomer or the partially hydrogenated cyclic diene-based thermoplastic elastomer according to any one of [1] to [5], which has a temperature of from 200 to 200 ° C.

[7] The cyclic diene-based thermoplastic elastomer according to any one of [1] to [5], wherein the molecular weight distribution (Mw / Mn) in terms of polystyrene determined by the GPC method is 1.2 or less. Or a partially hydrogenated cyclic diene-based thermoplastic elastomer. [8] Two equivalents of a monoorganic lithium initiator were added at -20 to 6
Reaction with 1,3-diisopropenylbenzene or a derivative thereof in the presence of a tertiary monoamine and / or an ether compound in a non-polar hydrocarbon at a temperature range of 0 ° C., and then reacting the reaction mixture with the Li concentration 0.05-0.49
Α, which is produced by adding a doubling mole of a tertiary diamine and / or an alkoxylithium compound and, if necessary, a conjugated diene monomer of 30 moles or less with respect to Li.
The ω-dilithium compound was used as an initiator without isolation, the B block was first polymerized, and then, if necessary, a tertiary diamine was added in an amount of 0.1 to 2.0 times mol of Li, and then A was added. The method for polymerizing a cyclic diene-based thermoplastic elastomer according to any one of claims 1 to 7, wherein the block is polymerized.

[9] The addition amount of the tertiary diamine and / or alkoxy compound to the Li concentration is 0.1 to 0.2.
The polymerization method according to [8], wherein the molar amount is 4 times the molar amount. [10] Using the initiators of [8] and [9], simultaneously adding a cyclic conjugated diene monomer and a linear conjugated diene monomer to carry out polymerization. ] The method for polymerizing a cyclic diene-based thermoplastic elastomer according to any one of the above items. [11] The tertiary monoamine is at least one compound selected from trimethylamine, triethylamine, and dimethylaniline, and the tertiary diamine is at least one compound selected from tetraethylethylenediamine, tetramethylethylenediamine, tetraphenylethylenediamine, and tetracyclohexylethylenediamine. Wherein the alkoxylithium compound is at least one compound selected from compounds having 1 to 10 carbon atoms [8]
-The polymerization method according to any one of items [10] to [10].

[12] In producing the partially hydrogenated thermoplastic elastomer according to the items [2] to [7], the following (A)
A method for producing a partially hydrogenated cyclic diene-based thermoplastic elastomer, comprising using the hydrogenation catalyst composition of the component (B). (A) a titanocene compound represented by the following general formula (3)

Embedded image (However, R ^1, R ² is hydrogen, represents C ₁ -C ₁₂ hydrocarbon radical selected group from, R ^1, R ² good .R ^3, R ⁴ be the same or different are Represents a group selected from hydrogen, a C _{1 to} C ₁₂ hydrocarbon group, an aryloxy group, an alkoxy group, a halogen group and a carbonyl group, and R ³ and R ⁴ may be the same or different.) (B) Li, N
at least one reducing agent selected from compounds containing at least one of a, K, Mg, Zn, Al, and Ca elements;

[13] In producing the partially hydrogenated thermoplastic elastomer according to the items [2] to [7], the following (A)
A method for producing a partially hydrogenated cyclic diene-based thermoplastic elastomer, comprising using a catalyst composition of component (C) in addition to component (B). (A) a titanocene compound represented by the following general formula (3)

Embedded image (However, R ^1, R ² is hydrogen, represents C ₁ -C ₁₂ hydrocarbon radical selected group from, R ^1, R ² good .R ^3, R ⁴ be the same or different are Represents a group selected from hydrogen, a C _{1 to} C ₁₂ hydrocarbon group, an aryloxy group, an alkoxy group, a halogen group and a carbonyl group, and R ³ and R ⁴ may be the same or different.) (B) Li, N
at least one reducing agent selected from compounds containing at least one of a, K, Mg, Zn, Al, and Ca elements; The fraction to the amount of heavy bonds is 0.3 to
1. The olefinically unsaturated double bond-containing polymer of 1.

[14] In producing the partially hydrogenated thermoplastic elastomer according to the items [2] to [7], the following (A)
A partially hydrogenated cyclic diene-based thermoplastic elastomer characterized by using a catalyst composition further comprising the following component (D) in addition to the component and the component (B) or the components (A), (B) and (C): Manufacturing method. (A) a titanocene compound represented by the following general formula (3)

Embedded image (However, R ^1, R ² is hydrogen, represents C ₁ -C ₁₂ hydrocarbon radical selected group from, R ^1, R ² good .R ^3, R ⁴ be the same or different are Represents a group selected from hydrogen, a C _{1 to} C ₁₂ hydrocarbon group, an aryloxy group, an alkoxy group, a halogen group and a carbonyl group, and R ³ and R ⁴ may be the same or different.) (B) Li, N
at least one reducing agent selected from compounds containing at least one of a, K, Mg, Zn, Al, and Ca elements; The fraction to the amount of heavy bonds is 0.3 to
1, an olefinically unsaturated double bond-containing polymer,
(D) alcohol compounds, alkoxylithium compounds,
Alkoxy sodium compounds, alkoxy potassium compounds, ether compounds, thioether compounds, ketone compounds, sulfoxide compounds, carboxylic acid compounds, carboxylic acid ester compounds, aldehyde compounds, lactone compounds, amine compounds, amide compounds, nitrile compounds, epoxy compounds And at least one polar compound selected from the group of oxime compounds.

[15] The hydrogenation temperature is 40 to 80 ° C., and the amount of the hydrogenation catalyst added is 0.01 to 100 g of the polymer.
The production method according to any one of [12] to [14], wherein the amount is from 5 to 5 mmol. The thermoplastic elastomer and the special transparent resin (composition) having impact resistance are composed of at least two constrained phases (blocks) and at least one rubber phase (block), and both blocks need to be microphase separated. is there. When the constrained phase is below its Tg, the molecule having such a structure acts as a physical cross-linking point, and exhibits elastomeric elasticity. Above the Tg of the hard segment, the constrained phase also flows,
Injection molding and recycling become possible.

In general, it is known that ΔG _mix > 0 must be satisfied in the following equation (1) in order for the AB type block polymer to undergo microphase separation. _{ΔG mix = ΔH mix -TΔS mix (} 1) ΔH mix = f (χ AB) (2) χ AB = (σ A -σ B) 2 M A / ρ A RT (3) [where, in formula (1) ΔG _mix indicates a change in free energy of mixing, ΔH _mix indicates a change in enthalpy of mixing, T indicates an absolute temperature, and ΔS _mix indicates a change in entropy of mixing. Also, in equation (2), χ _AB is the χ parameter between _AB blocks.
Enthalpy change is a function of χ _AB . In the equation (3), σ represents the solubility parameter, M represents the molecular weight, ρ represents the specific gravity, R represents the gas constant, and T represents the absolute temperature. In general, it is considered that the entropy of a polymer is smaller than that of a small molecule (ΔSmix ≒ 0), so that ΔG
ΔH _mix> 0 to become a _mix> 0, ie, (2)
Equation (3) needs to be large. That is, in order for the AB block to be microphase-separated, the difference in solubility parameter ([sigma] _{A- [} sigma] _B ) between the AB blocks or the molecular weight may be increased.

However, the solubility parameter of the hard segment in the present invention has not been determined in the known literature, and the solubility parameter of the soft segment can vary in the microstructure. The polymer structure cannot be determined from literature, calculations and the like. It is also known that microphase separation also depends on molding conditions, which mainly depends on the melt viscosity of the polymer. Therefore, it is very difficult to control the microphase-separated structure with a new polymer and express physical properties. In the present invention, the fact that the A block and the B block of the cyclic diene-based block copolymer surprisingly undergo microphase separation even at a high temperature by specifying the structure has been surprisingly studied based on this fact. Is completed. In the present invention, the constrained phase (hard segment) is formed by A
It is the block, and the B block forms the rubber phase (soft segment).

In the present invention, the cyclic diene-based thermoplastic elastomer, that is, the cyclic conjugated diene-based block copolymer refers to at least two A block units and at least one A block unit in a part of the molecular structural unit constituting the polymer chain. Is a block copolymer composed of B block units of As a molecular structural unit constituting such a polymer chain, at least two block units (A blocks) mainly composed of a cyclic conjugated diene monomer or a derivative thereof, and a linear conjugated diene monomer or a linear An example of a cyclic diene-based block copolymer having at least one block unit (B block) mainly composed of a monomer having a chiral conjugated diene monomer is represented by the following general formula (4). And a radial block copolymer represented by the general formula (5).

(AB) _a , A- (BA) _b , B- (AB) _c (4) (where a and c are integers of 2 or more and b is an integer of 1 or more) .) [(B-A) n] m + 2 X, [(A-B) n] m + 2 X, [(B-A) n -B] m + 2 X, [(A-B) n - A] _{m + 2} X (5) (where m is 0 or 1 or more and n is an integer of 1 or more. X is, for example, dimethyldichlorosilane, methylene chloride, silicon tetrachloride, tin tetrachloride, epoxy) Represents the residue of a polyfunctional coupling agent such as soybean oil or the residue of an initiator such as a polyfunctional organic alkali metal compound.)

In particular, when the block copolymer of the present invention is used as a thermoplastic elastomer, the molecular structural unit constituting the polymer chain of the block copolymer is represented by the general formula (4) or (5).
Must have two or more A blocks in the molecule. If such a molecule is contained, a in the general formula (4)
= 1, c = 1 block copolymer, ie, BA
-B triblock copolymer, AB diblock copolymer, etc. may be contained. In this case, the amount of the copolymer that does not contribute to the physical cross-linking can be used according to each application even if it is contained in an arbitrary ratio in the entire block copolymer. Less than 70 weight percent is preferred.

The connection point between the A block and the B block of the block copolymer may be such that the cyclic conjugated diene monomer and the linear conjugated diene monomer are directly bonded, or the residue of the bifunctional coupling agent may be used. (Eg, dimethyldichlorosilane, methylene chloride, etc.), an ester bond, an amide bond, a carbonate bond, and the like. In addition, the general formula [(AB) _n ] _{m + 2} X, [(AB) _n -A] _{m + 2} X
(Where m is 0 or 1 or more, and n is an integer of 1 or more) is a thermoplastic elastomer.
Where [(B−A) _n ] _{m + 2} X, [(B−
A) _n- B] _{m + 2 In the} radial block copolymer represented by X, n must be an integer of 2 or more (where m is an integer of 0 or 1 or more) so that the composition becomes a thermoplastic elastomer. Is). These radial block copolymers need not all have the same composition. For example, [(AB) _n ] _{m + 2} X in the general formula (5) is (AB) ₄ X, (A-
B) ₃ X, or a mixture of any composition of (A-B) ₂ X and (A-B).

The cyclic conjugated diene-based block copolymer in the present invention comprises at least two A block units and at least one B block unit in a part of the molecular structural units constituting the polymer chain. Since it is a block copolymer, it need not be composed of only A and B blocks. Therefore, for example, ABCA, ACB
-A, B-A-C-A (where C block is a block unit composed of one or more monomers selected from monomers copolymerizable with A and B monomer blocks and derivatives thereof, for example, Vinyl aromatic hydrocarbon monomers such as styrene and α-methylstyrene; polar monomers such as methyl methacrylate, acrylonitrile, ethylene oxide and propylene oxide; and cyclic polar compound monomers such as cyclic lactone and cyclic siloxane Etc.) are also included in the present invention.

Of course, a cyclic conjugated diene or a derivative thereof and / or a linear conjugated diene monomer may be copolymerized in the C block. Further, a plurality of different blocks (C, D, E...) May be included. D, E.
The monomers constituting the block are the same as the definition of the monomers constituting the C block. As a preferred production example, the cyclic diene-based thermoplastic elastomer of the present invention is obtained by polymerizing AB diblock by living anion polymerization using a combination of alkyllithium and various complexing agents, and a part thereof is cup-shaped. Although a process for producing the block copolymer composition of the present invention by ringing can be mentioned, substantially unreacted AB diblock copolymer remains in this method. The ratio of this diblock copolymer to the total block copolymer is 5 to 95 parts by weight.
Is a cent. If this ratio is less than 5% by weight, the effect of improving processability and fluidity may be reduced. 9
When the content is more than 5% by weight, the workability and the like are greatly improved, but the good mechanical properties (such as breaking strength and breaking elongation) as a thermoplastic elastomer or a special transparent resin having impact resistance are lost. It is not preferable.

In the present invention, the preferred molecular weight distribution (Mw / Mn) of the entire thermoplastic elastomer is 1.2 or less, and the ratio of this diblock copolymer is 10% by weight or less in the total block polymer. is there. The molecular weight of the cyclic diene-based thermoplastic elastomer of the present invention is 50 as a number average molecular weight (Mn) in terms of polystyrene by a GPC method.
000 to 500,000. If it is shorter than 50,000, although it depends on the hard / soft ratio, it is not preferable because it is inferior in high-performance thermoplastic elastomer physical properties, particularly high-temperature mechanical strength. When the number average molecular weight is more than 500,000, 300
In some cases, it is not plasticized even at a high temperature of not less than ℃, and it is practically difficult to use.

Further, the molecular weight distribution (Mw / Mn, where Mw
Is a weight average molecular weight) may be intentionally increased in order to enhance processability, but is preferably 1.01 to 1.2. Further, the cyclic diene-based thermoplastic elastomer of the present invention
, Ie, a monomer mainly composed of a cyclic conjugated diene monomer or a derivative thereof is 3 to 50% by weight. If this value exceeds 50% by weight, it becomes a soft resin region, and properties such as tensile elongation, low strain and high rebound required for thermoplastic elastomers are impaired. If this value is less than 3% by weight, the hard segment does not work as a physical cross-linking point, and heat resistance and the like cannot be expected.

The cyclic conjugated diene monomer or derivative thereof constituting the hard segment of the present invention is a cyclic conjugated diene having 5 or more membered rings formed by carbon-carbon bonds, preferably 1,3- Cyclopentadiene, 1,3-
Cyclohexadiene, 1,3-cycloheptadiene,
Examples thereof include 1,3-cyclooctadiene and derivatives thereof, and particularly preferred are 1,3-cyclohexadiene, 1,3-cyclohexadiene derivatives and cyclic conjugates having a six-membered ring structure in the molecule. Diene. In living anionic polymerization, the cyclic diene monomer has a microstructure represented by the general formula (1) (1,2-addition) or the general formula (2) (1,4-addition).

[0035]

Embedded image (However, n is a value selected from an integer from 1 to 4.)

[0036]

Embedded image (However, n is a value selected from an integer from 1 to 4.)

When 1,3-cyclohexadiene is used as a monomer, the ratio of 1,2 / 1,4 changes from about 10/90 to 50/50 in the present invention. In the present invention, this value is not particularly limited, but the preferred ratio is 1,2 / 1,4 from 30/70 to 50/50 in terms of heat resistance. In addition, the cyclic diene-based thermoplastic elastomer of the present invention
The meaning of "part or all" of the A block constituting, i.e., "a block unit partially or wholly composed of a cyclic conjugated diene monomer or a derivative thereof as a molecular structural unit constituting a polymer chain" is This means that not only a case where the cyclic conjugated diene monomer or its derivative is used alone, but also a copolymer block with another monomer which can be copolymerized with the cyclic conjugated diene monomer or its derivative. Examples of the copolymerizable monomer include, for example, conventionally known monomers that can be polymerized by anionic polymerization.

These include, for example, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene,
Linear conjugated diene monomers such as 1,3-pentadiene and 1,3-hexadiene, styrene, α-methylstyrene,
o-methylstyrene, p-methylstyrene, p-tert-
Vinyl aromatic hydrocarbon monomers such as butylstyrene, 1,3-dimethylstyrene, diphenylethylene, vinylnaphthalene, vinylanthracene or polar monomers such as methyl methacrylate, methyl acrylate, acrylonitrile, cyclic lactone, cyclic Examples include cyclic polar compound monomers such as siloxane. These monomers may be one kind or a mixture of two or more kinds. Of these, styrene and α-methylstyrene are preferred. These copolymerizable monomers are preferably contained in the A block in an amount of not more than 80% by weight, more preferably not more than 50% by weight.
It can be used within the range of weight percent or less. These copolymerizable monomers in the A block may be distributed in the molecular chain by random or alternating copolymerization, or may be distributed in a tapered manner even if a partial block is formed. It does not matter.

Further, the cyclic conjugated diene monomer constituting the B block, which constitutes the cyclic diene-based thermoplastic elastomer of the present invention, is a straight chain having a pair of conjugated carbon-carbon double bonds. A chain diolefin, 1,3-
Butadiene, isoprene, 2,3-dimethyl-1,3-
Examples thereof include butadiene, 1,3-pentadiene, and 1,3-hexadiene, and 1,3-butadiene and isoprene are particularly preferable. In addition, the block unit composed of a monomer mainly composed of the linear conjugated diene monomer constituting the B block may be a conventional block unit copolymerizable with the linear conjugated diene monomer, if necessary. It means a block unit obtained by copolymerizing a known monomer.

As monomers capable of anionic copolymerization with these linear conjugated diene monomers, for example, styrene, α-
Vinyl aromatic hydrocarbon monomers such as methyl styrene, o-methyl styrene, p-methyl styrene, p-tert-butyl styrene, 1,3-dimethyl styrene, diphenyl ethylene, vinyl naphthalene, vinyl anthracene or methyl methacrylate And polar monomers such as methyl acrylate and acrylonitrile, and cyclic polar compound monomers such as cyclic lactone and cyclic siloxane.
Of course, cyclic conjugated dienes and cyclic conjugated diene derivatives can also be copolymerized. These monomers may be one kind or a mixture of two or more kinds. Of these, styrene and α-methylstyrene are preferred. These copolymerizable monomers can be used in the B block in an amount of preferably 50% by weight or less, more preferably 30% by weight or less. These copolymerizable monomers in the B block may be distributed in the molecular chain of the B block by random or alternating copolymerization, or may be distributed in a tapered manner even if a partial block is formed. You can do it.

When 1,3-butadiene is used as the linear conjugated diene monomer constituting the B block, a polybutadiene block is formed. Polybutadiene has 1,4 bonds of cis and trans and 1,2 bonds of vinyl. In the case of polyisoprene, there are 3,4 bonds and 1,2 bonds in addition to 1,4 bonds of cis and trans. Polyisoprene hardly produces 1,2 in ordinary living anionic polymerization, and thus, usually, vinyl bond is 1,2 in polybutadiene.
In the case of polyisoprene, it means 3,4 bonds. The vinyl bond of the present invention is a 1,2-bond of polybutadiene and 1,2- and 3,4-bonds of polyisoprene.

The ratio of these vinyl bonds is an important factor in expressing the physical properties of the thermoplastic elastomer of the present invention. That is, this value is 15 to 55% by weight in the linear conjugated diene monomer in the cyclic diene-based thermoplastic elastomer. For a partially hydrogenated cyclic diene-based thermoplastic elastomer described later, 25 to 55% by weight, preferably 30% by weight.
~ 50 weight percent. If the amount of vinyl bonds in the linear conjugated diene monomer constituting the B block exceeds the upper limit, the mechanical properties at room temperature and high temperature and the low-temperature performance deteriorate, which is not preferable. If the lower limit is exceeded, especially in the case of a partially hydrogenated cyclic diene-based thermoplastic elastomer, the crystallization of the soft part occurs, and the flexibility and the low-temperature performance are unfavorable.

The olefinically unsaturated double bond in the B block is easily gelled by heat, oxygen, radicals, etc.
Since cross-linking and molecular chain scission occur, sufficient addition of existing stabilizers is essential during molding and processing. The primary structure of the partially hydrogenated cyclic diene-based thermoplastic elastomer of the second invention of the present invention is basically 1) the olefin in the B block of the cyclic diene-based thermoplastic elastomer of the first invention 90% or more hydrogenated double bond (B hydrogenation rate ≧ 90%)
And the hydrogenation rate of the olefinically unsaturated bond in the A block is kept at 50% or less, and 2) the vinyl bond content in the B block is 25 to 55%.

If the hydrogenation rate of the olefinically unsaturated bond in the B block is less than 90%, undesirable side reactions such as gelation and polymer chain breakage are likely to occur at the time of molding and the weather resistance is also increased. It is not preferable because it deteriorates.
In particular, since the glass transition temperature of the hard segment is high, the processing temperature is inevitably high, and side reactions tend to occur. In particular, when used for applications requiring heat resistance, it is essential that the hydrogenation rate be 90% or more. A more desirable hydrogenation rate is 95% or more. When the hydrogenation rate of the olefinically unsaturated double bond in the A block is 50% or more,
In addition, weather resistance and heat resistance are improved, but the processing temperature rises, and the microphase separation deteriorates depending on the molecular weight and the hard / soft ratio, and on the contrary, it exhibits sufficient performance as a high-performance thermoplastic elastomer. May not. The hydrogenation rate of the olefinically unsaturated double bond in the preferred A block is 25% or less.

The hydrogenation ratio of the olefinically unsaturated double bond in the A block and the B block is 95% or more, respectively.
A partially hydrogenated cyclic diene-based thermoplastic elastomer having a molecular weight, a hard / soft ratio and a microstructure within a predetermined range of 25% or less is preferred in terms of the most high-performance elastomer physical properties. Partially hydrogenated cyclic diene-based thermoplastic elastomer
Mainly, the vinyl conjugated diene monomer in the B block has a vinyl bond amount of 25 to 55%. Since the chain conjugated diene monomer in this B block is practically almost hydrogenated,
When the conjugated diene monomer is butadiene, the 1,4 bond becomes a polyethylene monomer and the vinyl bond becomes a 1-butene monomer. If the vinyl bond content before hydrogenation is smaller than 25%, when hydrogenated, a polyethylene crystal component is generated and the mechanical strength of the elastomer is improved, but the compression set (c-set) and the permanent set (p -Set) is deteriorated, and flexibility and low-temperature performance are lost.
If this value exceeds 55%, not only low temperature performance is lost but also mechanical strength at room temperature and high temperature, elongation and the like may be lost. A more preferable vinyl bond amount is 30 to 50%.
It is.

The cyclic diene-based thermoplastic elastomer and the partially hydrogenated thermoplastic elastomer can be used at room temperature to 250 ° C.
A micro phase-separated structure is formed in a temperature range up to about ℃, and the characteristic feature is that the temperature range showing good elastomer properties is wide. Usually, styrene-based thermoplastic elastomer
In the case of SBS or SEBS, for example, the glass transition temperature of the styrene domain portion is determined by a dynamic viscoelasticity measurement method such as DSC or Vibron. RMS (Rheometrics)
(Mechanical Spectrometer)
It was determined from the peak temperature of 800 "G. According to this, the glass transition temperature of the hard domain of the preferred thermoplastic elastomer of the present invention is from 130 to 200C, more preferably from 140 to 180C. .

The cyclic diene-based thermoplastic elastomer of the present invention can be preferably obtained by living anionic polymerization using a composite dilithium initiator according to the following method. This method involves adding 2 equivalents of monoorganic lithium initiator to -2.
In a non-polar hydrocarbon at a temperature in the range of 0 to 60 ° C in the presence of a tertiary monoamine and / or an ether compound, 1,3-
Reaction with diisopropenylbenzene or a derivative thereof, and then adding 0.05 to
0.49 moles of tertiary diamine and / or alkoxylithium compound and optionally 30
An α, ω-dilithium compound formed by adding a conjugated diene-based monomer in a molar amount of twice or less is used as an initiator without isolation.

The monoorganic lithium compound is an organic lithium compound having one lithium atom bonded to the molecule, for example, methyllithium, ethyllithium, n-propyllithium, isopropyllithium, n-butyllithium, sec-butyl. Lithium, tert-butyllithium, allyllithium, phenyllithium and the like. Among them, preferred lithium is sec-butyllithium or tert-butyllithium. 1,3
In the reaction of diisopropenylbenzene or a derivative thereof with monoorganic lithium, the reaction temperature is preferably-
The range is 10 to 50 ° C, more preferably 10 to 30 ° C.

In the reaction of 1,3-diisopropenylbenzene or a derivative thereof with monoorganic lithium, the concentration of monoorganic lithium is 0.3 mol / liter in a lithium / non-polar hydrocarbon solvent, preferably 0.6 mol / liter. 90 mol% or more, preferably 95 mol% or more, of all lithium atoms in the dilithium compound synthesized by reacting at a mol / liter, more preferably 1 mol / l or more, is composed of the dilithium compound.

The content of the dilithium compound is determined by deactivating the obtained dilithium compound with water in an inert atmosphere, and then measuring the GPC of the components contained in the organic layer. The column used has an exclusion limit of 1.
000 to 5000 are preferable, and an ultraviolet absorption spectrophotometer (254 nm) is used as a detector. It is possible to identify oligomer components in the water-inactivated compound from a column calibration curve using polystyrene as a standard sample, and to analyze the ratio of each component based on the molecular weight. Further, the unreacted monoorganic lithium compound contained in the catalyst is separately analyzed by gas chromatography from the water-inactivated sample and the active sample. Therefore, the true dilithium content can be calculated from the above analysis values.

Specific examples of the dilithium compound used as a polymerization initiator for the cyclic diene-based thermoplastic elastomer of the present invention include 1,3- or 1,4-bis (1-
(Lithio-1,3-dimethylpentyl) benzene, 1,3
-Or 1,4-bis (1-lithio-1-ethyl-3-
Methylpentyl) benzene, 1,3- or 1,4-bis (1-lithio-1,3-dimethylpentyl) -5-methylbenzene, 1,3- or 1,4-bis (1-lithio-1, 3-dimethylbutyl) benzene, 1,3- or 1,4-bis (1-lithio-1,3,3-trimethylbutyl) -5-methylbenzene and the like. Among such dilithium compounds, preferred initiators having a high dilithium content, excellent solubility, high living anionic polymerization activity, and synthesized from raw materials that are industrially easily available are 1,3-bis (1- Lithio-1,3-dimethylpentyl) benzene, 1,3-bis (1-lithio-1,
3,3-trimethylbutyl) benzene. That is, 1,3-diisopropenylbenzene and sec-butyllithium or tert-butyllithium are the most preferable combinations.

The non-polar hydrocarbon solvent used in the initiator synthesis reaction is preferably at least one solvent selected from alkanes and cycloalkanes having 5 to 8 carbon atoms, more preferably 5 or 6 carbon atoms. . A 1,3-diisopropenylbenzene derivative is one in which the methyl of an isopropenyl group is substituted by a phenyl group or an aryl group having 7 to 10 carbon atoms, and a part or all of the benzene ring is a methyl group. Refers to what has been replaced.

The tertiary monoamine and / or the ether compound used as a promoter in the reaction between the alkyl lithium and 1,3-diisopropenylbenzene are trimethylamine, triethylamine, dimethylaniline, tetrahydrofuran (THF), and tetramethyl THF. , Aniso-
And at least one compound selected from the group consisting of methyl, diethyl ether and tert-butylmethyl ether. If these compounds are present, some of them may be replaced with other ether compounds (eg, ethyl butyl ether) or other tertiary monoamine or tertiary diamine compounds (eg, TMEDA). The amount that can be replaced is up to 60 mole percent of the tertiary monoamine and / or ether compound. The tertiary diamine used in the polymerization of the A block is preferably at least one compound selected from tetraethylethylenediamine, tetramethylethylenediamine, tetraphenylethylenediamine, and tetracyclohexylethylenediamine.

The alkoxylithium compound used in the polymerization of the A block preferably has 3 to 6 carbon atoms, more preferably 4 carbon atoms, and particularly preferably tert-butoxylithium. Is done. The tertiary diamine and / or alkoxylithium compound is added at a concentration of 0.05 to 0.49 times the molar concentration of the Li concentration. When the addition amount is 0.05 mol or less,
Monodispersion may not cause polymerization. On the other hand, if the amount exceeds this, although the polymerization is carried out in a monodispersed state, the vinyl content in the conjugated diene monomer is increased, and the desired high-performance thermoplastic elastomer is obtained.
Is not preferred because it is not possible to obtain A more preferable addition amount is 0.1 to 0.24 times mol with respect to the Li concentration.

An example of a method for polymerizing a cyclic diene-based thermoplastic elastomer using the above-mentioned dilithium initiator is shown below. First, a block (B block) mainly composed of a linear conjugated diene monomer is polymerized.
And a block polymerization (A block) of a cyclic conjugated diene monomer or a derivative thereof after adding a tertiary diamine in an amount of 0.1 to 2.0 times the amount of the tertiary diamine.
Further, there is a monomer batch polymerization method in which a cyclic conjugated diene monomer and a linear conjugated diene monomer are simultaneously added and polymerized. In the case of the latter polymerization, additional addition of a tertiary diamine at the stage of polymerization is unnecessary because it has the effect of increasing the amount of vinyl in the linear conjugated diene monomer.

If necessary, a cyclic diene-based monomer or a derivative thereof, a linear conjugated diene monomer or a monomer mainly composed of a linear conjugated diene monomer is successively added to the polymer. Thus, a triblock, pentablock, or multiblock copolymer can be polymerized. Further, these polymerizations may be either isothermal polymerization or adiabatic polymerization. The polymerization temperature is 0 to 120C, preferably 20 to 1C.
The reaction is performed at a temperature of 00 ° C, more preferably 30 to 80 ° C. Further, the dilithium initiator of the present invention can be added with a conjugated diene-based monomer in an amount of 30 mol or less with respect to Li as needed before use in polymerization. 1,3-butadiene, isoprene, 2-
Ethyl-1,3-butadiene, 2,3-dimethyl-1,
It can be selected from 3-butadiene and 1,3-pentadiene or mixtures thereof.

When the polymerization is started at a molar ratio of 30 times or more, two or more types of growing species having different activities appear, and a high-speed portion and a low-speed portion are formed at the initiation and initial polymerization, respectively. The growth reaction may proceed with a molecular weight distribution of In this case, if necessary, the addition of a tertiary diamine is effective. On the other hand, if it is 30 moles or less,
The initiation reaction and the growth reaction of the polymerization occur completely in a unified manner, and the polymerization proceeds in a monodispersed state, so that a monodispersed polymer having a very narrow molecular weight distribution can be obtained. The molar ratio is appropriately selected at 30 or less, but when the diene-based monomer / dilithium initiator is mixed with the monomer and the initiator, heat generation is large,
When the polymer concentration is relatively high (about 25% by weight or more), the reaction system conditions fluctuate easily and control becomes difficult. Therefore, the preferred molar ratio of diene monomer / dilithium initiator at the start of polymerization is 10 to 30, more preferably 10 to 20. If it is selected in such a range, the heat generated by the initiation of polymerization is not large, and the dilithium initiators all have the same activity to initiate the polymerization initiation reaction. A narrow polymer can be obtained.

Such a conjugated diene monomer / dilithium initiator molar ratio needs to be realized at the start of polymerization. A monomer may be added. Further, another polymerization may be performed using the thus obtained dilithium oligomer as an initiator. More preferred chain conjugated diene monomers are 1,3-butadiene and isoprene. The α, ω-dilithium compound to be synthesized is used as it is as a polymerization initiator without isolation.

The method for polymerizing the cyclic conjugated diene-based thermoplastic elastomer of the present invention is solution polymerization, and usable solvents include butane, pentane, n-hexane, isohexane, isopentane, heptane, octane and isooctane. Hydrocarbons, cycloaliphatic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, and ethylcyclohexane; aromatic hydrocarbons such as benzene, toluene, ethylbenzene, and xylene; ethers such as diethyl ether and tetrahydrofuran Can be exemplified. These alone are 2
A mixture of more than one species may be used.

The amount of the polymerization initiator used in the preferred production method for obtaining the block copolymer composition of the present invention cannot be limited because it varies depending on the purpose, but is generally not limited. 1 × 10
^{Over 5} to 1 × 10 ^-1 mole% - in the range of St, preferably 1 × 10 ^{over 4} to 1 × 10 ^-2 mole% - can be implemented in cents range. The time required for the polymerization varies depending on the conditions, but is usually within 20 hours, particularly preferably 1 to 2.
5 hours. Further, it is desirable to replace the atmosphere of the polymerization system with an inert gas such as nitrogen, argon or helium. The polymerization pressure is not particularly limited, as long as the polymerization is performed at a pressure sufficient to maintain the monomer and the solvent in the liquid phase in the above-mentioned polymerization temperature range. Further, care must be taken to prevent impurities such as water, oxygen, carbon dioxide and the like, which inactivate the initiator and the active terminal, from being mixed into the polymerization system. The polymerization system can be used in any of a batch system, a continuous system, and a semi-batch system.

Further, prior to the polymerization, in the presence of a cyclic conjugated diene monomer and / or a monomer copolymerizable therewith,
Preliminary reaction or aging of some or all of the initiator components, preferably in the absence of the initiator component, is a preferable means in the method for suitably obtaining the block copolymer of the present invention. Depending on the conditions of these operations, polymerization activity is improved, and undesirable side reactions (chain transfer, elimination of active metal species) are prevented as much as possible, and as a result, effects such as narrowing of molecular weight distribution can be achieved. is there. After the polymerization reaction has reached a predetermined reaction rate, if necessary, in addition to the known coupling agent as described above, a terminal modifying agent or a terminal branching agent, further a polymerization terminator, a polymerization stabilizer, an antioxidant Is added to the reaction system. The addition of these at this stage is effective in preventing the polymer from undergoing oxidative deterioration or thermal deterioration when the solvent is removed in the next step. Examples of the terminal modifier include known compounds capable of reacting with the active terminal of ordinary living anionic polymerization.

These include halogen gas, carbon dioxide gas, carbon monoxide, alkylene oxide, alkylene sulfide, isocyanate compound, imino compound, aldehyde compound, ketone and thioketone compound, esters, lactones, amide-containing compounds, urea compounds, Acid anhydrides and the like can be mentioned. Examples of the terminal branching agent include compounds such as polyepoxide, polyisocyanate, polyimine, polyaldehyde, polyketone, polyanhydride, polyester, and polyhalide. These compounds may contain two or more functional groups in the molecule. These terminal modifiers or terminal branching agents may be used alone or in combination of two or more.

As the stabilizer and antioxidant, any of the conventionally known stabilizers may be used, and various stabilizers such as phenol, organic phosphate, organic phosphite, amine and sulfur can be used. The known antioxidants are used. The stabilizer is generally used in the range of 0.001 to 10 parts by weight based on 100 parts by weight of the block copolymer composition. As the polymerization terminator, a known terminator which can deactivate the active terminal of the organometallic compound complex which is a preferable initiator can be used.
Alcohols, ketones, polyhydric alcohols (ethylene glycol, propylene glycol, glycerin), phenol, hindered phenol which is also an antioxidant, acid, ketone, halogenated Hydrocarbons, amines and mixtures thereof. These are generally used in the range of 0.01 to 10 parts by weight based on 100 parts by weight of the polymer and the composition. The terminating agent may be added before adding the stabilizer, or may be added simultaneously with the stabilizer. Alternatively, deactivation may be performed by bringing molecular hydrogen into contact with the active terminal.

Next, the solvent is removed from the polymer solution, but a known desolvation method in the production of an ordinary conjugated diene-based polymer may be used. For example, a method in which the solvent is heated to evaporate, or the solution is heated in hot water A method of dispersing and blowing steam to evaporate the solvent (a steam stripping method); a method of adding a large amount of a precipitant such as methanol to separate the solvent; a method of drying the solution under vacuum; After evaporating a part of the solvent, a method of further removing the solvent with a vented extruder can be employed. The partially hydrogenated conjugated diene-based thermoplastic elastomer of the present invention can more selectively hydrogenate the olefinically unsaturated double bond in the B block among the olefinically unsaturated double bonds in the block copolymer polymerized by the above polymerization method or the like. This is a thermoplastic elastomer which has been further improved in weather resistance and oxidation resistance by hydrogenation.

The meaning of partial hydrogenation means that 90% or more, preferably 95% or more, of the olefinically unsaturated double bonds of the linear conjugated diene block in the B block is obtained by using a specific hydrogenation catalyst. It means that the hydrogenation rate of the olefinically unsaturated double bond of the cyclic conjugated diene or its derivative block in the A block is 50% or less, preferably 25% or less. Usually, the olefinically unsaturated double bond in the linear conjugated diene block is oxidized by oxygen, heat, and ozone, cross-linked, and cuts in the molecular chain, which may cause undesirable deterioration in physical properties as a thermoplastic elastomer. However, even if the olefinically unsaturated double bond in the cyclic diene conjugated diene block remains, it is hard to suffer from undesirable physical property deterioration.
Although the reason for this is not clear, the molecular chain of the cyclic conjugated diene block is usually easily broken. It is presumed that one is not seen.

Of course, if the hydrogenation rate of the olefinically unsaturated double bond of the cyclic conjugated diene unit in the A block is increased, a super heat and weather resistant block polymer can be obtained. It is not suitable for practical use unless the structure is limited. The present inventors have found that the partially hydrogenated conjugated diene-based thermoplastic elastomer of the present invention can be efficiently produced by the following method, and have completed the invention. In the method of the present invention, a partially hydrogenated cyclic diene-based thermoplastic elastomer characterized by using a hydrogenation catalyst composition comprising the following components (A) and (B) when producing a partially hydrogenated thermoplastic elastomer. It is a manufacturing method of.

The catalyst component (A) is a titanocene compound represented by the following general formula (3).

Embedded image (However, R ¹ and R ² represent a group selected from hydrogen and a hydrocarbon group of C _{1 to} C ₁₂ , and R ¹ and R ² may be the same or different. R ³ and R ⁴ are Represents a group selected from hydrogen, a C _{1 to} C ₁₂ hydrocarbon group, an aryloxy group, an alkoxy group, a halogen group and a carbonyl group, and R ³ and R ⁴ may be the same or different.)

The C ₁ -C ₁₂ hydrocarbon groups of R ¹ and R ² include, for example, substituents represented by the following general formula (4)

Embedded image (However, R ⁸ to R ¹⁰ represent hydrogen or a C ₁ to C ₄ alkyl hydrocarbon group, at least one of R ⁸ to R ¹⁰ is hydrogen, and n = 0 or 1.) Among 4), compounds in which all of R ⁸ to R ¹⁰ are alkyl hydrocarbon groups are not preferred because hydrogenation activity may possibly be slightly inferior due to steric hindrance. Compounds in which the alkyl hydrocarbon group is ortho to the central metal are active but are not desirable because they are difficult to synthesize.

Specific examples of the catalyst component (A) include bis (η ⁵ -methylcyclopentadienyl) titanium dimethyl, bis (η ⁵ -ethylcyclopentadienyl) titanium dimethyl, bis (η ⁵ -propylcyclo pentadienyl) titanium dimethyl, bis (eta ^5-n-butyl cyclopentadienyl) titanium dimethyl, bis (eta ⁵ - methyl cyclopentadienyl) titanium diethyl, bis (eta ⁵ - cyclopentadienyl) titanium diethyl, bis (eta ⁵ - propyl cyclopentadienyl) titanium diethyl, bis (eta ^5-n-butyl cyclopentadienyl) titanium diethyl, bis (eta ⁵ -
Cyclopentadienyl) titanium di-sec-butyl, bis (η ⁵ -methylcyclopentadienyl) titanium di-sec-butyl, bis (η ⁵ -ethylcyclopentadienyl) titanium di-sec-butyl, bis ( eta ⁵ - propyl cyclopentadienyl) titanium di -sec- butyl, bis (eta ^5-n-butyl cyclopentadienyl) titanium di -sec- butyl, bis (eta
⁵ -cyclopentadienyl) titanium dihexyl,

Bis (η ⁵ -methylcyclopentadienyl) titanium dihexyl, bis (η ⁵ -ethylcyclopentadienyl) titanium dihexyl, bis (η ^5-
Propylcyclopentadienyl) titanium dihexyl, bis (η ⁵ -n-butylcyclopentadienyl) titanium dihexyl, bis (η ⁵ -cyclopentadienyl) titanium dioctyl, bis (η ⁵ -methylcyclopentadienyl) titanium Dioctyl, bis (η ⁵ −
Ethylcyclopentadienyl) titanium dioctyl,
Bis (η ⁵ -propylcyclopentadienyl) titanium dioctyl, bis (η ⁵ -n-butylcyclopentadienyl) titanium dioctyl, bis (η ⁵ -cyclopentadienyl) titanium dimethoxide, bis (η ^5-
Methylcyclopentadienyl) titanium dimethoxide, bis (eta ⁵ - ethyl cyclopentadienyl) titanium dimethoxide, bis (eta ⁵ - propyl cyclopentadienyl) titanium dimethoxide, bis (eta ^5-n-
Butylcyclopentadienyl) titanium dimethoxide, bis (η ⁵ -cyclopentadienyl) titanium diethoxide, bis (η ⁵ -methylcyclopentadienyl) titanium diethoxide,

Bis (η ⁵ -ethylcyclopentadienyl) titanium diethoxide, bis (η ⁵ -propylcyclopentadienyl) titanium diethoxide, bis (η ⁵ -n-butylcyclopentadienyl) titanium diethoxide Ethoxide, bis (η ⁵ -cyclopentadienyl) titanium dipropoxide, bis (η ⁵ -methylcyclopentadienyl) titanium dipropoxide, bis (η ⁵
-Ethylcyclopentadienyl) titanium dipropoxide, bis (η ⁵ -propylcyclopentadienyl) titanium dipropoxide, bis (η ⁵ -n-butylcyclopentadienyl) titanium dipropoxide, bis (η ⁵ -Cyclopentadienyl) titanium dibutoxide, bis (η ⁵ -methylcyclopentadienyl) titanium dibutoxide, bis (η ⁵ -ethylcyclopentadienyl) titanium dibutoxide,

Bis (η ⁵ -propylcyclopentadienyl) titanium dibutoxide, bis (η ⁵ -n-butylcyclopentadienyl) titanium dibutoxide, bis (η ⁵ -cyclopentadienyl) titanium diphenyl, bis ( η ⁵ -methylcyclopentadienyl) titanium diphenyl, bis (η ⁵ -ethylcyclopentadienyl) titanium diphenyl, bis (η ⁵ -propylcyclopentadienyl) titanium diphenyl, bis (η
^5- n-butylcyclopentadienyl) titanium diphenyl, bis (η ⁵ -cyclopentadienyl) titanium di (m-tolyl), bis (η ⁵ -methylcyclopentadienyl) titanium di (m-tolyl), Screw (η ⁵ −
Ethylcyclopentadienyl) titanium di (m-tolyl), bis (η ⁵ -propylcyclopentadienyl) titanium di (m-tolyl), bis (η ⁵ -n-butylcyclopentadienyl) titanium di (m -Tolyl),

Bis (η ⁵ -cyclopentadienyl) titanium di (p-tolyl), bis (η ⁵ -methylcyclopentadienyl) titanium di (p-tolyl), bis (η
⁵ -ethylcyclopentadienyl) titanium di (p-
Tolyl), bis (eta ⁵ - propyl cyclopentadienyl) titanium di (p- tolyl), bis (eta ^5-n-butyl cyclopentadienyl) titanium di (p- tolyl), bis (eta ⁵ - cyclopenta Dienyl) titanium di (m, p-xylyl), bis (η ⁵ -methylcyclopentadienyl) titanium di (m, p-xylyl), bis (η ⁵ -ethylcyclopentadienyl) titanium di (m, p-xylyl), bis (η ⁵ -propylcyclopentadienyl) titanium di (m, p-xylyl), bis (η ⁵ -n-butylcyclopentadienyl) titanium di (m, p-xylyl), bis (Η ⁵ -cyclopentadienyl) titanium di (4-ethylphenyl), bis (η ⁵ -methylcyclopentadienyl) titanium di (4-ethylphenyl),

Bis (η ⁵ -ethylcyclopentadienyl) titanium di (4-ethylphenyl), bis (η ⁵
-Propylcyclopentadienyl) titanium di (4-
Ethylphenyl), bis (eta ^5-n-butyl cyclopentadienyl) titanium di (4-ethylphenyl) bis (eta ⁵ - cyclopentadienyl) titanium di (4-
Hexyl phenyl), bis (eta ⁵ - methyl cyclopentadienyl) titanium di (4-hexyl-phenyl), bis (eta ⁵ - ethyl cyclopentadienyl) titanium di (4-hexyl-phenyl), bis (eta ⁵ - propyl Cyclopentadienyl) titanium di (4-hexylphenyl), bis (η ⁵ -n-butylcyclopentadienyl)
Titanium di (4-hexylphenyl), bis (η ⁵ −
Cyclopentadienyl) titanium diphenoxide, bis (η ⁵ -methylcyclopentadienyl) titanium diphenoxide, bis (η ⁵ -ethylcyclopentadienyl) titanium diphenoxide, bis (η ⁵ -propylcyclopentadienyl) Titanium diphenoxide, bis (η ⁵ -n-butylcyclopentadienyl) titanium diphenoxide,

Bis (η ⁵ -n-butylcyclopentadienyl) titanium di (4-hexylphenyl), bis (η ⁵ -cyclopentadienyl) titanium difluoride, bis (η ⁵ -methylcyclopentadienyl) ) Titanium difluoride, bis (η ⁵ -ethylcyclopentadienyl) titanium difluoride, bis (η ^5-
Propylcyclopentadienyl) titanium difluoride, bis (η ⁵ -n-butylcyclopentadienyl)
Titanium difluoride, bis (eta ⁵ - cyclopentadienyl) titanium dichloride, bis (eta ⁵ - methylcyclopentadienyl) titanium dichloride, bis (eta ⁵ - ethyl cyclopentadienyl) titanium dichloride, bis (eta ⁵ - propyl cyclopentadienyl) titanium dichloride, bis (eta ^5-n-butyl cyclopentadienyl) titanium dichloride, bis (eta ⁵ - cyclopentadienyl) titanium dibromide, bis (eta ⁵ - cyclopentadienyl ) titanium dibromide, bis (eta ⁵ - ethyl cyclopentadienyl) titanium dibromide, bis (eta ⁵ - propyl cyclopentadienyl) titanium dibromide, bis (eta ^5-n-butyl cyclopentadienyl) titanium di Bromide, bis (η ⁵ -cyclopentadienyl)
Titanium diiodide, bis (η ⁵ -methylcyclopentadienyl) titanium diiodide, bis (η ⁵ −
Ethyl cyclopentadienyl) titanium di-iodide, bis (eta ⁵ - propyl cyclopentadienyl) titanium di-iodide, bis (eta ^5-n-butyl cyclopentadienyl) titanium di-iodide,

Bis (η ⁵ -cyclopentadienyl) titanium chloride methyl, bis (η ⁵ -methylcyclopentadienyl) titanium chloride methyl, bis (η
⁵ - ethyl cyclopentadienyl) titanium chloride methyl, bis (eta ⁵ - propyl cyclopentadienyl) titanium chloride methyl, bis (eta ^5-n-butyl cyclopentadienyl) titanium chloride methyl, bis (eta ⁵ - cyclo pentadienyl) titanium chloride ethoxide, bis (eta ⁵ - methylcyclopentadienyl) titanium dichloride ethoxide, bis (eta ⁵ - ethyl cyclopentadienyl) titanium dichloride ethoxide, bis (eta ⁵ - propyl cyclopentadienyl enyl) titanium chloride ethoxide, bis (eta ^5-n-butyl cyclopentadienyl) titanium dichloride ethoxide, bis (eta ⁵ - cyclopentadienyl) titanium chloride phenoxide, bis (eta ⁵ - cyclopentasiloxane Enyl) titanium chloride phenoxide, bis (eta ⁵ - ethyl cyclopentadienyl) titanium dichloride phenoxide, bis (eta ⁵ - propyl cyclopentadienyl) titanium dichloride phenoxide, bis (eta ^5-n-butyl cyclopentadienyl Enyl) titanium chloride phenoxide,

Bis (η ⁵ -cyclopentadienyl) titanium chloride benzyl, bis (η ⁵ -methylcyclopentadienyl) titanium chloride benzyl, bis (η ⁵ -cyclopentadienyl) titanium dibenzyl, bis (η ⁵ -Methylcyclopentadienyl) titanium dibenzyl, bis (η ⁵ -ethylcyclopentadienyl) titanium dibenzyl, bis (η ⁵ -propylcyclopentadienyl) titanium dibenzyl, bis (η
^5-n-butyl cyclopentadienyl) titanium dibenzyl, bis (eta ⁵ - methyl cyclopentadienyl) titanium dicarbonyl, bis (eta ⁵ - cyclopentadienyl) titanium dicarbonyl, bis (eta ⁵ - Echirushikuro pentadienyl) titanium dicarbonyl, bis (eta ⁵ - propyl cyclopentadienyl) titanium dicarbonyl, bis (eta ^5-n-butyl cyclopentadienyl) titanium dicarbonyl, and the like. These can be used alone or in combination with each other. These titanocene compounds are not limited to the above examples, and those having 0, 2, 3, or 4 substituents on the alkyl group of the cyclopentadienyl ring are also suitably used.

Each of these titanocene compounds hydrogenates the olefinically unsaturated double bond of the olefin compound to a high degree and is excellent in heat resistance. In particular, the linear conjugated diene unit in the cyclic diene-based block polymer is excellent. The hydrogenation activity and selectivity to the olefinically unsaturated double bond are high, and the unsaturated double bond is highly and selectively hydrogenated in a wide temperature range. Bis (η ⁵ -cyclopentadienyl) titanium dichloride, bis (η ⁵ -methylcyclopentadienyl) titanium dichloride, bis (η ⁵ -ethylcyclopentadienyl) titanium dichloride, bis (η
⁵ -propylcyclopentadienyl) titanium dichloride, bis (η ⁵ -n-butylcyclopentadienyl) titanium dichloride, bis (η ⁵ -cyclopentadienyl) titanium dimethyl,

Bis (η ⁵ -methylcyclopentadienyl) titanium dimethyl, bis (η ⁵ -ethylcyclopentadienyl) titanium dimethyl, bis (η ⁵ -propylcyclopentadienyl) titanium dimethyl, bis (η ^5- n-butylcyclopentadienyl) titanium dimethyl, bis (η ⁵ -cyclopentadienyl) titanium di (p-tolyl), bis (η ⁵ -methylcyclopentadienyl) titanium di (p-tolyl), bis ( η ⁵
-Ethylcyclopentadienyl) titanium di (p-tolyl), bis (η ⁵ -propylcyclopentadienyl)
Titanium di (p-tolyl), bis (η ⁵ -n-butylcyclopentadienyl) titanium di (p-tolyl),
Bis (η ⁵ -cyclopentadienyl) titanium diphenyl, bis (η ⁵ -methylcyclopentadienyl) titanium diphenyl, bis (η ⁵ -ethylcyclopentadienyl) titanium diphenyl, bis (η ⁵ -propylcyclopentadi enyl) titanium diphenyl, bis (eta ^5-n-butyl cyclopentadienyl) titanium diphenyl.

Further, it can be handled stably in air, and particularly preferable are bis (η ⁵ -cyclopentadienyl) titanium dichloride, bis (η ⁵ -methylcyclopentadienyl) titanium dichloride, bis (η
^5- n-butylcyclopentadienyl) titanium dichloride, bis (η ⁵ -methylcyclopentadienyl)
Titanium diphenyl, bis (η ⁵ -n-butylcyclopentadienyl) titanium diphenyl, bis (η ⁵ −
Cyclopentadienyl) titanium di (p-tolyl),
Bis (eta ⁵ - methyl cyclopentadienyl) titanium di (p- tolyl), bis (eta ^5-n-butyl cyclopentadienyl) titanium di (p- tolyl) can be mentioned.

On the other hand, as the catalyst component (B), among known organometallic compounds and metal-containing compounds capable of reducing the titanocene compound of the catalyst component (A), Li, Na,
At least one reducing agent selected from compounds containing at least one element of K, Mg, Zn, Al and Ca is used. These are organic lithium compounds, organic sodium compounds, organic potassium compounds, organic zinc compounds,
An organic magnesium compound, an organic aluminum compound, an organic calcium compound and the like can be mentioned, and an olefin compound can be hydrogenated by using alone or in combination of two or more kinds (A).

Specific examples of the lithium-containing compound include methyllithium, ethyllithium, n-propyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, isobutyllithium, tert-butyllithium, n-pentyllithium, n-pentyllithium and n-pentyllithium. -Hexyllithium, phenyllithium, cyclopentadienyllithium, m-tolyllithium, p-tolyllithium, xylyllithium, dimethylaminolithium, diethylaminolithium, various dilithium, trilithium compounds, methoxylithium, ethoxylithium, n -Propoxylithium, isopropoxylithium, n-butoxylithium, sec-butoxylithium, t-butoxylithium, pentyloxylithium, hexyloxylithium, heptyloxyli Um, octyloxy lithium, phenoxy lithium, 4-methylphenoxy lithium, benzyloxy lithium, 4-methyl-benzyloxy lithium, and the like.

Further, a lithium phenolate compound obtained by reacting a phenol-based stabilizer with an alkyl lithium is also used. Specific examples of such a phenol-based stabilizer include 1-oxy-3-methyl-4-isopropylbenzene, 2,6-di-tert-butylphenol,
6-di-tert-butyl-4-ethylphenol,
2,6-di-tert-butyl-p-cresol, 2,
6-di-tert-butyl-4-n-butylpheno-
4-hydroxymethyl-2,6-di-tert-butylphenol, butylhydroxyanisole, 2-
(1-methylcyclohexyl) -4,6-dimethylphenol, 2,4-dimethyl-6-tert-butylphenol, 2-methyl-4,6-dinonylphenol,
2,6-di-tert-butyl-α-dimethylamino-
p-cresol, methylenebis (dimethyl-4,6-phenol), 2,2'-methylenebis (4-methyl-6
-Tert-butylphenol), 2,2'-methylenebis (4-methyl-6-cyclohexylphenol),
2,2'-methylenebis (4-ethyl-6-tert-
Butylphenol), 4,4'-methylenebis (2,6
-Di-tert-butylphenol), 2,2'-methylenebis (6-α-methylbenzyl-p-cresol)
And the like.

The most versatile 2,6-di-t-butyl-p
2,6-di-t in which the hydroxyl group of cresol is -OLi
-Butyl-4-methylphenoxylithium is particularly preferably used. Further, organosilicon lithium compounds such as trimethylsilyllithium, diethylmethylsilyllithium, dimethylethylsilyllithium, triethylsilyllithium, and triphenylsilyllithium may be used. Containing Na
Specific examples of the compound include methyl sodium, ethyl sodium, n-propyl sodium, isopropyl sodium, n-butyl sodium, sec-butyl sodium, isobutyl sodium, tert-butyl sodium, n-pentyl sodium, n-hexyl sodium, phenyl Sodium, cyclopentadienyl sodium, m-tolyl sodium, p-tolyl sodium,
Xylyl sodium, sodium naphthalene, and the like.

Specific examples of the K-containing compound include methyl potassium, ethyl potassium, n-propyl potassium, isopropyl potassium, n-butyl potassium, sec-butyl potassium, isobutyl potassium, tert-butyl potassium, n-pentyl potassium, n-pentyl potassium -Hexyl potassium,
Triphenylmethyl potassium, phenyl potassium, phenylethyl potassium, cyclopentadienyl potassium,
Examples thereof include m-tolyl potassium, p-tolyl potassium, xylyl potassium, potassium naphthalene and the like.
The organic alkali metal compound, a part of the organic alkaline earth metal compound is used as a living anion polymerization initiator of a cyclic conjugated diene and a linear conjugated diene compound, and in some cases, a vinyl aromatic hydrocarbon compound.
When the olefin compound to be hydrogenated is a cyclic conjugated diene polymer (living polymer) having active terminals of these metals, these active terminals also act as the catalyst (B) component.

Examples of the Zn-containing compound include diethyl zinc, bis (η ⁵ -cyclopentadienyl) zinc, diphenyl zinc, and the like. Examples of the Mg-containing compound include dimethyl magnesium, diethyl magnesium, dibutyl magnesium, and ethyl butyl magnesium. , Methyl magnesium bromide, ethyl magnesium chloride, ethyl magnesium bromide, ethyl magnesium chloride, phenyl magnesium bromide, phenyl magnesium chloride, t-butyl magnesium chloride, t-butyl magnesium bromide and the like.

Further, as Al-containing compounds, trimethylaluminum, triethylaluminum, triisobutylaluminum, triphenylaluminum, diethylaluminum chloride, dimethylaluminum chloride, ethylaluminum dichloride, methylaluminum sesquichloride, ethylaluminum sesquichloride, diethylaluminum hydride, Examples thereof include diisobutylaluminum hydride, triphenylaluminum, tri (2-ethylhexyl) aluminum, (2-ethylhexyl) aluminum dichloride, methylaluminoxane, and ethylaluminoxane.

In addition to these, alkali (earth) metal hydrides such as lithium hydride, potassium hydride, sodium hydride and calcium hydride;
Sodium aluminum hydride, potassium aluminum hydride, diisobutyl sodium aluminum hydride, tri (t-butoxy) aluminum hydride, triethyl sodium aluminum hydride, diisobutyl sodium aluminum hydride, triethyl sodium aluminum hydride, triethoxy sodium aluminum hydride, triethyl lithium aluminum hydride, etc. A hydride containing more than one kind of metal may be used. Further, a complex synthesized by preliminarily reacting the organic alkali metal compound and the organic aluminum compound, a complex (art complex) synthesized by preliminarily reacting the organic alkali metal compound and the organic magnesium compound, and the like are also included. It is.

The catalyst components (A) and (B) are indispensable, and the catalyst composition composed of both components hydrogenates the unsaturated double bond of the olefin compound to a high degree in a wide temperature range.
By combining the components (A) and (B) with the component (C) or (D), the storage stability of the catalyst is increased, the reproducibility of the hydrogenation activity is expressed, and the handling becomes easier. In producing the partially hydrogenated thermoplastic elastomer of the present invention, the total amount of the olefinically unsaturated double bonds in the side chain olefinically unsaturated double bonds is added to the components (A) and (B) as catalyst components. It is a preferred embodiment to use a catalyst composition using, as the component (C), an olefinically unsaturated double bond-containing polymer having a fraction of 0.3 to 1 with respect to.

The component (C) of the catalyst is an olefinically unsaturated double bond-containing polymer having a fraction of 0.3 to 1 relative to the total amount of olefinically unsaturated double bonds in the side chain. As an example of a monomer used for the production of this polymer, a conjugated diene can be mentioned.
Conjugated dienes having from about 12 carbon atoms are included. Specific examples include 1,3-butadiene, isoprene, 2,3-dimethylbutadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 4,5-diethyl- Examples thereof include 1,3-octadiene, 3-butyl-1,3-octadiene, and 1,3-cyclohexadiene. These may be used alone or in combination of two or more. 1,3-butadiene and isoprene, which can be developed industrially and are relatively easy to handle, are particularly preferred, and polybutadienes, polyisoprenes, and butadiene / isoprene copolymers, which are homopolymers or copolymers thereof, are preferred.

Further, norbornadiene, cyclopentadiene, 2,3-dihydrodicyclopentadiene and their alkyl-substituted products may be homopolymerized or copolymerized. The polymer of the catalyst component (C) has a number average molecular weight of 5
It is sufficient if it is not less than 00 and not more than 1,000,000. When the number average molecular weight is less than 500, the effect of stabilizing the catalyst activity is reduced. A liquid rubber having a number average molecular weight of 500 or more, which is easy to handle and has excellent solvent solubility, is used. The liquid rubber is preferably liquid at room temperature, and has a number average molecular weight of 500 to 10
000 is particularly good. There is no particular problem in the performance of the catalyst composition except that when the number average molecular weight is 10,000 or more, handling as a liquid becomes difficult. In the polymer of the catalyst (C) component, the microstructure is most important. The “fraction of the olefinically unsaturated double bond in the side chain relative to the total olefinically unsaturated double bond” is defined as follows.

[Number of olefinically unsaturated carbon-carbon double bonds in the side chain of the component (C) polymer] / [total number of olefinically unsaturated carbon-carbon double bonds in the entirety of the component (C) polymer] Is preferably in the range of 0.3 to 1, and within this range, the terminal may have a functional group such as a hydroxyl group, a carboxyl group, an amino group, or an epoxy group. This value range means that when polybutadiene is used as a specific example of the catalyst (C) component, all olefinically unsaturated double bonds (cis 1,4 bond, trans 1,4 bond,
Olefinically unsaturated double bond (1,
(2 bonds) is preferably in the range of 0.3 to 1 (30 to 100%). If this ratio is less than 0.3, the hydrogenated catalyst composition after reduction becomes unstable and storage stability is poor, which is not preferable.

This polymer may be a copolymer of a conjugated diene and an aromatic vinyl compound. Specific examples of the aromatic vinyl compound include styrene, t-butylstyrene, α
-Methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylethylene, N, N-diethyl-p-aminoethylstyrene, and the like, with styrene being particularly preferred. As a specific example of the copolymer, a butadiene / styrene copolymer, an isoprene / styrene copolymer and the like are most preferable. These copolymers may be any of random, block, star block, tapered block, etc., and are not particularly limited. The amount of the bound aromatic vinyl compound is preferably 70% or less. When this amount exceeds 70%, the ratio of the olefinically unsaturated double bond in the side chain of the conjugated diene portion to the total copolymer decreases, so that the effect of stabilizing the catalyst decreases.
Since a relatively large amount of the catalyst component (C) is required, the physical properties of the hydrogenated conjugated diene-based polymer and the copolymer of the conjugated diene and the vinyl aromatic hydrocarbon may be changed. There is no.

Most importantly, it is necessary that the fraction of the olefinically unsaturated double bond in the side chain of the conjugated diene part of the component (C) with respect to the total olefinic double bond is from 0.3 to 1. The more desirable fraction is 0.5 to 0.99. These catalyst components (C) may be polymerized by any known method such as radical polymerization, cationic polymerization, anionic polymerization, and coordinating anionic polymerization, but the amount of the olefinically unsaturated double bond in the side chain is increased. This can be achieved by living anionic polymerization using an organic lithium or organic sodium compound as a catalyst in a polar solvent or in the presence thereof, by coordination anionic polymerization using a cobalt-type Ziegler-type catalyst, or by ethylene and dicyclohexane. It can be obtained by copolymerizing pentadienes.

Specific examples of such polar solvents include tetrahydrofuran, tetramethylethylenediamine, trimethylamine, triethylamine, ethyl ether, tetramethylfuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether,
And dipiperidinoethane. As a Li-based catalyst, methyllithium, ethyllithium, n-propyllithium, isopropyllithium, n-butylium, sec
-Butyllithium, isobutyllithium, tert-butyllithium, n-pentyllithium, n-hexyllithium, trimethylsilyllithium, and the like.
Examples of the Na-based catalyst include methyl sodium, ethyl sodium, n-propyl sodium, isopropyl sodium, n-butyl sodium, sec-butyl sodium, isobutyl sodium, phenyl sodium, sodium naphthalene, and cyclopentadienyl sodium.

In order to further improve the storage stability of the catalyst composition comprising the catalysts (A), (B), (C) or (A), (B), (D), the catalysts (A), (B)
The combination with the components (C) and (D) is most effective.
The component (D) includes an alcohol compound, an alkoxylithium compound, an alkoxysodium compound, an alkoxypotassium compound, an ether compound, a thioether compound, a ketone compound, a sulfoxide compound, a carboxylic acid compound, a carboxylic ester compound, and an aldehyde. Compound,
Examples include at least one polar compound selected from the group consisting of a lactone compound, an amine compound, an amide compound, a nitrile compound, an epoxy compound and an oxime compound.

Among these, specific examples of the alcohol compound include methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol, and the like. Tert-butyl alcohol, n-amyl alcohol, isoamyl alcohol, hexyl alcohol and its isomers, heptyl alcohol and its isomers, octyl alcohol and its isomers, caprylic alcohol ,
Nonyl alcohol and its isomers, decyl alcohol and its isomers, benzyl alcohol, phenol, cresol, 2,6-di-tert-butyl-p-cresol-
Monohydric alcohols such as ethylene glycol, ethylene glycol, propylene glycol, butanediol, pentyl glycol,
Examples thereof include neopentyl glycol, hexyl glycol, heptyl glycol, and glycol (divalent alcohol) which is an isomer of these glycols.
Further, compounds having other functional groups in one molecule, such as trivalent alcohol such as glycerin, ethanolamine, and glycidyl alcohol may be used.

Further, specific examples of the ether compound include:
Dimethyl ether, diethyl ether, di-n-propyl ether, diisopropyl ether, di-n-butyl ether, di-sec-butyl ether, diphenyl ether, methyl ethyl ether, ethyl butyl ether, Butyl vinyl ether, anisole, ethyl phenyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol
Examples thereof include rudibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, furan, tetrahydrofuran, α-methoxytetrahydrofuran, pyran, tetrahydropyran, and dioxane. Further, a compound having another functional group in one molecule, such as tetrahydrofurancarboxylic acid, may be used.

Specific examples of the thioether compound include dimethyl sulfide, diethyl sulfide, di-n
-Butyl sulfide, di-sec-butyl sulfide,
Di-t-butyl sulfide, diphenyl sulfide, methyl ethyl sulfide, ethyl butyl sulfide, thioanisole, ethyl phenyl sulfide, thiophene,
And tetrahydrothiophene. Further, specific examples of the ketone compound include acetone, diethyl ketone,
Di-n-propyl ketone, diisopropyl ketone, di-
n-butyl ketone, di-sec-butyl ketone, di-t
-Butyl ketone, benzophenone, methyl ethyl ketone, acetophenone, benzylphenyl ketone, propiophenone, cyclopentanone, cyclohexanone, diacetyl, acetylacetone, benzoylacetone and the like.

Further, specific examples of the sulfoxide compound include dimethylsulfoxide, diethylsulfoxide, tetramethylenesulfoxide, pentamethylenesulfoxide, diphenylsulfoxide, dibenzylsulfoxide, p-tolylsulfoxide and the like. Further specific examples of the carboxylic acid compound include formic acid, acetic acid, propionic acid, butyric acid, caproic acid, lauric acid, palmitic acid, stearic acid, cyclohexylpropionic acid, cyclohexylcaproic acid, benzoic acid, phenylacetic acid, o-
Toluic acid, m-toluic acid, p-toluic acid, acrylic acid, monobasic acid such as methacrylic acid, oxalic acid, maleic acid,
Malonic, fumaric, succinic, adipic, pimelic, suberic, sebacic, itaconic, phthalic,
In addition to dibasic acids such as isophthalic acid, terephthalic acid, naphthalic acid, and diphenic acid, trimellitic acid / pyromellitic acid and derivatives thereof can be given. Further, for example, a compound having another functional group in one molecule such as hydroxybenzoic acid may be used.

Further, specific examples of carboxylic acid esters include formic acid, acetic acid, propionic acid, butyric acid, caproic acid, lauric acid, palmitic acid, stearic acid, cyclohexylpropionic acid, cyclohexylcaproic acid, benzoic acid, phenylacetic acid, o- Toluic acid, m-toluic acid,
Monobasic acids such as p-toluic acid, acrylic acid, methacrylic acid, oxalic acid, maleic acid, malonic acid, fumaric acid, succinic acid,
Dibasic acids such as adipic acid, pimelic acid, suberic acid, sebacic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, naphthalic acid, diphenic acid and methyl alcohol
, N-propyl alcohol, isopropyl alcohol
, N-butyl alcohol, sec-butyl alcohol
Tert-butyl alcohol, amyl alcohol, hexyl alcohol, heptyl alcohol, isoheptyl alcohol, sec-heptyl alcohol, octyl alcohol and its isomers, phenol, cresol And esters with alcohols such as glycidyl alcohol, and β-ketoesters such as methyl acetoacetate and ethyl acetoacetate.

Further, specific examples of the lactone compound include:
Examples include β-propiolactone, δ-valerolactone, ε-caprolactone, and lactone compounds corresponding to the following acids. That is, as the acid, 2-methyl-
3-hydroxy-propionic acid, 3-hydroxynonanone or 3-hydroxypelargonic acid, 2-dodecyl-
3-hydroxypropionic acid, 2-cyclopentyl-3
-Hydroxypropionic acid, 3-phenyl-3-hydroxypropionic acid, 2-naphthyl-3-hydroxypropionic acid, 2-n-butyl-3-cyclohexyl-3-
Hydroxypropionic acid, 2-phenyl-3-hydroxytridecanoic acid, 2- (2-ethylcyclopentyl)-
3-hydroxypropionic acid, 2-methylphenyl-3
-Hydroxypropionic acid, 3-benzyl-3-hydroxypropionic acid, 2,2-dimethyl-3-hydroxypropionic acid, 2-methyl-5-hydroxyvaleric acid, 3-cyclohexyl-5-hydroxyvaleric acid,
4-phenyl-5-hydroxyvaleric acid, 2-heptyl-4-cyclopentyl-5-hydroxyvaleric acid,
2-methyl-3-phenyl-5-hydroxyvaleric acid, 3- (2-cyclohexylethyl) -5-hydroxyvaleric acid, 2- (2-phenylethyl) -4- (4
-Cyclohexylbenzyl) -5-hydroxyvaleric acid, benzyl-5-hydroxyvaleric acid, 3-ethyl-5-isopropyl-6-hydroxycaproic acid, 2-
Cyclopentyl-4-hexyl-6-hydroxycaproic acid, 2-cyclopentyl-4-hexyl-6-hydroxycaproic acid, 3-phenyl-6-hydroxycaproic acid, 3- (3,5-diethyl-cyclohexyl) -5
-Ethyl-6-hydroxycaproic acid, 4- (3-phenyl-propyl) -6-hydroxycaproic acid, 2-benzyl-5-isobutyl-6-hydroxycaproic acid,
7-phenyl-6-hydroxyl-octoenoic acid, 2,
2-di (1-cyclohexenyl) -5-hydroxy-5
-Heptenoic acid, 2,2-dipropenyl-5-hydroxy-5-heptenoic acid, 2,2-dimethyl-4-propenyl-3-hydroxy-3,5-heptadienoic acid and the like.

Further, specific examples of the amine compound include isopropylamine, n-butylamine, sec-butylamine, t-butylamine, n-amylamine, t-amylamine, n-hexylamine, n-heptylamine, aniline, benzylamine, o-anisidine, m-
Anisidine, p-anisidine, α-naphthylamine, dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, di-sec-butylamine, di-t-butylamine, di-
n-amylamine, diisoamylamine, dibenzylamine, N-methylaniline, N-ethylaniline, N-
Ethyl-o-toluidine, N-ethyl-m-toluidine, N-ethyl-p-toluidine, triethylamine,
Tri-n-propylamine, tri-n-butylamine,
Tri-n-amylamine, triisoamylamine, tri-n-hexylamine, tribenzylamine, triphenylmethylamine, N, N-dimethylbenzylamine,
N, N-dimethylaniline, N, N-diethylaniline, N, N-diethyl-o-toluidine, N, N-diethyl-m-toluidine, N, N-diethyl-p-toluidine, N, N-dimethyl- α-naphthylamine, N,
N, N ', N'-tetramethylethylenediamine, pyrrolidine, piperidine, N-methylpyrrolidine, N-methylpiperidine, pyridine, piperazine, 2-acetylpyridine, N-benzylpiperazine, quinoline, morpholine and the like.

Further, as the amide compound, at least one of -C (= O) -N <or -C (= S)
-N <is a compound having a bond, specifically, N, N
-Dimethylformamide, N-dimethylacetamide,
N-methylpyrrolidone, acetamide, propionamide, benzamide, acetanilide, benzanilide,
N-methylacetanilide, N, N-dimethylthioformamide, N, N-dimethyl-N, N '-(p-dimethylamino) benzamide, N-ethylene-N-methyl-
8-quinolinecarboxamide, N, N'-dimethylnicotinamide, N, N-dimethylmethacrylamide, N
-Methylphthalimide, N-phenylphthalimide, N
-Acetyl-ε-caprolactam, N, N, N ', N'
-Tetramethylphthalamide, 10-acetylphenoxazine, 3,7-bis (dimethylamino) -10-benzoylphenothiazine, 10-acetylphenothiazine, 3,7-bis (dimethylamino) -10-benzoylphenothiazine, N-ethyl -N-methyl-8-quinolinecarboxamide, N, N'-dimethylurea, N, N'-diethylurea, N, N'-dimethylethyleneurea, N, N, N ', N'-tetra Methyl urea,
N, N-dimethyl-N ′, N′-diethyl urea, N, N
And linear urea compounds such as -dimethyl-N ', N'-diphenylurea.

Further, specific examples of the nitrile compound include:
Acetonitrile, propionitrile, benzonitrile,
Benzyl nitrile, adiponitrile, malononitrile,
N, N-dimethylamino-benzylnitrile and the like. Further, specific examples of epoxy compounds include 1,3-
Butadiene monoxide, 1,3-butadiene oxide, 1,2-butylene oxide, 2,3-butylene oxide, cyclohexene oxide, 1,2-epoxycyclododecane, 1,2-epoxydecane, 1,2-epoxyeicosane 1,2-epoxyheptane, 1,2-epoxyhexadecane, 1,2-epoxyoctadecane,
1,2-epoxyoctane, ethylene glycol diglycidyl ether, 1,2-epoxytetradecane, hexamethylene oxide, isobutylene oxide, 1,7-
Octadiene epoxide, 2-phenylpropylene oxide, propylene oxide, trans-stilbene oxide, styrene oxide, epoxidized 1,2-polybutadiene, epoxidized linseed oil, glycidyl methyl ether, glycidyl n-butyl ether, glycidyl allyl ester -Tell, glycidyl methacrylate, glycidyl acrylate and the like.

Further, specific examples of the oxime compound include:
Acetoxime, methyl ethyl ketone oxime, diethyl ketone oxime, acetophenone oxime, benzophenone oxime, benzylphenyl ketone oxime, cyclopentanone oxime, cyclohexanone oxime,
And benzaldehyde oxime. Under the hydrogenation catalyst of the present invention and preferable hydrogenation conditions, when a vinyl-substituted aromatic hydrocarbon unit is copolymerized in a cyclic diene-based block copolymer, hydrogenation of this carbon-carbon double bond (aromatic ring) is substantially Does not happen. In the present invention, a partially hydrogenated cyclic olefin-based thermoplastic elastomer obtained by selectively hydrogenating the cyclic diene monomer unit in the B block rather than the olefinically unsaturated double bond of the cyclic diene monomer unit in the present invention. -Can be obtained efficiently. The meaning of partial hydrogenation is to use a specific hydrogenation catalyst to hydrogenate 90% or more, preferably 95% or more, of the olefinically unsaturated double bonds of the linear conjugated diene block in the B block,
And 50% of the olefinically unsaturated double bonds of the cyclic conjugated diene or its derivative block in the A block
In the following, it means that the hydrogenation rate is preferably kept to 25% or less.

The preferred embodiment of the hydrogenation reaction of the present invention is as follows:
The reaction is performed in a solution in which the polymer having an olefinically unsaturated double bond is dissolved in an inert organic solvent. As used herein, the term "inert organic solvent" means a solvent that does not react with any participant in the hydrogenation reaction. Suitable solvents are
For example, n-pentane, n-hexane, n-heptane,
An aliphatic hydrocarbon such as n-octane; an alicyclic hydrocarbon such as cyclohexane, cycloheptane and cycloheptane; and an ether such as diethyl ether and tetrahydrofuran, alone or in a mixture. Aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene can also be used only when the aromatic double bond is not hydrogenated under the selected hydrogenation conditions.

In the hydrogenation reaction of the present invention, generally, the above-mentioned solution to be hydrogenated is maintained at a predetermined temperature under hydrogen or an inert atmosphere, and a hydrogenation catalyst is added thereto with or without stirring. Then, hydrogen gas is introduced and pressurized to a predetermined pressure. The inert atmosphere means an atmosphere that does not react with any participant in the hydrogenation reaction, such as helium, neon, or argon. Air and oxygen are not preferred because they oxidize the catalyst components and deactivate the catalyst. Nitrogen acts as a catalyst poison during the hydrogenation reaction, and may reduce the hydrogenation activity. In particular, it is most preferable that the inside of the hydrogenation reactor be an atmosphere containing only hydrogen gas. The composite hydrogenation catalyst composition of the present invention is prepared by mixing the catalyst component (C) in a suitable solvent in a catalyst tank.
Is prepared by reducing the catalyst component (A) with the catalyst component (B) in the presence of and then adding the catalyst component (D) last. (A), (B) and (C) may be added in any order, but (D) must always be the last.

A cyclic conjugated diene polymer to be hydrogenated, or a cyclic conjugated diene and a linear conjugated diene, if necessary,
When a copolymer with a vinyl aromatic hydrocarbon is obtained by a living anionic polymerization method, usually at the time of terminating the active terminal, an inactivator not more than an equimolar amount of the active terminal or an excess is added. When an excess of an alcohol or ketone compound is used, an alkoxy alkali metal may be present in the system. The preparation atmosphere of the composite hydrogenation catalyst used in the present invention may be hydrogen in addition to the inert atmosphere. The reduction temperature and the storage temperature are from -50 ° C to 5
It is 0 ° C., and particularly preferably in the range of −20 ° C. to 30 ° C. The time required for the reduction varies depending on the reduction temperature, but at 25 ° C., is several seconds to 60 days, and 1 minute to 20 days.
A range of days is preferred.

It is necessary to handle the catalyst component (B) under the above-mentioned inert atmosphere. The catalyst component (A) may be stable even in the air, but is preferably handled under an inert atmosphere. The catalyst components (A), (B), (C), and (D) constituting the composite hydrogenation catalyst of the present invention are more preferably handled as a solution of the inert organic solvent because they are easier to handle. As the inert organic solvent used when used as a solution, the above-mentioned various solvents that do not react with any participant in the hydrogenation reaction can be used. Preferably, the same solvent as the solvent used for the hydrogenation reaction is used.

When the complex hydrogenation catalyst is added to the hydrogenation reactor (hydrogenation tank), it is most preferable to carry out the addition in a hydrogen atmosphere. The temperature at the time of addition is a temperature of -30 ° C to 100 ° C,
Preferably, it is added just before the hydrogenation reaction at a temperature in the range of -10 ° C to 50 ° C. The mixing ratio of each catalyst component for expressing high hydrogenation activity and hydrogenation selectivity is determined by the ratio of the number of moles of metal of the catalyst component (B) to the number of moles of the catalyst component (A) (hereinafter referred to as Metal (B) / Metal (A)
(Molar ratio) is about 20 or less. MetaL (B)
If the / Metal (A) molar ratio exceeds 20, excessive use of an expensive catalyst component (B) which does not contribute to substantial improvement in activity is not only uneconomical, but also tends to cause unnecessary side reactions. Absent. Metal (B) / Me
There is hydrogenation activity in the range of tal (A) molar ratio = 0.05 to 20. More preferably, it is in the range of 0.05 to 5, in which hydrogenation activity is significantly improved.

When the hydrogenated product in the hydrogenation tank is a living polymer obtained by living anionic polymerization, since the living terminal acts as a reducing agent, the polymer having a living active terminal is hydrogenated. In this optimal Metal
In order to achieve the (B) / Metal (A) molar ratio, it is preferable to inactivate the compound with various compounds having active hydrogen or halogen. Compounds having such active hydrogen include water and methanol, ethanol, n-propanol, n-butanol, sec-butanol, tert.
-Butanol, 1-pentanol, 2-pentanol,
3-pentanole, 1-hexanol, 2-hexano-
, 3-hexanol, 1-heptanol, 2-heptanol, 3-heptanol, 4-heptanol, octanol, nonanol, decanol, undecanol, lauryl alcohol Alcohols such as benzyl, allyl alcohol, cyclohexanol, cyclopentanol and benzyl alcohol, phenol, o-cresol, m-cresol, p-cresol, p -Allylphenol, 2,6
Phenols such as di-t-butyl-p-cresol, xylenol, dihydroanthraquinone, dihydroxycoumarin, 1-hydroxyanthraquinone, m-hydroxybenzyl alcohol, resorcinol, and leukoaurine;
And the like.

Examples of the acid include acetic acid, propionic acid, butyric acid, isoacetic acid, pentanoic acid, hexanoic acid, heptanoic acid,
Decalic acid, myristic acid, stearic acid, behenic acid,
Organic carboxylic acids such as benzoic acid can be mentioned. Examples of the compound having a halogen include benzyl chloride, trimethylsilyl chloride (bromide), t-butylsilyl chloride (bromide), methyl chloride (bromide), ethyl chloride (bromide), propyl chloride (bromide), and n-butyl chloride (bromide). ) And the like. These may be used alone or as a mixture of two or more.
The addition amount of the catalyst component (C) is preferably in the range of 10 to 500 by weight ratio to the catalyst of the catalyst component (A). If it is smaller than 10, the effect of stabilizing storage and reducing the amount of catalyst will be small. Although the hydrogenation activity is good even when this ratio exceeds 500, when the hydrogenated product is a polymer, it is difficult to separate the hydrogenated polymer from the catalyst component (C). Affects physical properties.

The hydrogenated product is an olefinically unsaturated double bond-containing polymer, wherein the content of the olefinically unsaturated double bond in the side chain is 0.3 to the entire olefinically unsaturated double bond. In the case of from 1 to 1, a part of this may be transferred to the catalyst tank and used as the catalyst component (C), or may be used in combination with another catalyst component (C). The amount of the catalyst component (D) to be added is such that (D) / (B) is in the range of 0.01 to 10 in molar ratio with respect to the catalyst of the catalyst component (B),
In this range, the hydrogenation activity is high, and the storage stability and the hydrogenation activity persistence are extremely high. When the catalyst component (E) is used, the amount added is such that the molar ratio of (E) / (A) to the catalyst component (A) is 30 or less, preferably 20 or less, more preferably 10. Even when this ratio exceeds 30, the catalytic activity of hydrogenation is retained, but a large amount of the component (E) which does not substantially contribute to the activity improvement is used,
In addition to being uneconomical, it is not preferable because side reactions such as gelation of the polymer may occur. In the case where the component to be hydrogenated in the hydrogenation tank is a living polymer obtained by living anionic polymerization, the component (E) inactivates the living active terminal thereof with a derivative such as alcohol or phenol. An alkali compound generated at that time may be used, or an alkali compound synthesized by separately reacting an alcohol or phenol with an alkali metal or an alkyl alkali compound may be used.

The catalyst was added in an amount of 0.1 to 100 g of the hydrogenated product.
A range of from 002 to 20 mmol is sufficient. Within this addition amount range, it is possible to hydrogenate the olefinically unsaturated double bond of the hydrogenated product preferentially, and hydrogenation of the aromatic double bond in the copolymer does not substantially occur. Therefore, extremely high hydrogenation selectivity is realized. Hydrogenation reaction is possible even when the amount exceeds 20 mmol, and the water conversion of the olefinically unsaturated double bond in the cyclic conjugated diene portion tends to increase. And deviates from the spirit of the present invention, or decatalyzes the catalyst after the hydrogenation reaction,
There are disadvantageous aspects such as complicated removal. The preferred amount of catalyst for quantitatively hydrogenating the unsaturated double bond of the linear conjugated diene unit of the polymer under the selected conditions is as follows:
It is 0.01 to 5 mmol / g. More preferably, it is in the range of 0.1 to 2 mmol.

The hydrogenation reaction of the present invention is carried out using elemental hydrogen, and is more preferably introduced into the hydrogenated product in gaseous form. The hydrogenation reaction is more preferably performed under stirring,
The introduced hydrogen can be brought into contact with the hydrogenated product sufficiently quickly. The hydrogenation reaction is generally performed in a temperature range from 0 to 150 ° C. If the temperature is lower than 0 ° C., the activity of the catalyst is reduced, and the hydrogenation rate is reduced, so that a large amount of the catalyst is required. Therefore, it is not economical. If the temperature exceeds 150 ° C., side reactions, decomposition, and gelation easily occur, and Hydrogenation of the unsaturated double bond in the cyclic conjugated diene portion is also likely to occur, and the hydrogenation activity due to heat deactivation is undesirably reduced. It is more preferably in the range of 20 to 120 ° C. Particularly preferably 40
８０80 ° C. The pressure of hydrogen used in the hydrogenation reaction is 1
To 100 kg / cm ² is preferred. 1kg /
If the hydrogenation rate is less than cm ² , the hydrogenation rate is slowed, and the hydrogenation rate substantially reaches a peak.
If the pressure exceeds cm ² , the hydrogenation reaction is almost completed at the same time as the pressure is increased, which is not meaningful, and undesired side reactions and gelation are caused. A more preferred hydrogenated hydrogen pressure is 2
From 30 to 30 kg / cm ² , but the optimum hydrogen pressure is selected in correlation with the amount of catalyst added, etc., and the hydrogen pressure is practically selected on the high pressure side as the amount of the suitable catalyst decreases. Is preferred.

The hydrogenation reaction time of the present invention is usually from several seconds to 5 hours.
0 hours. Depending on the selection of another hydrogenation reaction time, the hydrogenation reaction time is appropriately selected and carried out within the above range. According to the method of the present invention, a hydrogenation ratio of 90% or more is obtained for the olefinically unsaturated double bond in the linear conjugated diene portion in the cyclic diene-based block copolymer (thermoplastic elastomer).
Preferably, a hydrogenation ratio of 95% or more is sufficiently possible. From the solution obtained by the hydrogenation reaction using the catalyst of the present invention, the hydrogenated target product can be easily separated by chemical or physical means such as distillation and precipitation. In particular, catalyst residues can be removed from the polymer solution subjected to the hydrogenation reaction according to the method of the present invention, if necessary, and the hydrogenated polymer can be easily isolated from the solution. For example, a method in which a polar solvent which is a poor solvent for a hydrogenated polymer such as acetone or alcohol is added to the reaction solution after hydrogenation to precipitate and recover the polymer, and the reaction solution is poured into boiling water with stirring and then the solvent is added. It can be carried out by a method of recovering by distillation or a method of directly heating the reaction solution to distill off the solvent.

In the hydrogenation method of the present invention, first, the olefinically unsaturated double bond in the linear conjugated diene monomer unit in the cyclic diene-based block copolymer is hydrogenated at a high hydrogenation rate to obtain a cyclic diene. It is characterized by high selectivity in that it is not hydrogenated as much as possible in the monomer unit. Secondly, it has the feature that the amount of hydrogenation catalyst used is smaller. Therefore, even if the hydrogenation catalyst remains in the polymer as it is, it does not significantly affect the properties of the obtained hydrogenated polymer, and most of the catalyst is decomposed and removed in the process of isolating the hydrogenated polymer from the polymer. Since it is removed, no special operation is required to demineralize or remove the catalyst, and it can be carried out in a very simple process. Third, storage stability is extremely excellent. Therefore, the activity of the catalyst can maintain almost the original activity even after several months.

[0119]

The present invention will be described in more detail with reference to the following Examples and Comparative Examples, but the scope of the present invention is not limited by these Examples. The chemicals used in the present invention were of the highest purity available. The general solvent was degassed, refluxed over the active metal and then distilled. <Evaluation Method> [Molecular Weight] The weight average molecular weight, number average molecular weight, and molecular weight distribution of the block copolymer were represented by values in terms of polystyrene by the GPC method. [Composition and microstructure] The composition and microstructure of the block copolymer are ¹ H-NMR.
(200 MHz: FT-NMR manufactured by Brucker)
Integrating 64 times in 0 w / v% d chloroform solvent,
Quantified. The microstructure was confirmed by a Morero method using an infrared absorption spectrometer as required.

[Measurement of Viscoelastic Behavior and Glass Transition Temperature] The temperature change and tan δ of the dynamic storage modulus (E ′) of the block copolymer were measured using a DMA spectrometer (983 DMA manufactured by DuPont Instruments). The measurement was performed under the conditions shown in Table 1. In particular, the glass transition temperature on the low temperature side (soft segment) was determined exclusively from the tan δ peak temperature of DMA. Further, the glass transition temperature on the high temperature side (hard segment) is determined by changing the G "peak temperature in a shearing mode to Rheometrics Mesh manufactured by Rheometrics.
original Spectrometer (RMS-8
00). Table 1 shows the measurement conditions.

[0121]

[Table 1]

[Surface hardness] The JIS A hardness was measured at 25 ° C. [Break strength (MPa), Break elongation (%)] According to JIS K6301, length 20 mm x width 3 mm
X Using a compression molded piece having a thickness of 3 mm, a tensile test was performed at 25 ° C and 90 ° C under the conditions of a head speed of 20 mm / min. [Permanent strain (p-set)] The residual strain was determined from the recovery after 100% elongation at room temperature and 90 ° C. [Softening temperature] Using TMA100 manufactured by SEIKOI & E, load 50
g, measured by measuring a 100 μm penetration temperature at a temperature rising rate of 2 ° C./min.

[Dunlop rebound resilience] Measured in accordance with BS903 standard. [Compression Set (c-set)] A value was measured at 70 ° C for 22 hours in accordance with JIS K6301. 10. [Taber wear] 1kg load, H-22 according to ASTM D1044 standard
Using a wheel, evaluation was made based on the amount of wear (mg) after 100 rotations.

(Example 1): Synthesis of dilithium initiator 1 The dilithium initiator used in the present invention was synthesized by the following method. With dripping funnel and cooling tube fully degassed and replaced 3
1.27 mol / l sec-butyllithium (manufactured by Kanto Chemical Co., Ltd.) in a 00 ml three-necked flask in the presence of nitrogen
The cyclohexane solution and 0.1935 mol of triethylamine were stirred and mixed at room temperature with a magnetic stirrer.
Then, 0.09 was previously dehydrated and distilled under reduced pressure from the dropping funnel.
68 mol of 1,3-diisopropenylbenzene was added dropwise at 20 ° C. with stirring over 4 hours. The mixture was further stirred at the same temperature for 12 hours. The resulting dark red 1,3-bis (1-
(Lithio-1,3-dimethylpentyl) benzene was partially sampled and quenched with water in the presence of nitrogen. Water and triethylamine were removed by vacuum degassing, and the remaining viscous liquid was measured by GPC for low molecular weight analysis. The dilithium compound was obtained with a yield of 96%.

(Example 2): Synthesis of dilithium initiator 2 In Example 1, tert-butyl lithium was used instead of tert-butyl lithium.
-Performed similarly except that butyllithium (manufactured by Kanto Chemical Co., Ltd.) was used. The dilithium yield determined by GPC analysis of the water inactivating component was 100%. (Example 3): Synthesis of dilithium initiator 3 The procedure was the same as in Example 2, except that anisole was used instead of triethylamine. The dilithium yield was 98%.

(Comparative Production Example 1): Preparation of Organometallic / Amine Complex 1 Under a dry argon atmosphere, a predetermined amount of tetramethylenediamine (TMEDA) was dissolved in cyclohexane. The solution was cooled and maintained at -10 ° C, and an equimolar n-butyllithium n-hexane solution was slowly added under a dry argon atmosphere. After the start of the dropwise addition, the solution was cooled to −78 ° C. to precipitate and isolate a white crystalline complex solid. (Comparative Production Example 2): Preparation of Organometallic / Amine Complex 2 A white crystalline complex solid was prepared in the same manner as in Comparative Production Example 1, except that the molar ratio of TMEDA and n-butyllithium was changed to 1/4. Isolated.

Example 4 Polymerization of Triblock Copolymer To an autoclave equipped with a stirrer sufficiently purged with nitrogen, 2060 g of cyclohexane and 990 g of a 33% by weight butadiene cyclohexane solution were added.
DA was added so as to be 0.2 times the mole number of Li of the dilithium initiator of Example 1, and a composite dilithium initiator was added so that the mole number of Li was 18.46 mmol. Polymerized at ~ 70 ° C for 30 minutes. Next, the temperature in the system was lowered to 45 ° C., and TMEDA was charged in L
It was added in a 1-fold molar amount relative to the i atom. Next, 154 g of 1,3-cyclohexadiene was added, and the mixture was polymerized at the same temperature for 3 hours. The addition ratio of 1,3-cyclohexadiene determined by gas chromatography was 97.8%. At this time, a part of the polymer solution was extracted into methanol and subjected to GPC measurement. The color of the polymer solution was deep yellow, confirming that the reaction was proceeding by living polymerization.

Methyl alcohol was added in an amount equivalent to Li to deactivate the solvent, the solvent was evaporated, and a portion was compression molded at 250 ° C. to form a sheet having a pressure of 2 mm and subjected to various physical property tests. Table 2 summarizes the molecular weight, composition, and various physical properties of the obtained block copolymer. The low-temperature glass transition temperature of the cyclic diene-based block copolymer obtained from the DMA spectrum (tan δ peak temperature) was calculated using RMS800.
The glass transition temperature on the high temperature side determined from (G "peak temperature) is shown in Table 2. Fig. 1 shows the GPC chart of the components sequentially extracted. It was confirmed that the peak was shifted, that the polymerization was proceeding by living anionic polymerization, and that the desired cyclic diene block copolymer was formed. In order to examine the structure, the microstructure was examined by the Morello method from the IR spectrum of polybutadiene sampled on the way, and the ¹ H-NMR (200 MHz) spectrum of this block copolymer is shown in FIGS. A signal derived from an olefinic proton was observed at around 0.4 ppm.

The assignment of the olefinic proton is shown below. 4.5 to 4.9 ppm: 1,2 bond vinyl proton (2H) in the butadiene portion 4.9 to 6. ppm: -C of 1,2 bond of butadiene moiety
H = C protons (IH) + butadiene portion of 1,4 linkage -CH = CH- protons (2H) + cyclohexanol After completion of the polymerization of the olefinic protons polybutadiene block diene unit, by IR or ¹ H-NMR by sampling The microstructure of the butadiene portion was calculated and the microstructure of the polybutadiene portion was determined. Next, ¹ H-NMR was measured by sampling the polymerized portion of the CHD block, and the CHD content of the block polymer was determined by using the signal of the 1,2 bond in the butadiene portion as an internal standard.

(Example 5): Polymerization of triblock copolymer In Example 4, the amount of butadiene in cyclohexane was changed to 97.
0 g, the amount of 1,3-cyclohexadiene is 80 g,
The same operation was performed except that the polymerization time of the 1,3-cyclohexadiene portion was changed to 2 hours. The conversion of 1,3-cyclohexadiene was 99.7%. Table 2 shows the molecular weight, microstructure, composition, and various physical properties of the obtained block copolymer.
Are shown together. Table 2 also shows the glass transition temperatures on the low temperature side and the high temperature side. GPC is shown in FIG. 3 and ¹ H-NMR spectrum is shown in FIG.

Example 6: Polymerization of triblock copolymer NE-58 In Example 4, the amount of cyclohexane was 1577 g, the mixture of 33% by weight butadiene cyclohexane was 1030 g.
-The same operation was performed except that the amount of cyclohexadiene was changed to 60 g. The conversion of 1,3-cyclohexadiene is 99.5%.
Met. The molecular weight and composition of the obtained block copolymer
Table 2 shows various physical properties. Table 2 also shows the glass transition temperatures on the low temperature side and the high temperature side. In Figure 5 the GPC, ¹ H-
The NMR spectrum is shown in FIG.

(Example 7): Polymerization of triblock copolymer In Example 4, instead of adding TMEDA prepared in advance with the dilithium initiator, a solvent, butadiene monomer and the like were added to the reactor. , Followed by the addition of the dilithium initiator. G
As a result of PC analysis, the obtained block copolymer was monodispersed. Table 2 shows the results.

Example 8 Polymerization of Triblock Copolymer: Batch Addition Method In an autoclave equipped with a stirrer sufficiently purged with nitrogen, 2060 g of siloxane and 990 g of a 33% by weight butadiene cyclohexane solution were prepared. After adding 154 g of cyclohexadiene and adding the dilithium initiator obtained in Example 2, TMEDA was added to the number of moles of Li (Li
(As the number of moles of 18.46 mmol). Polymerization was carried out at 40 to 50 ° C for 120 minutes. 1,3 determined by gas chromatography
-The addition ratio of cyclohexadiene was 95.1%.
At this time, a part of the polymer solution was extracted into methanol and subjected to GPC measurement. The obtained block polymer was monodispersed, the color of the polymer solution was dark yellow, and it was confirmed that the reaction was progressing by living polymerization.

The solvent was evaporated, and the resulting sheet was dried.
It was compression molded at 50 ° C. and subjected to various physical property tests. Table 2 summarizes the molecular weight, composition, and various physical properties of the obtained block copolymer. Further, the glass transition temperature on the low temperature side obtained from the DMA spectrum (tan δ peak temperature) of this cyclic diene-based block copolymer, and the glass transition temperature on the high temperature side obtained from RMS800 (G ″ peak temperature) The temperatures are shown in Table 2. Tg on the low temperature side and the Tg on the high temperature side were clearly observed, indicating that a polybutadiene block and a polycyclohexadiene block were formed.

(Comparative Example 1): Polymerization of Triblock Copolymer In Example 4, a composite prepared by adding TMEDA in advance so as to be 0.5 times the mol number of Li of the dilithium initiator of Example 1 in advance. The same operation was performed except that the dilithium initiator was 18.46 mmol as the number of moles of Li.
The conversion of 1,3-cyclohexadiene was 99.3%. Table 2 summarizes the molecular weight, composition, and various physical properties of the obtained block copolymer. Table 2 also shows the glass transition temperatures on the low temperature side and the high temperature side. (Comparative Example 2): Polymerization of triblock copolymer In Comparative Example 1, TMEDA was used as the dilithium initiator of Example 1.
Was performed in the same manner except that no was added. The resulting polymer
Was analyzed by GPC and found to have a bimodal molecular weight distribution.

(Comparative Example 3): Polymerization of triblock copolymer with complex To a 5-liter autoclave equipped with a stirrer sufficiently purged with nitrogen, 2060 g of siloxane and 77 g of 1,3-cyclohexadiene were added, and the internal temperature was lowered to 40 ° C. -Ludo. Next, the complex synthesized in Comparative Production Example 1 was added so as to have a molar number of Li of 9.23 mmol, and polymerized at the same temperature for 120 minutes (first step). Then, 990 g of a 33% by weight solution of butadiene in cyclohexane was added, and
Polymerization was carried out at 0 ° C. for 45 minutes (second step). Next, the temperature in the system was lowered to 45 ° C., 77 g of 1,3-cyclohexadiene was added, and polymerization was carried out at the same temperature for 5 hours (third step). 1,3 determined by gas chromatography
The cyclohexadiene addition rate was 99.
8% and 95.6% in the second step. At this time, a part of the polymer solution was extracted into methanol and subjected to GPC measurement. The color of the polymer solution was deep yellow, confirming that the reaction was proceeding by living polymerization. After deactivating the active Li with ethanol, the solvent was evaporated, and the obtained sheet was compression-molded at 250 ° C. and subjected to various physical property tests. The molecular weight, microstructure,
Table 2 summarizes the composition and various physical properties. FIG. 7 shows the GPC for each step.

(Comparative Example 4): Polymerization of triblock copolymer by complex The same procedure was performed except that the polymerization initiator obtained in Comparative Production Example 2 was used in Comparative Example 3. First and third steps 1,
The conversion of 3-cyclohexadiene was 99.2 each.
%, 95.1%. Table 2 summarizes the molecular weight, microstructure, composition, and various physical properties of the obtained block copolymer. FIG. 8 shows the GPC for each step.

[0138]

[Table 2]

Hereinafter, the partial hydrogenation of the cyclohexadiene-based triblock copolymer will be specifically described with reference to Examples and the like, but the present invention is not limited thereto. The hydrogenation catalyst used in carrying out the examples and comparative examples is shown below. [Catalyst (A) Component] Bis (η ⁵ -methylcyclopentadienyl) titanium dichloride, which was obtained by recrystallizing a reagent manufactured by Kanto Chemical Co. in dichloromethane, was used. Bis (eta ^5-n-butyl cyclopentadienyl) titanium dichloride; similar bis (eta ⁵ - cyclopentadienyl) titanium dichloride; a Reagent produced by Kanto Kagaku Co., Ltd. primary was used recrystallized in dichloromethane. Bis (η ⁵ -cyclopentadienyl) titanium di (p-tolyl); a product obtained by recrystallizing a reaction product of titanocene dichloride and p-tolyl lithium in cyclohexane was used.

[Catalyst (B) Component] A sec-butyllithium; hexane solution (a reagent manufactured by Kanto Chemical Co., Ltd.) was filtered off under an inert atmosphere, and a yellow transparent portion was used. Ethyl butyl magnesium; pentane solution (Kanto Chemical Co., Ltd. reagent) was used as it was. Triethylaluminum; hexane solution (manufactured by Toso-Akzo) was used as it was. Trimethylaluminum; hexane solution (manufactured by Toso-Akzo) was used as it was.

[Catalyst (C) Component] Liquid 1,2-polybutadiene (Niss, manufactured by Nippon Soda Co., Ltd.)
o B-1000: 85% 1,2-vinyl bond) Liquid 1,2-polybutadiene (B-70, manufactured by Nisseki Chemical Co., Ltd.)
0: 1,2-vinyl bond amount 57%)) Liquid polybutadiene (R-45M: manufactured by Idemitsu Petrochemical Co., Ltd.)
The hydrogenation rate was determined by ¹ H-NMR based on the decrease in the signal intensity of olefinic hydrogen before and after the reaction, using the signal intensity of hydrogen of the chloroform impurity (7.26 ppm) as an internal standard. I asked.

(Example 9): Preparation of partially hydrogenated triblock copolymer NE-56H The triblock copolymer solution obtained in Example 5 was inactivated with an equivalent amount of living Li methanol to obtain a polymer solution. 3 liter stainless steel autoclave which was previously hydrogen-substituted so as to be 500 g (polymer amount: 50 g).
Transferred to Bis (η ⁵ -methylcyclopentadienyl) titanium dichloride is used as the catalyst component (A).
The catalyst component (B) was added with sec-butyllithium to Ti in an amount of 50 ppm.
Double molar addition was performed. Immediately, a hydrogen pressure of 10 kg / cm ² G was applied, and the mixture was stirred at 75 ° C. for 1 hour and hydrogenated. Table 3 shows the results. Table 4 shows the physical properties of this partially hydrogenated polymer.

(Comparative Example 5) The procedure of Comparative Example 3 was repeated except that the charged butadiene cyclohexane solution was 1130 g, and the feed amounts of 1,3-cyclohexadiene in the first and third steps were each 53 g. Was. Hydrogenation was performed in the same manner as in Example 9. Table 3 shows the structure of the obtained partially hydrogenated polymer, and Table 4 shows its physical properties. (Example 10): partially hydrogenated triblock copolymers - bis as the catalyst component (A) in Production Example 9 (eta ⁵ - cyclopentadienyl) titanium dichloride catalyst component (B)
Was performed in the same manner except that trimethylaluminum was used and the Al / Ti molar ratio was 1.2. Table 3 shows the results.

Example 11 Preparation of partially hydrogenated triblock copolymer Bis (η ⁵ -cyclopentadienyl) titanium dichloride as the catalyst component (A), ethylbutylmagnesium as the catalyst component (B), and the catalyst component ( C) Niss as
o 25 ppm each of B-1000 as Ti, M
g / Ti = 2 times as much as in Example 9 except that a catalyst was prepared by dissolving 0.2 g of liquid rubber in 20 g of cyclohexane. Table 3 shows the results. (Example 12): partially hydrogenated triblock copolymers - manufacturing the catalyst component (A) as a bis (eta ^5-n-butyl cyclopentadienyl) titanium dichloride catalyst component (B)
As triethylaluminum and B-7 as a catalyst component
Example 11 was carried out in the same manner as in Example 11. Table 3 shows the results.

(Example 13): Preparation of partially hydrogenated triblock copolymer In Example 11, sec-butyllithium was used as the catalyst component (B) and tert-butyl alcohol was used as the catalyst component (D).
(Molar ratio to Li: 1.0). Table 3 shows the results. (Example 14): Production of partially hydrogenated triblock copolymer The same operation as in Example 13 was carried out except that acetone (molar ratio to Li: 1.5) was used as the catalyst component (D). Table 3 shows the results.

(Example 15): Preparation of partially hydrogenated triblock copolymer NE-58H The triblock copolymer solution obtained in Example 6 was treated with Li
It was deactivated with an equal amount of isoheptanol, and transferred to a 3-liter stainless steel autoclave which had been previously hydrogen-purged so as to have a polymer solution of 500 g (polymer amount: 50 g). Bis (η ⁵ -methylcyclopentadienyl) titanium di-p-tolyl is used as the catalyst component (A) with Ti
The catalyst was added so as to have a concentration of 50 ppm, and diethyl aluminum chloride was added as a catalyst component (B) in an amount twice as much as that of Ti. Immediately increase the hydrogen pressure to 10 kg / cm
^The mixture was stirred at 75 ° C. for 1 hour over ² G and hydrogenated. Table 3 shows the results. Further, ¹ H-NMR of the obtained polymer,
DMA, GPC are shown in FIGS. Table 4 shows the physical properties of the obtained polymer.

(Comparative Example 6): Preparation of partially hydrogenated triblock copolymer The triblock copolymer solution obtained in Example 5 was inactivated with an equivalent amount of living Li methanol to obtain 500 g of a polymer solution ( 5 liter stainless steel autoclave which has been previously hydrogen-substituted so as to have a polymer amount of 50 g).
Transferred to As a catalyst, a 5% by weight Pd / C catalyst was added to the polymer so as to be 10% by weight with Pd, a hydrogen pressure was applied at 50 kg / cm ² G, the mixture was stirred at 160 ° C. for 1 hour, and hydrogenated. Table 3 shows the results. Table 4 shows the physical properties of the partially hydrogenated triblock copolymer.

(Example 16): Production of partially hydrogenated triblock copolymer The rest of the deactivated triblock polymer obtained in Example 4 was partially hydrogenated in the same manner as in Example 15. Table 3 shows the results. Further, ¹ H-NMR, DMA,
The GPC is shown in FIGS. Table 4 shows the physical properties of the partially hydrogenated triblock copolymer.

[0149]

[Table 3]

[0150]

[Table 4]

[0151]

The partially hydrogenated cyclic diene-based block copolymer of the present invention comprises an A block composed of a part or all of a cyclic diene monomer or a derivative thereof, and a linear copolymerizable with the A block. Composed of a monomer mainly composed of a linear conjugated diene monomer or a linear conjugated diene monomer
Block is a specific unit, and the block B is a novel thermoplastic elastomer selectively hydrogenated. That is, in addition to the excellent heat-resistant mechanical properties of the cyclic conjugated diene block, the excellent low-temperature performance of the hydrogenated conjugated diene block,
It has become possible to design a low-hardness elastomer material having an extremely wide operating temperature range and having a distortion performance and the like. In some cases, additives such as stabilizers, ultraviolet absorbers, light stabilizers, fillers, etc. are added, and terminal modification is performed, and unsaturated carboxylic acids and / or their derivatives are graft-modified to hard segments and / or soft segments. By letting
Not only as a thermoplastic elastomer alone, but also for the purpose of modifying other polymer materials such as polyamide, polyester, polyether, polyphenylene sulfide, polyolefin, etc. -It can be used in a wide range of application fields such as Also, by combining with paraffin oil, naphthene oil, ester plasticizer, etc., appropriate plasticizers, resins, etc., it is excellent in compression set,
As a low-hardness thermoplastic elastomer compound, it can be suitably used in application fields such as tubes, hoses and rubber contact materials.

[Brief description of the drawings]

FIG. 1 shows GPC of the block copolymer obtained in Example 4.
It is a chart.

FIG. 2 shows ¹ H- of the block copolymer obtained in Example 4.
It is an NMR spectrum figure.

FIG. 3 shows GPC of the block copolymer obtained in Example 5.
It is a chart.

FIG. 4 shows ¹ H- of the block copolymer obtained in Example 5.
It is an NMR chart.

FIG. 5 GPC of the block copolymer obtained in Example 5
It is a chart.

FIG. 6 shows ¹ H- of the block copolymer obtained in Example 6.
It is an NMR spectrum figure.

FIG. 7 shows GPC of the block copolymer obtained in Comparative Example 3.
It is a chart.

FIG. 8 shows GPC of the block copolymer obtained in Comparative Example 4.
It is a chart.

FIG. 9 shows ¹ H of the block copolymer obtained in Example 15.
-It is an NMR spectrum figure.

FIG. 10 is a DMA spectrum diagram of the fifteenth embodiment.

FIG. 11 is a GPC chart of the fifteenth embodiment.

FIG. 12 shows ^{1 of the} block copolymer obtained in Example 16.
It is an H-NMR spectrum figure.

FIG. 13 is a DMA spectrum diagram of the sixteenth embodiment.

FIG. 14 is a GPC chart of the sixteenth embodiment.

Claims (15)

[Claims] 1. (a) Part or all of molecular structural units constituting a polymer chain is composed of a cyclic conjugated diene monomer represented by the following general formulas (1) and (2) or a derivative thereof. A block unit composed of at least two block units (hereinafter, referred to as “A block”) and a monomer mainly composed of a linear conjugated diene monomer or a linear conjugated diene monomer (hereinafter, referred to as “B block”) Block "), the number average molecular weight in terms of polystyrene by GPC is 50,000 to 500,000, the weight ratio of A / B is in the range of 3/97 to 50/50, and the B block is A cyclic diene-based thermoplastic elastomer, wherein the amount of a vinyl bond in the constituting linear conjugated diene monomer unit is 15 to 55%. Embedded image (However, n is a value selected from integers from 1 to 4.) (However, n is a value selected from an integer from 1 to 4.) 2. (a) Part or all of the molecular structural units constituting a polymer chain is composed of a cyclic conjugated diene monomer represented by the following general formulas (1) and (2) or a derivative thereof. A block unit composed of at least two block units (hereinafter, referred to as “A block”) and a monomer mainly composed of a linear conjugated diene monomer or a linear conjugated diene monomer (hereinafter, referred to as “B block”) Block "), the number average molecular weight in terms of polystyrene by GPC is 50,000 to 500,000, the weight ratio of A / B is in the range of 3/97 to 50/50, and the B block Wherein the amount of vinyl bonds before hydrogenation in the linear conjugated diene monomer unit constituting (a) is 25 to 55%, and the degree of hydrogenation of the unsaturated double bond in the monomer unit constituting A block (Hereinafter referred to as "A hydrogenation rate" ) Is 50% or less, and B
A partially hydrogenated cyclic diene-based thermoplastic elastomer having a hydrogenation rate of an unsaturated double bond in a monomer unit constituting a block (hereinafter, referred to as "B hydrogenation rate") of 90% or more. Embedded image (However, n is a value selected from integers from 1 to 4.) (However, n is a value selected from an integer from 1 to 4.) 3. The partially hydrogenated cyclic diene-based thermoplastic elastomer according to claim 2, wherein the A hydrogenation rate is 25% or less and the B hydrogenation rate is 95% or more. 4. A vinyl bond before hydrogenation of a linear conjugated diene monomer unit in a B block having an A hydrogenation ratio of 25% or less, a B hydrogenation ratio of 95% or more, and 30 ~
3. The partially hydrogenated cyclic diene-based thermoplastic elastomer according to claim 2, wherein the content is 50%. 5. A cyclic conjugated diene monomer in which part or all of the monomer constituting the A block is 1,3-cyclohexadiene, a 1,3-cyclohexadiene derivative, or a 6-membered ring structure in the molecule thereof. And the monomer constituting the B block is 1,3-butadiene and / or isoprene, or a monomer mainly composed of 1,3-butadiene and / or isoprene. The cyclic diene-based thermoplastic elastomer or the partially hydrogenated cyclic diene-based thermoplastic elastomer according to any of the above. 6. The glass transition temperature of the hard segment obtained from the G ″ peak temperature by dynamic viscoelasticity measurement is 130.
The cyclic diene-based thermoplastic elastomer or partially hydrogenated cyclic diene-based thermoplastic elastomer according to any one of claims 1 to 5, wherein the temperature is from 200 to 200 ° C. 7. The cyclic diene-based thermoplastic elastomer or partially hydrogenated cyclic according to claim 1, wherein the molecular weight distribution (Mw / Mn) in terms of polystyrene determined by GPC is 1.2 or less. Diene-based thermoplastic elastomer. 8. The method of claim 1, wherein two equivalents of monoorganic lithium initiator are added to
In a non-polar hydrocarbon at a temperature in the range of 0 to 60 ° C in the presence of a tertiary monoamine and / or an ether compound, 1,3-
Reaction with diisopropenylbenzene or a derivative thereof, and then adding 0.05 to
0.49 moles of tertiary diamine and / or alkoxylithium compound and optionally 30
The α, ω-dilithium compound formed by adding the conjugated diene-based monomer in a molar amount of not more than twice is used as the initiator without isolation, the B block is first polymerized, and then, if necessary, with respect to Li. The method for polymerizing a cyclic diene-based thermoplastic elastomer according to any one of claims 1 to 7, wherein the A block is sequentially polymerized after adding 0.1 to 2.0 times mol of a tertiary diamine. . 9. The polymerization method according to claim 8, wherein the amount of the tertiary diamine and / or the alkoxy compound added is 0.1 to 0.24 moles relative to the Li concentration. 10. A polymerization method using the initiator according to claim 8 or 9, wherein a cyclic conjugated diene monomer and a linear conjugated diene monomer are simultaneously added and polymerized.
A method for polymerizing a cyclic diene-based thermoplastic elastomer described in any of the above. 11. The tertiary monoamine is trimethylamine,
At least one compound selected from triethylamine and dimethylaniline, wherein the ether compound is tetrahydrofuran (THF), tetramethyl THF, aniso-
, Diethyl ether, tert-butyl methyl ether, at least one compound selected from the group consisting of tertiary diamine, tetraethylethylenediamine, tetramethylethylenediamine, tetraphenylethylenediamine,
The polymerization method according to any one of claims 8 to 10, wherein the polymerization method is at least one compound selected from tetracyclohexylethylenediamine, and the alkoxylithium compound is at least one compound selected from compounds having 1 to 10 carbon atoms. 12. In producing the partially hydrogenated thermoplastic elastomer according to claim 2, the following component (A):
A method for producing a partially hydrogenated cyclic diene-based thermoplastic elastomer, comprising using a hydrogenation catalyst composition comprising the component (B). (A) a titanocene compound represented by the following general formula (3): (However, R ¹ and R ² represent a group selected from hydrogen and a hydrocarbon group of C _{1 to} C ₁₂ , and R ¹ and R ² may be the same or different. R ³ and R ⁴ are Represents a group selected from hydrogen, a C _{1 to} C ₁₂ hydrocarbon group, an aryloxy group, an alkoxy group, a halogen group and a carbonyl group, and R ³ and R ⁴ may be the same or different.) (B) at least one reducing agent selected from compounds containing at least one element of Li, Na, K, Mg, Zn, Al and Ca. 13. In producing the partially hydrogenated thermoplastic elastomer according to claim 2, the following component (A):
A method for producing a partially hydrogenated cyclic diene-based thermoplastic elastomer, characterized by further using a catalyst composition of the component (C) as the component (B). (A) a titanocene compound represented by the following general formula (3): (However, R ¹ and R ² represent a group selected from hydrogen and a hydrocarbon group of C _{1 to} C ₁₂ , and R ¹ and R ² may be the same or different. R ³ and R ⁴ are Represents a group selected from hydrogen, a C _{1 to} C ₁₂ hydrocarbon group, an aryloxy group, an alkoxy group, a halogen group and a carbonyl group, and R ³ and R ⁴ may be the same or different.) (B) at least one reducing agent selected from compounds containing at least one element of Li, Na, K, Mg, Zn, Al, and Ca; (C) the total number of olefinically unsaturated double bonds in the side chain. An olefinically unsaturated double bond-containing polymer having a fraction of 0.3 to 1 based on the amount of the olefinically unsaturated double bond. 14. In producing the partially hydrogenated thermoplastic elastomer according to claim 2, the following components (A) and (B), or components (A), (B) and (C): A method for producing a partially hydrogenated cyclic diene-based thermoplastic elastomer, further comprising using a catalyst composition containing the following component (D): (A) a titanocene compound represented by the following general formula (3): (However, R ¹ and R ² represent a group selected from hydrogen and a hydrocarbon group of C _{1 to} C ₁₂ , and R ¹ and R ² may be the same or different. R ³ and R ⁴ are Represents a group selected from hydrogen, a C _{1 to} C ₁₂ hydrocarbon group, an aryloxy group, an alkoxy group, a halogen group and a carbonyl group, and R ³ and R ⁴ may be the same or different.) (B) at least one reducing agent selected from compounds containing at least one element of Li, Na, K, Mg, Zn, Al, and Ca; (C) the total number of olefinically unsaturated double bonds in the side chain. An olefinically unsaturated double bond-containing polymer having a fraction based on the amount of the olefinically unsaturated double bond of 0.3 to 1, (D) an alcohol compound, an alkoxylithium compound,
Alkoxy sodium compounds, alkoxy potassium compounds, ether compounds, thioether compounds, ketone compounds, sulfoxide compounds, carboxylic acid compounds, carboxylic acid ester compounds, aldehyde compounds, lactone compounds, amine compounds, amide compounds, nitrile compounds, epoxy compounds And at least one polar compound selected from the group of oxime compounds. 15. The method according to claim 12, wherein the hydrogenation temperature is 40 to 80 ° C., and the amount of the hydrogenation catalyst added is 0.01 to 5 mmol per 100 g of the polymer.