JP3234699B2 - Tetracyclododecene polymer and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel tetracyclododecene polymer and a method for producing the same. More specifically, the present invention 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 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 of ring-opening polymerization of a norbornene-based monomer with a catalyst having these alkylidene complexes, and has conducted detailed studies on the stereochemistry of the polymer. However, these polymers have a low glass transition temperature and are not industrially sufficient as heat-resistant polymers.

[0004]

SUMMARY OF THE INVENTION The present invention relates to a tetracyclododecene-based polymer which can solve at least some of the above-mentioned disadvantages 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 solved the above-mentioned problems and have intensively studied a tetracyclododecene-based polymer having a high glass transition temperature and a narrow molecular weight distribution, and a method for producing the same. The present invention has been completed. That is, in the present invention, the glass transition temperature represented by the general formula (1) is 150 ° C. or higher, and the ratio of the weight average molecular weight Mw to the number average molecular weight Mn measured by GPC (Mw / Mn). Is 1.
0-1.8 is a tetracyclododecene-based polymer.

[0006]

Embedded image (Wherein, R _{1 to} R ₄ may be the same or different, and each represents 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. A group, 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.) The present invention also provides a compound represented by the general formula (2):
A glass transition temperature represented by the general formula (1), wherein at least one kind of tetracyclododecene-based monomer represented by the following formula is polymerized with a living ring-opening metathesis catalyst. Is 150 ° 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.

[0007]

Embedded image (Wherein, R _{1 to} R ₄ may be the same or different, and each represents 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, or a methylcarboxyl group, and x represents an integer of 1 to 3.)

[0008]

Embedded image (Wherein, R _{1 to} R ₄ may be the same or different, and each represents 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, or a methylcarboxyl group, and x represents an integer of 1 to 3, and n represents an integer greater than 1.)

Specific examples of the tetracyclododecene-based monomer represented by formula (2) in the present invention include: x
Is 1, a hexacycloheptacene and a derivative thereof where x is 2, an octacyclodcocene and a derivative thereof where x is 3. Among these derivatives, R _{1 to} R _{4 each} have 1 carbon atom.
Derivatives such as alkyl substitution of 12 to 12, aryl substitution, aralkyl substitution, etc., halogen substitution wherein R _{1 to} R ₄ are chlorine, bromine, iodine, etc., alkyl substitution including halogen such as chloromethyl, bromomethyl, nitrile substitution, carboxyl substitution,
Derivatives such as methylcarboxy substitution,

[0010]

Embedded image (Wherein, R _{1 to} R ₄ may be the same or different, and each represents 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, or a methylcarboxyl group, and x represents an integer of 1 to 3, and n represents an integer greater 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.
^12.5 . 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 can be used 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 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.

[0013] 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. 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. ) Tungsten-based, such as alkylidene catalyst, 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 A butyl group,
Me represents a methyl group, and Ph represents a phenyl group. ), Molybdenum-based alkylidene catalysts such as 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
Rhenium-based alkylidene catalysts such as (CBu ^t ) (CHBu ^t ) (2,6-dimethylphenoxide), (where But represents a ^t -butyl group), 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- diisopropyl phenoxide) _3, (Me represents a methyl group in the formula, Ph represents a phenyl group.) Tantalum-based such as alkylidene catalyst, Ru (CHCHCPh ₂₎ (PPh ₃ ) Ruthenium-based alkylidene catalysts such as Cl ₂ and (where 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. 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, These may be used alone or in combination of two or more.

The glass transition temperature of the tetracyclododecene polymer obtained in the present invention is 150.degree.
The above is preferred. When the glass transition temperature is less than 150, it is insufficient as a heat-resistant polymer. Further, the ratio (Mw / Mn) of the weight average molecular weight Mw and the number average molecular weight Mn in terms of polystyrene measured by GPC of the tetracyclododecene polymer obtained in the present invention 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 preferred because they are not uniform with the polymer.

The production of the tetracyclododecene polymer of the present invention is carried out by dissolving the above tetracyclododecene polymer and a living ring-opening metathesis catalyst in a solvent. The reaction temperature is usually from 0 to 150 ° C, and from 10 to 100 ° C.
Is preferred. The reaction time is usually 1 minute to 10 hours, and the living polymer is converted to aldehydes, ketones,
The reaction can be stopped by substituting the generated terminal with a quenching agent such as an alcohol. Generally, the concentration of the raw material monomer / catalyst and the solvent is selected in the range of 0.1 to 100 mol / l. Done.

[0018]

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: The obtained polymer was dissolved in dichloromethane, and the molecular weight was calibrated by a polystyrene standard at room temperature using Shodexk-805, 804, 803, 802.5 as a column. Glass transition temperature: measured using a polymer powder at a heating rate of 16 ° C./min in nitrogen by Shimadzu DSC-50. 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, then add 7 ml of tetrahydrofuran
Was dissolved. Mo (N-2,6-C ₆ H ₃ Pr ⁱ ₂ ) (CHCMe ₂ Ph) (OB
63 mg (0.115 mmol) of u ^t ) ₂ were added and reacted at room temperature for 2 hours. Then benzaldehyde 60mg
(0.566 mmol) was added and stirred for 30 minutes to extinguish 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 and further separated.
The polymer was 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 is 19300, and the number average molecular weight Mn is 18
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
Instead except for using _{Mo (N-2,6-C 6} H 3 Pr i 2) (CHBu t) (OCMe 2 CF 3) 2) 2) , a living ring-opening in the same manner as in Example 1 to Polymerization was performed to obtain a white powdery ring-opened polymer. The yield of the ring-opened polymer obtained as described above is 99%,
The weight average molecular weight Mw measured in C was 18,800, the number average molecular weight Mn was 16,200, and Mw / Mn was 1.16.
Met. The glass transition temperature measured by DSC is 27.
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 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.

Example 4 Mo (N-2,6-C ₆ H ₃ Pr ⁱ ₂ ) (CHCMe ₂ Ph) (OBu ^t ) ₂ as a catalyst
The place except for using _{Mo (N-2,6-C 6} H 3 Pr i 2) (CHBu t) (OCMe 2 CF 3) 2) , a living ring-opening polymerization in the same manner as in Example 3 to As a result, a ring-opened polymer in the form of a white powder was obtained. The yield of the ring-opened polymer obtained as described above is 98% and GPC
The weight average molecular weight Mw measured in the above 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.
° C.

Comparative Example 1 Bicyclo was placed in a 30 ml flask equipped with a magnetic stirrer.
[2.2.1] 0.42 g of hept-2-ene (4.55)
mmol) and 7 ml of tetrahydrofuran, and Mo (N-2,6-C ₆ H ₃ Pr) dissolved in 7 ml of tetrahydrofuran.
ⁱ ₂ ) (CHCMe ₂ Ph) (OBu ^t ) 25 mg (0.0455 mm
ol) and reacted at room temperature for 1 hour. Thereafter, 25 mg (0.234 mmol) of benzaldehyde was added, and 30
The mixture was stirred for minutes and the living reaction was extinguished. This polymerization 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 was 99.9%, the weight average molecular weight Mw measured by GPC was 9,780, the number average molecular weight Mn was 10,760, and Mw / Mn was 1. However, 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 (0.0351 mol
l), 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, and 0.1 ml of a 2.4 M toluene solution of diethylaluminum chloride as a co-catalyst.
ml, 1-hexene 0.059 g as molecular weight regulator
(0.702 mmol) was added and reacted at 60 ° C. for 2 hours. This polymer solution was added to a large amount of methanol to precipitate a ring-opened polymer. After filtration and separation, the polymer was 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 as low as 32%, and the weight average molecular weight Mw measured by GPC is 2450.
0, the number average molecular weight Mn was 6,980, and Mw / Mn was 3.51 with a wide molecular weight distribution.

[0024]

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 can be expected as a heat-resistant polymer.
In addition, the method for producing a tetracyclododecene-based polymer of the present invention can provide a heat-resistant polymer efficiently 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 (3)

(57) [Claims] A glass transition temperature represented by the general formula (1) [Chemical Formula 1] is 150 ° C. or more, and a ratio (Mw / M) of a weight average molecular weight Mw to a number average molecular weight Mn measured by GPC.
n) is a tetracyclododecene-based polymer having a value of 1.0 to 1.8. Embedded image (Wherein, R _{1 to} R ₄ may be the same or different, and each represents 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, or a methylcarboxyl group, and x represents an integer of 1 to 3, and n represents an integer greater than 1.) 2. A method according to claim 1, wherein at least one tetracyclododecene monomer represented by the general formula (2) is polymerized with a living ring-opening metathesis catalyst. And the ratio (Mw / Mn) of the weight average molecular weight Mw to the number average molecular weight Mn measured by GPC is from 1.0 to 1.8.
A method for producing a tetracyclododecene polymer. Embedded image (Wherein, R _{1 to} R ₄ may be the same or different, and may be hydrogen, a hydrocarbon group, a halogen group, a hydrocarbon group having 1 to 12 carbon atoms substituted with a halogen atom, a nitrile group, a carboxyl group, And x represents an integer of 1 to 3.) (Wherein, R _{1 to} R ₄ may be the same or different, and each represents 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, or a methylcarboxyl group, and x represents an integer of 1 to 3, and n represents an integer greater 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. The method for producing a tetracyclododecene-based polymer according to Item 2.