JPH07179575A - Tetracyclododecene polymer and its production - Google Patents

Abstract

PURPOSE:To obtain a new tetracyclododecene polymer having high glass transition temperature and narrow molecular weight distribution and useful as a heat-resistant polymer by polymerizing a specific tetracyclododecene monomer in the presence of a living ring-opening metathesis catalyst. CONSTITUTION:This tetracyclododecene polymer expressed by formula II ((n) is an integer of >1) and having a glass transition temperature of >=150 deg.C and a (weight-average molecular weight Mw)/(number-average molecular weight Mn) of 1-1.8 measured by GPC is produced by polymerizing a tetracyclododecene monomer of formula I (R1 to R4 each is H, a hydrocarbon group, a halogen, etc.; (x) is 1-3) (e.g. tetracyclo[4.4.0.1<2.5>.1<7.10>]-3-dodecene) in the presence of a living ring-opening metathesis catalyst usually in a solvent. The catalyst is e.g. a ruthenium-based alkylidene catalyst of formula III (Ph is phenyl). The polymerization temperature is preferably 10-100 deg.C.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel tetracyclododecene polymer and a method for producing the same. More specifically, it relates to a 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 a tetracyclododecene-based monomer is generally carried out by using a tungsten or molybdenum-based catalyst as a polymerization catalyst and a promoter such as an organoaluminum compound. However, when these polymerization catalysts are used, only specific monomers can be polymerized, or conversely, the molecular weight increases, which makes it difficult to control the molecular weight distribution. In order to solve this problem, it is known to use α-olefins such as 1-pentene and 1-hexene as a molecular weight regulator, and they are disclosed in JP-A-5-105743 and JP-A-5-132545.
The publication discloses a method for producing a polymer using them. However, although these methods 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 an imidoalkylidene complex of molybdenum or tungsten. When these catalysts are used, the reaction proceeds in living polymerization and the molecular weight distribution can be controlled to be monodisperse. Further, Macromolecules, 24 , 4495 (1991). Discloses an example of ring-opening polymerization of a norbornene-based monomer with a catalyst having these alkylidene complexes, and detailed stereochemical studies of the polymer have been conducted. However, these polymers have low glass transition temperatures and are industrially insufficient as heat-resistant polymers.

[0004]

DISCLOSURE OF THE INVENTION The present invention is directed to a tetracyclododecene polymer capable of solving at least some of the above-mentioned drawbacks of the prior art, for example, tetracyclododecene having a high glass transition temperature and a narrow molecular weight distribution. An object of the present invention is to provide a system polymer and a method for producing such a polymer.

[0005]

Means for Solving the Problems The present inventors have diligently studied a tetracyclododecene polymer having a high glass transition temperature and a narrow molecular weight distribution by solving the above problems, and a method for producing the same. The present invention has been completed. That is, the present invention has a glass transition temperature represented by the general formula (1) [Chemical Formula 4] of 150 ° C. or higher and a ratio (Mw / Mn) of the weight average molecular weight Mw and the number average molecular weight Mn measured by GPC. Is 1.
It is a tetracyclododecene polymer having a molecular weight of 0 to 1.8.

[0006]

[Chemical 4] (In the formula, R _{1 to} R ₄ may be the same or different and each is hydrogen, a hydrocarbon group having 1 to 12 carbon atoms, a halogen group, or a hydrocarbon group having 1 to 12 carbon atoms substituted with a halogen atom. Group, a nitrile group, a carboxyl group, a methylcarboxyl group, x represents an integer of 1 to 3, and n represents an integer greater than 1.) The present invention also provides a compound represented by the general formula (2):
A glass transition temperature represented by the general formula (1) [Chemical formula 6], characterized in that at least one tetracyclododecene monomer represented by the [Chemical formula 5] is polymerized with a living ring-opening metathesis catalyst. Is 150 ° C. or higher, and the ratio (Mw) of the weight average molecular weight Mw and the number average molecular weight Mn measured by GPC.
/ Mn) is 1.0 to 1.8, and is a method for producing a tetracyclododecene polymer.

[0007]

[Chemical 5] (In the formula, R _{1 to} R ₄ may be the same or different and each is hydrogen, a hydrocarbon group having 1 to 12 carbon atoms, a halogen group, or a hydrocarbon group having 1 to 12 carbon atoms substituted with a halogen atom. Represents a group, a nitrile group, a carboxyl group, a methylcarboxyl group, and x represents an integer of 1 to 3.)

[0008]

[Chemical 6] (In the formula, R _{1 to} R ₄ may be the same or different and each is hydrogen, a hydrocarbon group having 1 to 12 carbon atoms, a halogen group, or a hydrocarbon group having 1 to 12 carbon atoms substituted with a halogen atom. Represents a group, a nitrile group, a carboxyl group, a methylcarboxyl group, x represents an integer of 1 to 3, and n represents an integer larger than 1.)

Specific examples of the tetracyclododecene-based monomer represented by the formula (2) (Formula 7) in the present invention include x
1 is tetracyclododecene and its derivative, x is 2 hexacycloheptacene and its derivative, and x is 3 octacyclodococene and its derivative. As these derivatives, R _{1 to} R ₄ have 1 carbon atoms.
To 12 derivatives such as alkyl substitution, aryl substitution and aralkyl substitution, halogen substitution where R _{1 to} R ₄ are chlorine, bromine, iodine and the like, alkyl substitution containing halogen such as chloromethyl and bromomethyl, nitrile substitution, carboxyl substitution,
Examples include derivatives such as methylcarboxy substitution,

[0010]

[Chemical 7] (In the formula, R _{1 to} R ₄ may be the same or different and each is hydrogen, a hydrocarbon group having 1 to 12 carbon atoms, a halogen group, or a hydrocarbon group having 1 to 12 carbon atoms substituted with a halogen atom. Represents a group, a nitrile group, a carboxyl group, a methylcarboxyl group, x represents an integer of 1 to 3, and n represents an integer larger than 1.)

More specifically, 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-ethyltetracyclo [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-carboxymethyltetracyclo [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-ethoxytetracyclo [4.4.0.1 ^2,5 .
1 ^7,10 ] -3-Dodecene, 8,9-dimethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8
-Methyl-8-carboxymethyltetracyclo [4.
4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-phenyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-
Tetracyclododecenes such as dodecene and hexacyclo [6.6.1.1 ^3,6 . 0 ^2,7 . 0 ^9,14] -4-heptadecene, 11-methyl-hexa cyclo [6.6.1.1
^3,6 . 0 ^2,7 . 0 ^9,14] -4-heptadecene, 11-cyanohexadecanoic cyclo [6.6.1.1 ^3,6 · 0 ^2,7. 0
^9,14] -4 polycycloalkane such as heptadecene can be mentioned. These tetracyclododecene-based monomers may be copolymerized alone or in combination of two or more.

Further, these tetracyclododecene-based polymers may be those obtained by ring-opening polymerization of the above-mentioned specific monomer alone, but a monomer having a copolymerizability with the specific monomer. It may be obtained by ring-opening polymerization of the body. Specific examples of the copolymerizable monomer include cyclobutene,
Cycloolefins such as cyclopentene, cycloheptene and cyclooctene can be mentioned. Further, bicyclo [2.2.1] hept-2-ene, 2-methylbicyclo [2.2.1] hept-5-ene, 2-cyanobicyclo [2.2.1] hept-5-ene, etc. You may carry out ring-opening polymerization by copolymerizing a norbornene derivative and dicyclopentadiene.

The living ring-opening metathesis catalyst used in the present invention may be any catalyst as long as it is a catalyst for living ring-opening metathesis polymerization, and specific examples 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 ) (CHBu ^t )
(OCMe ₂ 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 2 CF 3) 2) 2), (Pr i is i- propyl group in the formula, Bu ^t is t- butyl ,
Me represents a methyl group and Ph represents a phenyl group. ) Etc., tungsten-based alkylidene catalysts, Mo (N-2,6-C ₆ H ₃ Pr ⁱ ₂ ) (CHBu ^t ) (OBu ^t ) ₂ , Mo (N-2,6-C ₆ H ₃ P
r ⁱ ₂ ) (CHBu ^t ) (OCMe ₂ CF ₃ ) ₂ , Mo (N-2,6-C ₆ H ₃ Pr ⁱ ₂ ) (CHB
u ^t ) (OCMe ₂ 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) (CHCMe 2 Ph) (OCMe 2 CF 3)
_{2, Mo (N-2,6-} C 6 H 3 Pr i 2) (CHCMe 2 Ph) (OCMe 2 CF 3) 2) 2), (Pr i is i- propyl group in the formula, Bu ^t is t -Butyl group,
Me represents a methyl group and Ph represents a phenyl group. ) Etc. molybdenum-based alkylidene catalysts, Re (CBu ^t ) (CHBu ^t ) (2,6-diisopropylphenoxide),
Re (CBu ^t ) (CHBu ^t ) (ortho-t-butylphenoxide),
Re (CBu ^t ) (CHBu ^t ) (trifluoro-t-butoxide), Re
(CBu ^t ) (CHBu ^t ) (hexafluoro-t-butoxide), Re
(CBu ^t ) (CHBu ^t ) (2,6-dimethylphenoxide), (wherein But represents a ^t -butyl group), a rhenium-based alkylidene catalyst, 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
(CMeCH ₂ CCMe ₃ ) CH ₂ ] (2,6-diisopropylphenoxide) ₃ , (in the formula, Me represents a methyl group, Ph represents a phenyl group), a tantalum-based alkylidene catalyst, Ru (CHCHCPh ₂ ) (PPh ₃ ) Cl ₂ , and ruthenium-based alkylidene catalysts such as (wherein Ph represents a phenyl group) and titanacyclobutanes.
The living ring-opening metathesis catalyst may be used alone or in combination of two or more kinds.

The molar ratio of the tetracyclododecene-based monomer to the living ring-opening metathesis catalyst is a living polymerization in the ring-opening metathesis polymerization. Therefore, by controlling the molar ratio of the monomer to the catalyst, a desired molecular weight can be obtained. The polymer can be obtained. That is, with respect to 100 moles of the monomer, 1 catalyst
The polymer obtained by reacting moles has a molecular weight of almost 100 mer, and although these molecular weights are slightly different depending on the properties of the monomer, the ratio Mw of the weight average molecular weight Mw and the number average molecular weight Mn is Mw. / Mn is controlled within 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 10000: 1, preferably 1
The range is 00: 01-1000: 1.

Examples of the solvent used in the living ring-opening metathesis polymerization include ethers such as tetrahydrofuran, dibutyl ether and dimethoxyethane, aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene, and fats such as pentane, hexane and heptane. Group hydrocarbons, cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, alicyclic hydrocarbons such as decalin, methylene dichloride, dichloroethane, dichloroethylene, tetrachloroethane, chlorobenzene, halogenated hydrocarbons such as trichlorobenzene, and the like, You may use these individually or in mixture of 2 or more types.

The glass transition temperature of the tetracyclododecene polymer obtained in the present invention is 150 ° C. and 180 ° C.
The above is preferable. When the glass transition temperature is less than 150, it is insufficient as a heat resistant polymer. Further, the ratio (Mw / Mn) of the polystyrene-equivalent weight average molecular weight Mw and the number average molecular weight Mn of the tetracyclododecene-based polymer obtained in the present invention measured by GPC is 1.0 to 1.8,
The range of 1.0 to 1.5 is more preferable. Those having an Mw / Mn of more than 1.8 are not preferable because they are not uniform with the polymer.

The tetracyclododecene polymer of the present invention is produced by dissolving the above tetracyclododecene polymer and the living ring-opening metathesis catalyst in a solvent. The reaction temperature is usually 0 to 150 ° C, and 10 to 100 ° C.
Is preferred. The reaction time is usually 1 minute to 10 hours, and the living polymer is treated with aldehydes, ketones,
The reaction can be stopped by substituting the generated end with a quenching agent such as alcohols. Generally, the concentration of the monomer / catalyst as a raw material and the solvent is selected in the range of 0.1 to 100 mol / l. The selection of this concentration depends on the reactivity of the monomer and the solubility in the polymerization solvent. Done.

[0018]

EXAMPLES The present invention will be described in detail below 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: The polymer obtained was dissolved in dichloromethane and the molecular weight was calibrated with polystyrene standards at room temperature using Shodexk-805,804,803,802.5 as column. Glass transition temperature: Measured with a polymer powder in Shimadzu DSC-50 at a temperature rising rate of 16 ° C./min in nitrogen. Example 1 50ml flask equipped with a magnetic stirrer 8-methyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene 2.0 g (11.5 mmol) and tetrahydrofuran 28. Add 5 ml, and further 7 ml of tetrahydrofuran
Dissolved in. Mo (N-2,6-C ₆ H ₃ Pr ⁱ ₂ ) (CHCMe ₂ Ph) (OB
u ^t) were reacted for 2 hours ₂ 63 mg of (0.115 mmol) was added at room temperature. Then benzaldehyde 60mg
(0.566 mmol) was added and stirred for 30 minutes to quench the living reaction. This polymerization liquid is added to a large amount of methanol to precipitate a ring-opening polymer, and after separation by filtration,
The polymer was washed with methanol and dried to obtain a white powdery ring-opening polymer. The yield of the ring-opening polymer obtained as described above was 99.8%, the weight average molecular weight Mw measured by GPC was 19,300, and the number average molecular weight Mn was 18,
It was 200 and Mw / Mn was 1.06. Also D
The glass transition temperature measured by SC was 205 ° C.

Example 2 Mo (N-2,6-C ₆ H ₃ Pr ⁱ ₂ ) (CHCMe ₂ Ph) (OBu ^t ) ₂ as a catalyst
The living ring-opening was performed in the same manner as in Example 1 except that Mo (N-2,6-C ₆ H ₃ Pr ⁱ ₂ ) (CHBu ^t ) (OCMe ₂ CF ₃ ) ₂ ) ₂ ) was used instead. Polymerization was carried out to obtain a white powdery ring-opening polymer. The yield of the ring-opening polymer obtained as described above was 99%.
The weight average molecular weight Mw measured by C was 18,800, the number average molecular weight Mn was 16200, and Mw / Mn was 1.16.
Met. The glass transition temperature measured by DSC is 27.
It was 5 ° C.

Example 3 8-Methyltetracyclo [4.4.0.1 ^2,5 .
1 ^7,10] -3-dodecene in place with 8-cyano-tetracyclo [4.4.0.1 ^{2, 5.} Living ring-opening polymerization was carried out in the same manner as in Example 1 except that 1 ^7,10 ] -3-dodecene was used to obtain a white powdery ring-opening polymer. The yield of the ring-opening polymer obtained as described above was 99%.
The weight average molecular weight Mw measured by 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
It was 2 ° C.

Example 4 Mo (N-2,6-C ₆ H ₃ Pr ⁱ ₂ ) (CHCMe ₂ Ph) (OBu ^t ) ₂ as a catalyst
Living ring-opening polymerization was conducted in the same manner as in Example 3 except that Mo (N-2,6-C ₆ H ₃ Pr ⁱ ₂ ) (CHBu ^t ) (OCMe ₂ CF ₃ ) ₂ ) was used instead. Conducted to obtain a white powdery ring-opening polymer. The yield of the ring-opening polymer obtained as described above was 98%.
The weight average molecular weight Mw measured in 1. was 51300, the number average molecular weight Mn was 42400, and Mw / Mn was 1.21. The glass transition temperature measured by DSC is 280.
It was ℃.

Comparative Example 1 A 30 ml flask equipped with a magnetic stirrer was charged with bicyclo.
[2.2.1] Hept-2-ene 0.42 g (4.55
mmol) and 7 ml of tetrahydrofuran, and further dissolved in 7 ml of tetrahydrofuran Mo (N-2,6-C ₆ H ₃ Pr
^{_{i 2) (CHCMe 2 Ph)}} (OBu t) 25mg (0.0455mm
was added and reacted at room temperature for 1 hour. Then, add 25 mg (0.234 mmol) of benzaldehyde to 30
Stir for a minute to quench the living reaction. This polymerization solution was added to a large amount of methanol to precipitate a ring-opened polymer, which was separated by filtration, washed with methanol and dried to obtain a white powdery ring-opened polymer. The yield of the ring-opening polymer obtained as described above was 99.9%, the weight average molecular weight Mw measured by GPC was 9780, the number average molecular weight Mn was 10760, and Mw / Mn was 1. Although it was as narrow as 01, the glass transition temperature measured by DSC was as low as 38 ° C.

[0023] Comparative Example 2 magnetic stirrer, a 100ml flask equipped with a condenser 8-methyl tetracyclo [4.4.0.1 ^{2, 5} .1
^7,10 ] -3-Dodecene 6.12 g (0.0351mo
1), 50 mol of 1,2-dichloroethane, 0.1 ml of a 0.25M toluene solution of a W-based catalyst prepared from tungsten hexachloride and acetal, and 0.1 ml of a 2.4M toluene solution of diethylaluminum chloride as a cocatalyst.
ml, 0.059 g of 1-hexene as a molecular weight regulator
(0.702 mmol) 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-opening polymer, which was separated by filtration, washed with methanol and dried to obtain a white powdery ring-opening polymer. The yield of the ring-opening polymer obtained as described above was as low as 32%, and the weight average molecular weight Mw measured by GPC was 2450.
0, the number average molecular weight Mn was 6980, and the Mw / Mn was 3.51 with a wide molecular weight distribution.

[0024]

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

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Masanori Asanuma 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemical Co., Ltd.

Claims (3)

[Claims] 1. A glass transition temperature represented by the general formula (1) [Chemical formula 1] is 150 ° C. or higher, and a ratio (Mw / M) of the weight average molecular weight Mw and the number average molecular weight Mn measured by GPC.
A tetracyclododecene polymer in which n) is 1.0 to 1.8. [Chemical 1] (In the formula, R _{1 to} R ₄ may be the same or different and each is hydrogen, a hydrocarbon group having 1 to 12 carbon atoms, a halogen group, or a hydrocarbon group having 1 to 12 carbon atoms substituted with a halogen atom. Represents a group, a nitrile group, a carboxyl group, a methylcarboxyl group, x represents an integer of 1 to 3, and n represents an integer larger than 1.) 2. A general formula (1) [wherein at least one tetracyclododecene-based monomer represented by the general formula (2) [Chemical formula 2] is polymerized with a living ring-opening metathesis catalyst. The glass transition temperature represented by the formula 3] is 150 ° C. or higher, and the ratio (Mw / Mn) of the weight average molecular weight Mw and the number average molecular weight Mn measured by GPC is 1.0 to 1.8.
Which is a tetracyclododecene polymer. [Chemical 2] (In the formula, R _{1 to} R ₄ may be the same or different and each is hydrogen, a hydrocarbon group, a halogen group, a hydrocarbon group having 1 to 12 carbon atoms substituted with a halogen atom, a nitrile group, or a carboxyl group. Represents a group, 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 is hydrogen, a hydrocarbon group having 1 to 12 carbon atoms, a halogen group, or a hydrocarbon group having 1 to 12 carbon atoms substituted with a halogen atom. Represents a group, a nitrile group, a carboxyl group, a methylcarboxyl group, x represents an integer of 1 to 3, and n represents an integer larger than 1.) 3. The living ring-opening metathesis catalyst is at least one selected from a tungsten-based alkylidene catalyst, a molybdenum-based alkylidene catalyst, a rhenium-based alkylidene catalyst, a tantalum-based alkylidene catalyst, a ruthenium-based alkylidene catalyst and titanacyclobutanes. Item 4. A method for producing a tetracyclododecene polymer according to Item 2.