JP3234700B2 - Hydrogenated tetracyclododecene polymer and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel hydrogenated tetracyclododecene polymer and a method for producing the same.
More specifically, the present invention relates to a hydrogenated tetracyclododecene polymer having a high glass transition temperature and a narrow molecular weight distribution, and a method for producing the same.

[0002]

2. Description of the Related Art Ring-opening metathesis polymerization of tetracyclododecene monomers is generally carried out by using a tungsten or molybdenum catalyst as a polymerization catalyst and a cocatalyst such as an organic aluminum compound. However, when these polymerization catalysts are used, only specific monomers can be polymerized, or on the contrary, the molecular weight increases, and it is difficult to control the molecular weight distribution. It has been known to use α-olefins such as 1-pentene and 1-hexene as molecular weight regulators in order to solve this problem, as disclosed in JP-A-5-105743 and JP-A-5-132545.
Japanese Patent Application Publication No. JP-A-2005-115139 discloses a method for producing a polymer using them. However, although these techniques can control the average molecular weight, it is difficult to narrow the molecular weight distribution.

On the other hand, US Pat. Nos. 4,681,956 and 4,727,215 disclose catalysts using imidoalkylidene complexes of molybdenum and tungsten. When these catalysts are used, the reaction proceeds in living polymerization, and the molecular weight distribution can be controlled to be monodispersed.

Further, Macromolecules, 24 , 4495 (1991) discloses an example in which a ring-opening polymerization of a norbornene monomer is carried out with a catalyst having an alkylidene complex. However, these polymers have low glass transition temperatures and are not industrially sufficient as heat-resistant polymers.

Furthermore, these ring-opening metathesis polymers are:
Due to the presence of a double bond in the molecule, it is inferior in terms of weather resistance, heat resistance and the like, and these are often modified by hydrogenation. In recent years, the hydrogenated products of these ring-opening metathesis polymers have attracted attention as transparent resins with heat resistance.However, hydrogenated tetracyclododecene polymers having a high glass transition temperature and a narrow molecular weight distribution Was not known.

[0006]

SUMMARY OF THE INVENTION The present invention relates to a hydrogenated tetracyclododecene polymer which can at least partially solve the above-mentioned disadvantages of the prior art, for example, a tetracyclododecene-based hydrogenated polymer having a high glass transition temperature and a narrow molecular weight distribution. An object of the present invention is to provide a hydrogenated cyclododecene polymer and a method for producing such a polymer.

[0007]

Means for Solving the Problems The present inventors have solved the above-mentioned problems and have intensively studied a hydrogenated tetracyclododecene polymer having a high glass transition temperature and a narrow molecular weight distribution, and a method for producing the same. Thus, the present invention has been completed.
That is, in the present invention, the glass transition temperature represented by the general formula (Formula 6) is 100 ° C. or higher, and the ratio (Mw / Mn) between the weight average molecular weight Mw and the number average molecular weight Mn measured by GPC.
Is a hydrogenated product of a tetracyclododecene polymer having a value of 1.0 to 1.8.

[0008]

Embedded image (In the formula, R _{1 to} R ₄ may be the same or different and each represents hydrogen, a hydrocarbon group, a halogen group, a hydrocarbon group substituted with a halogen atom, a nitrile group, a carboxyl group, or a methylcarboxyl group. Further, x represents an integer of 1 to 3, and n represents an integer greater than 1.) The present invention also provides at least one kind of tetracyclododecene-based monomer represented by the general formula (Formula 7). After polymerization with a living ring-opening metathesis catalyst, hydrogenation is performed under a hydrogenation catalyst. The glass transition temperature represented by the general formula (Chem. 8) is 100 ° C. or higher, and measured by GPC. This is a method for producing a hydrogenated tetracyclododecene polymer having a ratio (Mw / Mn) of the weight average molecular weight Mw to the number average molecular weight Mn of 1.0 to 1.8.

[0009]

Embedded image (In the formula, R _{1 to} R ₄ may be the same or different and each represents hydrogen, a hydrocarbon group, a halogen group, a hydrocarbon group substituted with a halogen atom, a nitrile group, a carboxyl group, or a methylcarboxyl group. X represents an integer of 1 to 3.)

[0010]

Embedded image (In the formula, R _{1 to} R ₄ may be the same or different and each represents hydrogen, a hydrocarbon group, a halogen group, a hydrocarbon group substituted with a halogen atom, a nitrile group, a carboxyl group, or a methylcarboxyl group. Further, x represents an integer of 1 to 3, and n represents an integer greater than 1.) As a specific example of the tetracyclododecene-based monomer represented by the formula (9) in the present invention, x is 1 is tetracyclododecene and a derivative thereof; x is 2; hexacycloheptadecene and a derivative thereof; and x is 3; These derivatives include:
R _{1 to} R _{4 each} have a C _{1 to} C 12 alkyl-substituted, aryl-substituted or aralkyl-substituted derivative; R _{1 to} R ₄ are halogen-substituted such as chlorine, bromine or iodine; Derivatives such as alkyl substitution, nitrile substitution, carboxyl substitution, methylcarboxyl substitution, and the like,

[0011]

Embedded image(Where R₁~ R_FourMay be the same or different
Often substituted with hydrogen, hydrocarbon group, halogen group, halogen atom
Substituted hydrocarbon, nitrile, carboxyl,
Represents a tylcarboxyl group. X is an integer of 1 to 3
And n represents an integer greater than 1. ) More specifically
Is tetracyclo [4.4.0.1^2,5. 1^7,10] -3
-Dodecene, 8-methyltetracyclo [4.4.0.1
^2,5. 1^7,10] -3-dodecene, 8-ethyltetracyclic
B [4.4.0.1^2,5. 1^7,10] -3-dodecene, 8
-Cyanotetracyclo [4.4.0.1^2,5. 1^7,10]
-3-dodecene, 8-carboxytetracyclo [4.
4.0.1.^2,5. 1^7,10] -3-Dodecene, 8-carbo
Xymethyltetracyclo [4.4.0.1^2,5.
1^7,10] -3-dodecene, 8-chlorotetracyclo
[4.4.0.1^2,5. 1^7,10] -3-dodecene, 8-
Bromotetracyclo [4.4.0.1^2,5. 1^7,10]-
3-dodecene, 8-methoxytetracyclo [4.4.
0.1^2,5. 1^7,10] -3-dodecene, 8-ethoxy
Toracyclo [4.4.0.1^2,5. 1^7,10] -3-Dode
Sen, 8,9-dimethyltetracyclo [4.4.0.1
^2,5. 1^7,10] -3-dodecene, 8-methyl-8-cal
Boxymethyltetracyclo [4.4.0.1^2,5. 1
^7,10] -3-dodecene, 8-phenyltetracyclo
[4.4.0.1^2,5. 1^7,10] -3-Dodecene
Tracyclododecenes and hexacyclo [6.6.1.1
^3,6. 0^2,7. 0^9,14] -4-heptadecene, 11-meth
Tylhexacyclo [6.6.1.1^3,6. 0^2,7. 0
^9,14] -4-heptadecene, 11-cyanohexacyclo
[6.6.1.1^3,6. 0^2,7. 0^9,14] -4-hepta
And polycycloalkanes such as decene.
You. In particular, 8-methyltetracyclo [4.4.0.1
^2,5. 1 ^7,10] -3-dodecene, 8-cyanotetracyclic
B [4.4.0.1^2,5. 1^7,10] -3- From dodecene
The resulting polymer has a high glass transition temperature and is preferred. this
Tetracyclododecene monomer is always used alone
It is not necessary to copolymerize using two or more
it can.

Further, these tetracyclododecene-based polymers may be those obtained by ring-opening polymerization of the above-mentioned specific monomer alone, but may be a monomer having a copolymerizability with the specific monomer. It may be obtained by subjecting a body to ring-opening polymerization. Specific examples of this copolymerizable monomer include cyclobutene,
Examples thereof include cycloolefins such as cyclopentene, cycloheptene and cyclooctene. Furthermore, bicyclo [2.2.1] hept-2-ene, 2-methylbicyclo [2.2.1] hept-5-ene, 2-cyanobicyclo [2.2.1] hept-5-ene, and the like Ring-opening polymerization may be performed by copolymerizing a norbornene derivative or dicyclopentadiene.

The living ring-opening metathesis catalyst used in the present invention may be any catalyst as long as it is a catalyst capable of living ring-opening metathesis polymerization. Specific examples thereof include W (N-2,6- C ₆ H ₃ Pr ⁱ ₂ ) (CHBu ^t ) (OBu ^t ), W (N-2,6-C
₆ H ₃ Pr ⁱ ₂ ) (CHBu ^t ) (OCMe ₂ CF ₃ ) ₂ , W (N-2,6-C ₆ H ₃ Pr ⁱ ₂ ) (CH
(Bu ^t ) (OCMe (CF ₃ ) ₂ ) ₂ , W (N-2,6-C ₆ H ₃ Pr ⁱ ₂ ) (CHCMe ₂ Ph) (OBu
_{^{t) 2, W (N-}} 2,6-C 6 H 3 Pr i 2) (CHCMe 2 Ph) (OCMe 2 CF 3) 2, W (N-
2,6-C ₆ H ₃ Pr ⁱ ₂ ) (CHCMe ₂ Ph) (OCMe (CF ₃ ) ₂ ) ₂ ,
ⁱ represents an i-propyl group, But represents a ^t -butyl group, Me represents a methyl group, and Ph represents a phenyl group. ), A tungsten-based alkylidene catalyst such as Mo (N-2,6-C ₆ H ₃ Pr ⁱ ₂ ) (CHBu ^t ) (OB
u ^t ) ₂ , Mo (N-2,6-C ₆ H ₃ Pr ⁱ ₂ ) (CHBu ^t ) (OCMe ₂ CF ₃ ) ₂ , Mo
(N-2,6-C ₆ H ₃ Pr ⁱ ₂ ) (CHBu ^t ) (OCMe (CF ₃ ) ₂ ) ₂ , Mo (N-2,6-
C ₆ H ₃ Pr ⁱ ₂ ) (CHCMe ₂ Ph) (OBu ^t ) ₂ , Mo (N-2,6-C ₆ H ₃ Pr ⁱ ₂ ) (C
HCMe ₂ Ph) (OCMe ₂ CF ₃ ) ₂ , Mo (N-2,6-C ₆ H ₃ Pr ⁱ ₂ ) (CHCMe ₂ Ph)
_{(OCMe (CF 3) 2)} 2, (Pr i is i- propyl group in the formula, Bu ^t
Represents a t-butyl group, Me represents a methyl group, and Ph represents a phenyl group. ) And other molybdenum-based alkylidene catalysts, Re (CBu ^t ) (C
HBu ^t ) (2,6-diisopropylphenoxide), Re (CBu ^t ) (C
HBu ^t ) (ortho-t-butylphenoxide), Re (CBu ^t ) (C
HBu ^t ) (trifluoro-t-butoxide), Re (CBu ^t ) (CHB
u ^t ) (hexafluoro-t-butoxide), Re (CBu ^t ) (CHB
u ^t) (2,6-dimethyl-phenoxide), (the Bu ^t in Formula t-
Represents a butyl group. ) And other rhenium-based alkylidene catalysts,
Ta [C (Me) C (Me) CHCMe ₃ ] (2,6-diisopropylphenoxide) ₃ (pyridine), Ta [C (Ph) C (Ph) CHCMe ₃ ] (2,6-diisopropylphenoxide) ₃ (pyridine ), Ta [C (Me) C (Me) C
Tantalum-based alkylidene catalysts such as (CMeCH ₂ CCMe ₃ ) CH ₂ ] (2,6-diisopropylphenoxide) ₃ (wherein Me represents a methyl group and Ph represents a phenyl group), Ru (CHCHCPh ₂ )
Ruthenium-based alkylidene catalysts such as (PPh ₃ ) Cl ₂ (wherein Ph represents a phenyl group) and titanacyclobutanes. The living ring-opening metathesis catalysts may be used alone or as a mixture of two or more.

The molar ratio between the tetracyclododecene monomer and the living ring-opening metathesis catalyst is controlled by controlling the molar ratio between the monomer and the catalyst because the ring-opening metathesis polymerization is living polymerization. Can be obtained. That is, with respect to 100 moles of the monomer, the catalyst 1
The polymer obtained by the reaction of the moles has a molecular weight of about 100-mers, and these molecular weights are slightly different depending on the nature of the monomers, but the ratio Mw of the weight average molecular weight Mw to the number average molecular weight Mn is Mw. / Mn is controlled in a narrow range of 1.0 to 1.8. Therefore, the molar ratio of the monomer to the catalyst is usually in the range of 10: 1 to 10,000: 1, preferably 1: 1.
The range is from 00: 1 to 1000: 1. .

Solvents used in living ring-opening metathesis polymerization include, for example, ethers such as tetrahydrofuran, dibutyl ether and dimethoxyethane, aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene, and fatty acids such as pentane, hexane and heptane. Aliphatic hydrocarbons, cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, alicyclic hydrocarbons such as decalin, methylene dichloride, dichloroethane, dichloroethylene, tetrachloroethane, chlorobenzene, halogenated hydrocarbons such as trichlorobenzene, and the like; These may be used in combination of two or more.

The hydrogenation catalyst in the present invention may be any of a heterogeneous catalyst and a homogeneous catalyst. Examples of the heterogeneous catalyst include noble metals such as palladium, platinum, nickel, and ruthenium, such as carbon, silica, alumina and titania. And the like. A solid catalyst supported on a carrier such as As the homogeneous catalyst, nickel naphthenate /
Triethyl aluminum, nickel acetylacetonate / triethyl aluminum, cobalt octenoate / n
-Butyllithium, titanocene dichloride / diethylaluminum monochloride, rhodium acetate, tris (triphenylphosphine) rhodium (I) chloride and the like, in particular, tris (triphenylphosphine) rhodium (I) chloride has a high activity, This is preferable because the hydrogenation reaction proceeds completely.

The glass transition temperature of the hydrogenated tetracyclododecene polymer obtained in the present invention is 100 ° C. or higher, preferably 130 ° C. or higher. Glass transition temperature is 10
If the temperature is lower than 0 ° C., the heat-resistant polymer is insufficient.

Further, the ratio of the weight average molecular weight Mw to the number average molecular weight Mn (Mw / Mn) of the hydrogenated tetracyclododecene polymer obtained by the present invention, as measured by GPC, in terms of polystyrene is 1.0 to 1.0. 1.8, and 1.0 to
A range of 1.5 is more preferred. A polymer having Mw / Mn of more than 1.8 is not preferable because it becomes non-uniform as a polymer.

The production of the hydrogenated product of the tetracyclododecene polymer of the present invention is carried out by using the above-mentioned tetracyclododecene polymer and the above-mentioned hydrogenation catalyst in the presence of a solvent.

The hydrogenation reaction is usually carried out at normal pressure to 300 atm.
The reaction is preferably performed using hydrogen gas at 20 to 200 atm, and the reaction temperature is usually 0 to 200 ° C,
A temperature range of 10 to 100C is preferred.

Generally, the weight ratio of polymer to catalyst is 100:
0.1-100: 100, preferably 100: 1-10
0:50, and the hydrogenation reaction is also performed using the same solvent as that used in living ring-opening metathesis polymerization.

The hydrogenation rate in the hydrogenation reaction is measured by ¹ H-NMR or IR. In this case, the hydrogenation rate is preferably 80% or more, more preferably 90% or more.

[0023]

The present invention will be described below in detail with reference to examples.
The physical properties of the polymers obtained in Examples and Comparative Examples were measured by the following methods. Average molecular weight: using GPC, the obtained polymer was dissolved in dichloromethane, and Shodex k-805,804,80 was used as a column.
The molecular weight was calibrated with polystyrene standards at room temperature using 3,802.5. Glass transition temperature: measured using a polymer powder in nitrogen at a heating rate of 16 ° C./min in a DSC-50 manufactured by Shimadzu Corporation.

Example 1 In a 50 ml flask equipped with a magnetic stirrer was placed 8-methyltetracyclo [4.4.0.1 ^2,5 . 2.0 g (11.5 mmol) of ^1,7,10 ] -3-dodecene and tetrahydrofuran 2
Put 8.5 ml, it was further dissolved in tetrahydrofuran 7ml Mo (N-2,6-C 6 H 3 Pr i 2) (CHCMe 2 Ph) (OBu t) 2 63mg
(0.115 mmol) was added and reacted at room temperature for 2 hours. Thereafter, 60 mg (0.566 mmol) of benzaldehyde was added and the mixture was stirred for 30 minutes to extinguish the living reaction. This polymer solution was added to a large amount of methanol to precipitate a ring-opened polymer, which was separated by filtration and further washed with methanol and dried to obtain a white powdery ring-opened polymer. The yield of the ring-opened polymer obtained as described above is 99.8%,
The weight average molecular weight Mw measured by GPC was 19300,
The number average molecular weight Mn is 18,200 and Mw / Mn is 1.
06. The glass transition temperature measured by DSC was 205 ° C. Further, 0.5 g of this ring-opened polymer and 5% palladium carbon 0.0 were added to a 100 ml autoclave.
5 g and 40 ml of cyclohexane were added, and the hydrogen pressure was 70 kg / c.
A hydrogenation reaction was performed at 140 ° C. for 4 hours at m ² . The hydrogenation rate of the obtained hydrogenated product calculated from ¹ H-NMR was 1
And the weight average molecular weight Mw measured by GPC.
Was 20,100, the number average molecular weight Mn was 18,800, and Mw / Mn was 1.07. The glass transition temperature measured by DSC was 140 ° C.

[0025] Example 2 catalyst as _{Mo (N-2,6-C 6} H 3 Pr i 2) (CHCMe 2 Ph) (OBu t) 2 in place of _{Mo (N-2,6-C 6} H 3 Pr Living ring-opening polymerization was carried out in the same manner as in Example 1 except that ⁱ ₂ ) (CHCMe ₂ Ph) (OCMe (CF ₃ ) ₂ ) was used to obtain a ring-opened polymer in the form of a white powder. The yield of the ring-opened polymer obtained as described above is 99%,
The weight average molecular weight Mw measured by GPC is 18,800,
The number average molecular weight Mn was 16,200, and Mw / Mn was 1.
It was 16. The glass transition temperature measured by DSC was 275 ° C. Further, 0.5 g of this ring-opening polymer and 5% palladium carbon in a 100 ml autoclave were added.
05g and cyclohexane 40ml, hydrogen pressure 70kg / c
A hydrogenation reaction was performed at 140 ° C. for 4 hours at m ² . The hydrogenation rate of the obtained hydrogenated product calculated from ¹ H-NMR was 9
9.5%, the weight average molecular weight Mw measured by GPC
Was 23,400, the number average molecular weight Mn was 19,800, and Mw / Mn was 1.18. The glass transition temperature measured by DSC was 161 ° C.

Example 3 8-Methyltetracyclo [4.4.0.1 ^2,5 .
8-cyanotetracyclo [4.4.0.1 ^2,5 ... Instead of 1 ^7,10 ] -3-dodecene. Living ring-opening polymerization was carried out in the same manner as in Example 1 except for using ^1,7,10 ] -3-dodecene to obtain a ring-opened polymer in the form of a white powder. The yield of the ring-opened polymer obtained as described above is 99%,
The weight average molecular weight Mw measured at C was 60900, the number average molecular weight Mn was 51600, and Mw / Mn was 1.18.
Met. The glass transition temperature measured by DSC is 16
2 ° C. Further, in a 100 ml autoclave, 0.5 g of the ring-opened polymer, 0.07 g of tris (triphenylphosphine) rhodium (I) chloride, THF40
Then, a hydrogenation reaction was carried out at a hydrogen pressure of 70 kg / cm ² and 100 ° C. for 8 hours. The hydrogenation rate of the obtained hydrogenated product was 99% as calculated from ¹ H-NMR, the weight average molecular weight Mw measured by GPC was 62400, and the number average molecular weight M
n was 52000 and Mw / Mn was 1.20.
The glass transition temperature measured by DSC was 211 ° C.

[0027] Example 4 catalyst as _{Mo (N-2,6-C 6} H 3 Pr i 2) (CHCMe 2 Ph) (OBu t) 2 in place of _{Mo (N-2,6-C 6} H 3 Pr Living ring-opening polymerization was carried out in the same manner as in Example 3 except that ⁱ ₂ ) (CHCMe ₂ Ph) (OCMe (CF ₃ ) ₂ ) was used to obtain a ring-opened polymer in the form of a white powder. The yield of the ring-opened polymer obtained as described above is 98%.
The weight average molecular weight Mw measured by PC was 51300, the number average molecular weight Mn was 42400, and Mw / Mn was 1.2.
It was one. The glass transition temperature measured by DSC is 2
80 ° C. Further, in a 100 ml autoclave, 0.5 g of the ring-opened polymer, 0.07 g of tris (triphenylphosphine) rhodium (I) chloride, THF40
Then, a hydrogenation reaction was carried out at a hydrogen pressure of 70 kg / cm ² and 100 ° C. for 8 hours. The hydrogenation rate of the obtained hydrogenated product was 99%, as calculated from ¹ H-NMR, the weight average molecular weight Mw measured by GPC was 56400, and the number average molecular weight M
n was 43400 and Mw / Mn was 1.30.
The glass transition temperature measured by DSC was 217 ° C.

Comparative Example 1 8-methyltetracyclo [4.4.0.1 ^2,5 ... Was placed in a 100 ml flask equipped with a magnetic stirrer and a condenser. 1
^7,10 ] -3-dodecene 6.12 g (0.0351 mol)
, 50 ml of 1,2-dichloroethane, 0.1 ml of a toluene solution of a 0.25 M W-based catalyst prepared from tungsten hexachloride and acetal, 0.1 ml of a 2.4 M toluene solution of diethylaluminum chloride as a cocatalyst, a molecular weight regulator 0.059 g of 1-hexene (0.702 m
mol) was added and reacted at 60 ° C. for 2 hours. This polymerization solution was added to a large amount of methanol to precipitate a ring-opened polymer,
After separation by filtration, the polymer was further washed with methanol and dried to obtain a ring-opened polymer in the form of a white powder. The yield of the ring-opened polymer obtained as described above was as low as 32%, the weight average molecular weight Mw measured by GPC was 24,500, the number average molecular weight Mn was 6,980, and Mw / Mn was 3.51, which was 3.51. The distribution was wide. Further, 0.5 g of this ring-opened polymer and 5% palladium carbon 0.0 were added to a 100 ml autoclave.
5 g and 40 ml of cyclohexane were added, and the hydrogen pressure was 70 kg / c.
A hydrogenation reaction was performed at 140 ° C. for 4 hours at m ² . The hydrogenation rate of the obtained hydrogenated product calculated from ¹ H-NMR was 8
2%, and the weight average molecular weight Mw measured by GPC is:
30,200, the number average molecular weight Mn was 7,200, and Mw /
Mn was as wide as 4.2.

[0029]

The hydrogenated tetracyclododecene polymer of the present invention has a high glass transition temperature and a narrow molecular weight distribution, is uniform in molecular weight, and can be expected as a heat-resistant polymer. Further, the method for producing a hydrogenated tetracyclododecene polymer of the present invention can efficiently provide a heat-resistant polymer, and is extremely valuable industrially.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-4-170425 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08G 61/06-61/08

Claims (5)

(57) [Claims] A glass transition temperature represented by the general formula (Chemical formula 1) is 100 ° C. or higher, and a ratio (Mw / Mn) of weight average molecular weight Mw to number average molecular weight Mn measured by GPC is 1.0. To 1.8 hydrogenated tetracyclododecene polymer. Embedded image (In the formula, R _{1 to} R ₄ may be the same or different and each represents hydrogen, a hydrocarbon group, a halogen group, a hydrocarbon group substituted with a halogen atom, a nitrile group, a carboxyl group, or a methylcarboxyl group. X represents an integer of 1 to 3, and n represents an integer greater than 1.) 2. The tetracyclodide according to claim 1, wherein R ₁ represented by the general formula (Chemical Formula 2) is a methyl group or a cyano group, and R _{2 to} R ₄ are an H group. A hydrogenated decene polymer. Embedded image 3. A method of polymerizing at least one tetracyclododecene monomer represented by the general formula (Chem. 3) with a living ring-opening metathesis catalyst and hydrogenating it under a hydrogenation catalyst. The glass transition temperature represented by the general formula (Formula 4) is 100 ° C. or higher, and the ratio (Mw) between the weight average molecular weight Mw and the number average molecular weight Mn measured by GPC.
/ Mn) is from 1.0 to 1.8, and is a method for producing a hydrogenated tetracyclododecene polymer. Embedded image (In the formula, R _{1 to} R ₄ may be the same or different and each represents hydrogen, a hydrocarbon group, a halogen group, a hydrocarbon group substituted with a halogen atom, a nitrile group, a carboxyl group, or a methylcarboxyl group. And x represents an integer of 1 to 3.) (In the formula, R _{1 to} R ₄ may be the same or different and each represents hydrogen, a hydrocarbon group, a halogen group, a hydrocarbon group substituted with a halogen atom, a nitrile group, a carboxyl group, or a methylcarboxyl group. X represents an integer of 1 to 3, and n represents an integer greater than 1.) 4. The tetracyclodide according to claim 3, wherein R ₁ represented by the general formula (Formula 5) is a methyl group or a cyano group, and R _{2 to} R ₄ are H groups. A method for producing a hydrogenated decene polymer. Embedded image 5. The method for producing a hydrogenated tetracyclododecene polymer according to claim 3, wherein the hydrogenation catalyst is tris (triphenylphosphine) rhodium (I) chloride.