JP2001342217A - Cyclopentadiene-based polymer and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a high-molecular weight cyclopentadiene-based polymer with narrow molecular weight distribution. SOLUTION: This cyclopentadiene-based polymer with (A) a number-average molecular weight(Mn) of 1×103 to 1×106 and (B) the ratio of the weight-average molecular weight(Mw) to Mn of 1.0-2.6 is obtained by polymerizing the corresponding cyclopentadiene-based monomer using a catalyst comprising (a) a cationically polymerizable monomer's protonic acid adduct and (b) a Lewis acid.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a high molecular weight cyclopentadiene-based polymer having a narrow molecular weight distribution and a method for producing the same.

[0002]

2. Description of the Related Art Polymers of cyclopentadiene-based monomers such as cyclopentadiene are described in Kobunshi Kagaku, Vol.
-109 (1970), it is synthesized by cationic polymerization of the same monomer using a Lewis acid such as a metal halide as a catalyst. The cyclopentadiene polymer is a polymer composed of 1,2-addition units and 1,4-addition units of a monomer. However, the active species in the polymerization reaction is carbonium ion, and it is difficult to control its reactivity.Therefore, there was no polymer whose molecular weight, molecular weight distribution, terminal structure or addition form of monomers were controlled. .

[0003] On the other hand, Catalyst in Pre
cision Polymerization, Cha
pter 7, Wiley, New York, 199
As described in 7, it is known that a polymer having a controlled structure can be obtained by cationic polymerization using a catalyst composed of a protonic acid and a Lewis acid. However, these include vinyl ethers, isobutene, styrenic monomers and N-
It is a polymer of a monomer such as vinylcarbazole, and no report has been made on a cyclopentadiene-based polymer.

[0004]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems of the prior art, and provides a high molecular weight cyclopentadiene polymer having a narrow molecular weight distribution. It is another object of the present invention to provide a method for producing the same.

[0005]

SUMMARY OF THE INVENTION The present invention has been found as a result of intensive studies on the above objects. That is, the present invention provides the following general formula (1)

[0006]

Embedded image

(Wherein R is each independently a hydrogen atom or a hydrocarbon group having 1 to 50 carbon atoms.) (A) A number average molecular weight (A) obtained by polymerizing a cyclopentadiene monomer represented by the following formula: (Mn) is 1 × 10 ³ or more and 1 × 10 ⁶ or less, and (B) the ratio (Mw / Mn) between the weight average molecular weight (Mw) and the number average molecular weight is 1.0 or more and 2.6 or less. A cyclopentadiene-based polymer is provided. Further, the present invention provides a method for producing the polymer.

The cyclopentadiene monomer in the present invention includes cyclopentadiene, 1-methylcyclopentadiene, 2-methylcyclopentadiene, 1-ethylcyclopentadiene, 2-ethylcyclopentadiene, 5-methylcyclopentadiene, 1,2- Dimethylcyclopentadiene, 1,3-dimethylcyclopentadiene, 2,3-dimethylcyclopentadiene, 3-ethyl-1-methylcyclopentadiene, 1-methyl-3-
Examples thereof include propylcyclopentadiene and 5,5-dimethylcyclopentadiene.

Further, two or more of the above cyclopentadiene-based monomers can be used as a mixture.

In the present invention, M _n , M _w and M _w / M
_n is a value measured by gel permeation chromatography (GPC), and is a value calibrated with a polystyrene sample having a known molecular weight.

The _Mn of the cyclopentadiene polymer in the present invention is from 1 × 10 ^{3 to} 1 × 10 ⁶ , preferably from 2 × 10 ^{3 to} 1 × 10 ⁶ . More preferably, it is 3 × 10 ³ or more and 1 × 10 ⁶ or less.

The _Mw / _Mn of the cyclopentadiene polymer in the present invention is from 1.0 to 2.6, preferably from 1.0 to 2.0. More preferably, it is 1.0 or more and 1.4 or less.

In the present invention, when the cyclopentadiene-based polymer is a polymer of cyclopentadiene alone, in addition to (A) and (B), (C) the ratio of the amount of olefin protons to the amount of aliphatic protons is 45% or more and 50% or less, and (D) 1,2-added unit is 20 mol
It is preferable that the amount is not less than 1% and not more than 100 mol%.

In the present invention, the ratio of the amount of olefinic protons to the amount of aliphatic protons {[H (unsaturated) / H (saturated)]%} is described in Kobunshi Kagaku, Vol. 27, 97-109 (1).
970) by substituting the peak integral ratio obtained by proton nuclear magnetic resonance spectroscopy ( ¹ H-NMR) of the polymer into the following formula (2).

[H (unsaturated) / H (saturated)]% = W / (X + Y + Z) × 100 (2) (where X is an integral ratio of a peak corresponding to a methylene proton of 1,4-addition unit) Y is the integral ratio of the peak corresponding to the methylene proton of the 1,2-addition unit,
Is the integral ratio of the peaks corresponding to the methine proton of the 1,4-addition unit and the methine proton of the 1,2-addition unit, and W is the olefin proton of the 1,4-addition unit and the olefin of the 1,2-addition unit. This is the integration ratio of the peak corresponding to the proton. ) In addition, the amount of the 1,2-addition unit {[1,2-addition unit] mol%} is the peak integration ratio obtained by ¹ H-NMR according to the method described in the above-mentioned literature, by the following formula (3). Alternatively, it is a value calculated by two methods by substituting into (4).

Method 1: [1,2-addition unit] mol% = (Y + Z−X) / (X + Y + Z) × 100 (3) Method 2: [1,2-addition unit] mol% = (1-X / W) × 100 (4) In the present invention, the cyclopentadiene-based polymer is
It is produced by polymerizing a cyclopentadiene monomer using a catalyst comprising (a) a proton acid adduct of a cationically polymerizable monomer and (b) a Lewis acid.

The component (a) in the present invention is a reaction product of a cationically polymerizable monomer and a protonic acid.

Here, the cationically polymerizable monomer for obtaining the component (a) is a monomer capable of cationic polymerization, and includes the above-mentioned cyclopentadiene monomer, methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, 2-chloroethyl vinyl ether, Vinyl ether such as 2-acetoxyethyl vinyl ether or styrene, α-methylstyrene, p-methylstyrene, p
Styrene-based monomers such as -methoxystyrene, p-chlorostyrene, and vinylnaphthalene can be exemplified. These may be used in combination of two or more.

Examples of the protonic acid for obtaining the component (a) include hydrogen chloride, hydrogen fluoride, hydrogen bromide, hydrogen iodide, sulfuric acid, acetic acid, methylsulfonic acid, trichloroacetic acid, trifluoroacetic acid and trifluoromethylsulfone. Acid or perchloric acid can be exemplified. These may be used in combination of two or more.

The Lewis acid of component (b) in the present invention includes tin tetrachloride, tin tetrabromide, titanium tetrachloride, titanium tetrabromide, aluminum chloride, aluminum bromide, zinc chloride,
Zinc bromide, boron trichloride, boron trifluoride, ethylaluminum chloride, diethylaluminum chloride, isopropoxytitanium trichloride, diisopropoxytitanium dichloride, phenoxytitanium trichloride, diphenoxytitanium dichloride, bis (2
Examples thereof include 6-dichlorophenoxy) titanium dichloride and bis (2,6-diisopropylphenoxy) titanium dichloride. These may be used in combination of two or more.

The catalyst comprising the component (a) and the component (b) in the present invention is preferably used as the component (a) for the purpose of controlling the molecular weight of the obtained polymer more preferably as a hydrogen chloride adduct of cyclopentadiene. And a combination using tin tetrachloride or zinc chloride as the component (b) can be used.

Further, the cyclopentadiene-based polymer of the present invention is preferably added to the catalyst comprising the above components (a) and (b) to further control (c) Lewis base and / or It is also produced by adding salts and polymerizing a cyclopentadiene-based monomer.

Examples of the Lewis base used for the component (c) include esters such as ethyl acetate and ethyl p-methoxybenzoate; ethers such as dioxane, tetrahydrofuran and diethyl ether; 2,6-dimethylpyridine;
4,6-trimethylpyridine, 2,6-di-tert-
Butylpyridine, 2,6-di-tert-butyl-4-
Pyridine derivatives such as methylpyridine, sulfides such as dimethylsulfide and tetrahydrothiophene, 1-methyl-2-pyrrolidone, N, N-diethylacetamide;
Examples thereof include 1-butylimidazole and dimethylsulfoxide.

The salts of the component (c) include tetrabutylammonium salts such as tetrabutylammonium chloride, tetrabutylammonium perchlorate, tetrabutylammonium tetrafluoroborate and tetrabutylammonium hexafluorophosphate, and tetrabutylphosphonium chloride. , Tetraalkylphosphonium salts such as tetrabutylphosphonium acetate, and triphenylmethyl chloride.

In the polymerization according to the present invention, a cyclopentadiene-based monomer and a catalyst comprising component (a) and component (b) or a catalyst comprising component (a), component (b) and component (c) are mixed in a solvent. The contact is performed by contact, but the contact method is not particularly limited.

The polymerization solvent may be any commonly used organic solvent, specifically, benzene,
Aromatic hydrocarbons such as toluene and xylene, propane, butane, isobutane, pentane, hexane, heptane, octane, aliphatic hydrocarbons such as cyclopentane, cyclohexane, methylcyclohexane, decalin, carbon tetrachloride, chloroform, methylene chloride, And halogenated hydrocarbons such as 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2-trichloroethane and 1,1,2-trichloroethylene. These may be used in combination of two or more.

The amount of the polymerization solvent used is not particularly limited, but the concentration of the cyclopentadiene monomer is 1 × 10 ⁻⁶ mol.
/ L to 10 mol / l can be used.

The amount of component (a) used is not particularly limited.
1 × 10 per mol of cyclopentadiene monomer
^-5 mol to 1 mol, preferably 1 × 10 ^-4 mol to
The range is 0.5 mol.

There is no particular limitation on the amount of component (b) to be used, but 1 × 10 ^-1 mol per mol of component (a).
1 × 10 ⁴ mol, preferably 5 × 10 ⁻¹ mol to ¹ ×
It is in the range of 10 ³ mol.

There are no particular restrictions on the amount of component (c) used, but from 0 mol to 1 × 10 5 per mol of component (a).
³ mol, preferably ^{1 × 10 -4 mol~1 × 10 3} mo
l, more preferably 1 × 10 ⁻³ mol to 1 × 10 ² m
ol range.

The polymerization temperature is not particularly limited, but is -200 ° C.
To 300 ° C, preferably -100 ° C to 200 ° C.

The cyclopentadiene-based polymer of the present invention comprises
It can be used by adding hydrogen by a known method.
Hydrogenated cyclopentadiene-based polymers in which 1,4-addition units or 1,2-addition units are highly controlled,
It has excellent heat resistance and can be used for various molding materials.

The cyclopentadiene polymer of the present invention can be used for block copolymerization with a cationically polymerizable monomer.

[0034]

EXAMPLES The present invention will now be described specifically with reference to examples, but the present invention is not limited to these examples.

The purification of cyclopentadiene, the purification of the polymerization solvent, and the polymerization reaction were all performed under a dry nitrogen atmosphere.
The solvent, diethyl ether and ethyl acetate used for the polymerization reaction were all those which had been previously deoxygenated, dried and purified by a known method. Cyclopentadiene was obtained by thermally decomposing dicyclopentadiene at 160 ° C. and collecting it at −78 ° C., distilling it over calcium hydride immediately before use, collecting it again at −78 ° C., and using it for polymerization. Cyclopentadiene, isobutyl vinyl ether, 2-chloroethyl vinyl ether, styrene, a hydrogen chloride adduct of α-methylstyrene and a hydrogen bromide adduct of cyclopentadiene are
Macromolecules, 32 , 6407-64
11 (1999). Tin tetrachloride, zinc chloride, zinc bromide, titanium tetrachloride, 2,6-di-tert-butyl-4-methylpyridine, and boron trifluoride diethyl ether complex were used directly from Aldrich. Tetrabutylammonium chloride and triphenylmethyl chloride used by Tokyo Chemical Industry Co., Ltd. were used as they were. As trifluoroacetic acid, Wako Pure Chemical Industries, Ltd. was used as it was.
Methylsulfonic acid was used directly from Nacalai Tesque, Inc. Diisopropoxytitanium dichloride and isopropoxytitanium trichloride are available from Macrom
olecules, 28 , 5671-5675 (199
A product synthesized and recrystallized by the method described in 5) was used.

The conversion in the polymerization of cyclopentadiene in Examples and Comparative Examples was determined from the amount of residual monomers measured by gas chromatography using carbon tetrachloride as an internal standard.

As a gas chromatography method,
GC8A manufactured by Shimadzu Corporation was used as an apparatus, PEG 1500 was used as a column, and helium was used as a carrier gas. Injection temperature is 120
° C and the column temperature were set to 80 ° C.

Further, the structures of the cyclopentadiene polymers in Examples and Comparative Examples were evaluated by the following methods.

The number average molecular weight (M _n ), weight average molecular weight (M _w ) and the ratio of M _w to M _n (M _w / M _n ) were determined by gel permeation chromatography (GPC). As a GPC device, PU- made by Jasco
The measurement was carried out using 980 and 930-RI manufactured by Jasco, using three K-805L manufactured by Shodex as a column, using chloroform as an eluent, and setting the column temperature to 40 ° C. The calibration curve of the molecular weight was obtained by a universal calibration method using a polystyrene sample of a known molecular weight (M _n = 580 to 1,547,000, M _w / M
_n ≦ 1.1).

The ratio of the amount of olefinic protons to the amount of aliphatic protons {[H (unsaturated) / H (saturated)]%} is the peak obtained by proton nuclear magnetic resonance spectroscopy ( ¹ H-NMR) of the polymer. The integral ratio was calculated by substituting into the equation (2).

The amount of the 1,2-addition unit was calculated by the above two methods, Method 1 and Method 2. The amount of the 1,2-added unit {[1,2-added unit] mol% (method 1)} according to the method 1 is obtained by substituting the peak integral ratio obtained by ¹ H-NMR of the polymer into the formula (3). Was calculated. Method 2
Amount of 1,2-addition unit according to ｛[1,2-addition unit] m
ol% (method 2)} was calculated by substituting the peak integral ratio obtained by ¹ H-NMR of the polymer into the formula (4).

The ¹ H-NMR measurement of the polymer was performed at room temperature using LNM-LA500 manufactured by JEOL as an apparatus and deuterated chloroform as a measuring solvent.

EXAMPLE 1 0.165 ml of cyclopentadiene was placed in a glass container.
(2.0 mmol) and 3.2 ml of a toluene solution containing 0.165 ml of carbon tetrachloride were added, and the mixture was cooled to −78 ° C., and then 2.05 mg of a hydrogen chloride adduct of cyclopentadiene was added.
(0.02 mmol) in toluene solution 0.4 ml, followed by tin tetrachloride 52.1 mg (0.2 mmol)
Was added to initiate a polymerization. Cyclopentadiene concentration at the start of polymerization is 500 mm
ol / l, the hydrogen chloride adduct concentration of cyclopentadiene was 5.0 mmol / l, and the tin tetrachloride concentration was 50 mmol / l.
mmol / l. After stirring at −78 ° C. for 30 minutes, 2.0 ml of methyl alcohol containing ammonia was added to terminate the polymerization. The conversion was 95%. The obtained reaction mixture was washed with dilute hydrochloric acid and then with an aqueous sodium hydroxide solution and water to remove a catalyst residue. The obtained solid was dried under reduced pressure to obtain a polymer.

[0044] M _n and M _w / M _n of the obtained polymer was as follows.

M _n = 7,800 M _w / M _n = 1.59 From the analysis of the obtained polymer by ¹ H-NMR,
1.6 ppm 1,4-addition unit methylene protons,
1. A methylene proton of 1,2-addition unit at 2 ppm.
The methine proton of the 1,4-addition unit and the methine proton of the 1,2-addition unit are 5.7 pp at 3-2.9 ppm.
m represents a 1,4-addition unit of an olefin proton and 1,
An olefin proton of the 2-addition unit was observed. These integral ratios were substituted into Expressions (2), (3) and (4) as X, Y, Z and W, respectively, to obtain the following values.

[H (unsaturated) / H (saturated)]% = 49.3 [1,2-addition unit] mol% (method 1) = 45.8 [1,2-addition unit] mol% (method 2) = 45.0 The results are shown in Table 1. Also, the ¹ H-N
FIG. 1 shows the results of the MR measurement.

Examples 2 to 6 Polymerization was carried out in the same manner as in Example 1 except that the polymerization conditions were changed as shown in Table 1. Table 1 shows the results.

Comparative Example 1 Polymerization was carried out in the same manner as in Example 3 except that the hydrogen chloride adduct of cyclopentadiene was not used and the polymerization time was 1,140 minutes. The conversion was 33%.

The results of the structural analysis of the obtained polymer are as follows, and it was a polymer having M _w / M _{n of} more than 2.6.

M _n = 11,500 M _w / M _n = 2.85 The above results are shown in Table 1.

Comparative Example 2 Polymerization was carried out in the same manner as in Example 3 except that trifluoroacetic acid was used instead of the hydrogen chloride adduct of cyclopentadiene, and that the polymerization time was 30 minutes. The conversion was 91%.

The results of the structural analysis of the obtained polymer are as follows, and it was a polymer having M _w / M _{n of} more than 2.6.

_Mn = 16,300 _Mw / _Mn = 2.97 The above results are shown in Table 1.

Examples 7 to 10 Polymerization was carried out in the same manner as in Example 1 except that the polymerization conditions were changed as shown in Table 1. Table 1 shows the results.

Examples 11 to 21 Polymerization was carried out in the same manner as in Example 1 except that the polymerization conditions were changed as shown in Table 2. Table 2 shows the results.

Examples 22 to 26 Polymerization was carried out in the same manner as in Example 1 except that the polymerization conditions were changed as shown in Table 3. Table 3 shows the results.

Example 27 0.165 ml of cyclopentadiene was placed in a glass container.
(2.0 mmol) and 3 ml of a toluene solution containing 0.165 ml of carbon tetrachloride were added thereto, and the mixture was cooled to -78 ° C, and then 2.05 mg of hydrogen chloride adduct of cyclopentadiene (0.
0.5 mmol of a methylene chloride solution containing 0.22 mmol) followed by 5.21 mg (0.02 mmol) of tin tetrachloride.
And 2.22 mg of tetrabutylammonium chloride
(0.008 mmol) in methylene chloride solution 0.5
ml was added to initiate polymerization. The cyclopentadiene concentration at the start of the polymerization was 500 mmol / l, and the hydrogen chloride adduct concentration of cyclopentadiene was 5.0 mmol / l.
And the concentration of tin tetrachloride is 5 mmol / l, and the concentration of tetrabutylammonium chloride is 2.0 mmol / l.
l. After stirring at -78 ° C for 1 minute, 2.0 ml of methyl alcohol containing ammonia was added to terminate the polymerization. The conversion was 28%. The obtained reaction mixture was washed with dilute hydrochloric acid and then with an aqueous sodium hydroxide solution and water to remove a catalyst residue. The obtained solid was dried under reduced pressure to obtain a polymer. Table 3 shows the results.

Examples 28 to 30 Polymerization was carried out in the same manner as in Example 27 except that the polymerization conditions were changed as shown in Table 3. Table 3 shows the results.

Examples 31 to 46 Polymerization was carried out in the same manner as in Example 27 except that the polymerization conditions were changed as shown in Table 4. Table 4 shows the results.

Examples 47 to 52 Polymerization was carried out in the same manner as in Example 27 except that the polymerization conditions were changed as shown in Table 5. Table 5 shows the results.

Examples 53 to 66 Polymerization was carried out in the same manner as in Example 27, except that the polymerization conditions were changed as shown in Table 6. Table 6 shows the results.

Examples 67 to 80 Polymerization was carried out in the same manner as in Example 27 except that the polymerization conditions were changed as shown in Table 7. Table 7 shows the results.

Examples 81 to 92 Polymerization was carried out in the same manner as in Example 1 except that the polymerization conditions were changed as shown in Table 8. Table 8 shows the results.

Comparative Example 3 The same procedure as in Example 3 was carried out except that the hydrogen chloride adduct of cyclopentadiene was not used, tin tetrachloride was replaced by titanium tetrachloride, and the polymerization time was changed to 3 minutes. To perform polymerization. The conversion was 80%.

The results of the structural analysis of the obtained polymer are as follows, and it was a polymer having M _w / M _{n of} more than 2.6.

M _n = 10,100 M _w / M _n = 2.84 [H (unsaturated) / H (saturated)]% = 48.1 [1,2-added unit] mol% (method 1) = 48.1 [1,2-added unit] mol% (method 2) = 46.0 The above results are shown in Table 8.

Comparative Example 4 The procedure of Example 1 was repeated except that the hydrogen chloride adduct of cyclopentadiene was not used, tin tetrachloride was replaced by boron trifluoride diethyl ether complex, and the polymerization time was 240 minutes. Polymerization was carried out in the same manner as in Example 1. 0% conversion
Met.

Examples 93 to 98 Polymerization was carried out in the same manner as in Example 27 except that the polymerization conditions were changed as shown in Table 9. Table 9 shows the results.

Example 99 In a glass container, 2.94 mg (0.02 mmol) of a hydrogen bromide adduct of cyclopentadiene and 0.1% of carbon tetrachloride were placed.
Put 3.2 ml of methylene chloride solution containing 65 ml,
After cooling to 78 ° C., 90.1 mg of zinc bromide (0.4 m
mol) and 285 mg of diethyl ether (3.84 mm
ol), followed by cyclopentadiene 0.165 m
0.4 m in methylene chloride solution containing 1 (2.0 mmol)
1 was added to initiate polymerization. The cyclopentadiene concentration at the start of the polymerization was 500 mmol / l, the hydrogen bromide adduct concentration of cyclopentadiene was 5.0 mmol / l, the zinc bromide concentration was 100 mmol / l, and the diethyl ether concentration was 960 mmol / l. Met. -7
After stirring at 8 ° C. for 240 minutes, 2.0 ml of methyl alcohol containing ammonia was added to terminate the polymerization. The conversion was 40%. The obtained reaction mixture is washed with dilute hydrochloric acid, then with an aqueous sodium hydroxide solution and water,
The catalyst residue was removed. The obtained solid is dried under reduced pressure,
A polymer was obtained. Table 9 shows the results.

Example 100 Polymerization was carried out in the same manner as in Example 99 except that the polymerization conditions were changed as shown in Table 9. Table 9 shows the results.

Comparative Example 5 No tin tetrachloride was used, the hydrogen chloride adduct of cyclopentadiene was changed to methylsulfonic acid, the polymerization time was changed to 20 minutes, and the polymerization solvent was changed to methylene chloride. Polymerization was carried out in the same manner as in Example 3 except for the above. The conversion was 78%.

The results of structural analysis of the obtained polymer are as follows, and it was a polymer having M _w / M _{n of} more than 2.6.

_Mn = 37,200 _Mw / _Mn = 4.20 [H (unsaturated) / H (saturated)]% = 49.3 [1,2-added unit] mol% (method 2) = Table 9 shows the results of 49.0 and above.

Comparative Example 6 Polymerization was carried out in the same manner as in Example 35, except that the hydrogen chloride adduct of cyclopentadiene was changed to methylsulfonic acid, and the polymerization time was changed to 60 minutes. Conversion rate is 0
%Met.

Table 1, Table 2, Table 3, Table 4, Table 5, Table 6, and Table 5 show the polymerization conditions and the polymerization results in the above Examples and Comparative Examples.
The results are shown in Tables 7, 8, and 9.

[0076]

[Table 1]

[0077]

[Table 2]

[0078]

[Table 3]

[0079]

[Table 4]

[0080]

[Table 5]

[0081]

[Table 6]

[0082]

[Table 7]

[0083]

[Table 8]

[0084]

[Table 9]

[0085]

The cyclopentadiene polymer of the present invention is a high molecular weight polymer having a narrow molecular weight distribution, and exhibits high heat resistance when used as a molding material. This cyclopentadiene-based polymer can be synthesized using a specific catalyst.

[Brief description of the drawings]

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 shows ¹ H- of the polymer obtained in Example 1.
3 shows an NMR spectrum.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J015 DA05 DA32 DA33 EA02 EA03 EA04 EA06 EA09 4J100 AR17P CA01 CA16 DA01 DA04 FA08 FA12

Claims (5)

[Claims] (1) The following general formula (1): (Wherein, R is each independently a hydrogen atom or a carbon number of 1 to 5)
0 hydrocarbon group. (A) Number average molecular weight (Mn) of 1 × 10 ³ or more and 1 × 10 ⁶ obtained by polymerizing a cyclopentadiene-based monomer represented by the following formula:
(B) a cyclopentadiene-based polymer, wherein the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight is 1.0 or more and 2.6 or less. 2. The cyclopentadiene-based polymer according to claim 1, wherein the ratio of the olefin proton amount to the aliphatic proton amount (C) is 45% or more and 50% or less;
A cyclopentadiene-based polymer, wherein the 1,2-addition unit is at least 20 mol% and at most 100 mol%. 3. The method according to claim 1, wherein the cyclopentadiene monomer is polymerized using a catalyst comprising (a) a proton acid adduct of a cationically polymerizable monomer and (b) a Lewis acid. A method for producing a cyclopentadiene-based polymer. 4. A (a) proton acid adduct of a cationically polymerizable monomer, (b) a Lewis acid and (c) a Lewis base and / or
The method for producing a cyclopentadiene-based polymer according to claim 1 or 2, wherein the cyclopentadiene-based monomer is polymerized using a salt catalyst. 5. The process for producing a cyclopentadiene polymer according to claim 3, wherein (a) the proton acid adduct of the cationic polymerizable monomer is a proton acid adduct of a cyclopentadiene monomer. .