JP2001278959A - Polymerization method for cyclic monomer having two or more aliphatic unsaturated bonds and its polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymerization method which polymerizes a cyclic monomer having two or more aliphatic unsaturated bonds in the molecular by using Fischer carbene complex, which has been considered that there has been no catalytic activity up to now and to provide its polymer. SOLUTION: The polymerization method of the cyclic monomer having two or more aliphatic unsaturated bonds is applied by Fischer carbene complex as a metathesis polymerization catalyst, further more this polymerization is carried out by the monomer having a metathesis reactive unsaturated bond and the polymer obtained by the above polymerization process.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polymerization method using a Fischer-type carbene complex as a metathesis polymerization catalyst, and a polymer thereof.

[0002]

2. Description of the Related Art Among carbene complexes having a metal-carbon multiple bond, an alkylidene complex represented by a Shrock type complex or a Grubbs type complex is widely known as a good polymerization catalyst for metathesis polymerization. ing. However, the alkylidene complex is
Due to its high activity, there is a problem that it is difficult to control the reaction selectivity and the molecular weight in the polymerization reaction. on the other hand,
In a carbene complex having a metal-carbon multiple bond,
Fischer having a hetero substituent on the α-carbon (Fis
The cher) -type carbene complex was considered to be a complex formed when the catalyst was deactivated in the metathesis polymerization reaction and had no catalytic activity. (Macromolecule
es, 1995, 28, 6311).

[0003]

DISCLOSURE OF THE INVENTION In view of the above, the present invention provides a cyclic monomer having two or more aliphatic unsaturated bonds in a molecule using a Fischer-type carbene complex which has been considered to have no catalytic activity. To provide a method and a polymer for polymerizing

[0004]

The present invention is a method for polymerizing a cyclic monomer having two or more aliphatic unsaturated bonds, which comprises using a Fischer-type carbene complex as a metathesis polymerization catalyst. Hereinafter, the present invention will be described in detail.

[0005] Examples of the cyclic monomer having two or more aliphatic unsaturated bonds in the present invention include a norbornene-based monomer and cyclohexadiene. Among the above monomers, it is particularly preferable to use a norbornene-based monomer.

As the norbornene-based monomer, a polycyclic norbornene-based monomer having two or more rings is preferred. By using a polycyclic compound having two or more rings, a polymer having a high heat distortion temperature can be obtained.

The bicyclic norbornene-based monomer is not particularly limited, and examples thereof include 2-norbornene and 5-norbornene.
Examples thereof include methyl-2-norbornene, 5-ethylidene-2-norbornene, and 5-phenylnorbornene.

The above-mentioned tricyclic or higher norbornene-based monomer is not particularly restricted but includes, for example, tricyclics such as dicyclopentadiene (hereinafter referred to as DCPD), dihydrodicyclopentadiene and cyclohexenylnorbornene, and tetracyclododecene. And pentacyclics such as tricyclopentadiene, heptacyclics such as tetracyclopentadiene, and alkyl-substituted, alkylidene-substituted and aryl-substituted polycyclics thereof. Examples of the polycyclic alkyl substituent include methyl, ethyl, propyl, and butyl substituents. Examples of the polycyclic alkylidene-substituted product include an ethylidene-substituted product. Examples of the polycyclic aryl substituent include phenyl, tolyl, and naphthyl substituents. Of these, tricyclic or pentacyclic norbornene-based monomers are preferred from the viewpoints of availability, reactivity, heat resistance, and the like. Norbornene monomers having three or more rings can also be obtained by heat-treating DCPD.

The polycyclic norbornene monomer does not necessarily have to have an unsaturated bond in the ring, and a monomer substituted with a vinyl group, an allyl group, or the like may be used. Examples of such a monomer include, for example, 5-
And vinyl-2-norbornene.

The above-mentioned norbornene monomers may be used alone or in combination of two or more.

The polymerization of the cyclic monomer having two or more aliphatic unsaturated bonds of the present invention is preferably carried out in the presence of a monomer having a metathesis-reactive unsaturated bond.

The monomer having a metathesis-reactive unsaturated bond in the present invention is not particularly limited as long as it can efficiently control crosslinking and molecular weight.
Preference is given to dodecene, allyl acetate, vinyl acetate, and compounds having in the molecule at least one selected from the group consisting of aromatic rings, sulfur atoms, oxygen atoms, nitrogen atoms and selenium atoms. More preferred are compounds having a sulfur atom in the molecule.

The above-mentioned monomers having a metathesis-reactive unsaturated bond and having an aromatic ring in the molecule include styrene, 1,4-divinylbenzene and the like adjacent to a carbon atom forming an unsaturated bond. Those having an aromatic ring bonded to a carbon atom are preferred. The presence of a structure having a large steric hindrance can efficiently control crosslinking of a cyclic monomer having two or more aliphatic unsaturated bonds.

The above-mentioned monomer having a metathesis-reactive unsaturated bond and having at least one selected from a sulfur atom, an oxygen atom, and a selenium atom in the molecule is a compound represented by the following general formula (1): It is preferably at least one compound selected from the group consisting of the compounds represented by (10).

[0015]

Embedded image ^{Wherein, Y 1, Y 2, Y} 3 and Y ⁴ are the same or different and each represents a sulfur atom, an oxygen atom and a selenium atom, R ^1,
R ² , R ³ and R ⁴ are the same or different and are each a hydrogen atom,
An alkenyl group having 2 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, 1 to 10 carbon atoms
An alkoxyl group, a carboxyl group having 2 to 10 carbon atoms,
An alkenyloxy group having 2 to 10 carbon atoms, 6 to 10 carbon atoms
Represents an aryloxy group, an alkoxycarbonyl group having 2 to 10 carbon atoms, or an alkylthio group, acetyl group, or thioacetyl group having 1 to 10 carbon atoms.

Of these, allyl acetate, vinyl acetate, phenyl vinyl sulfide, benzyl vinyl sulfide, phenyl vinyl selenide, and ethyl vinyl ether are more preferred in view of cost and reactivity. More preferred are phenyl vinyl sulfide, benzyl vinyl sulfide and allyl acetate, and still more preferred are phenyl vinyl sulfide and benzyl vinyl sulfide.

The monomer having a metathesis-reactive unsaturated bond and having a nitrogen atom in the molecule is selected from the group consisting of compounds represented by the following general formulas (11) to (20). It is preferably at least one compound.

[0018]

Embedded image

Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R
⁶ , R ⁷ and R ⁸ are the same or different and are a hydrogen atom, an alkenyl group having 2 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, Alkoxyl group, carboxyl group having 2 to 10 carbon atoms, alkenyloxy group having 2 to 10 carbon atoms, aryloxy group having 6 to 10 carbon atoms, alkoxycarbonyl group having 2 to 10 carbon atoms, or 1 to 10 carbon atoms Represents an alkylthio group, an acetyl group, or a thioacetyl group. Incidentally, R ⁿ and R ^{n + 1} directly bonded to the nitrogen atom may be integrated to represent a heterocyclic ring together with the N atom to which they are bonded.

It is preferable to use a Fischer-type carbene complex as the metathesis polymerization catalyst in the present invention. The Fischer-type carbene complex referred to here is a metal-
In a metal complex having a carbon multiple bond, a complex in which a heteroatom substituent is bonded to the carbon is meant.

The above-mentioned metathesis polymerization catalyst is preferably a stable catalyst in terms of the polymerization activation process. For example, tungsten, molybdenum, tantalum, ruthenium, rhenium, osmium, titanium, zirconium, vanadium, niobium, chromium, technitium, Examples include halides such as cobalt, oxyhalides, oxides, and organic ammonium salts. Further, the polymerization catalyst,
Depending on the metal used, a Fischer-type carbene complex may be generated in the reaction system.

Among the above metathesis polymerization catalysts, when it is necessary to carry out the polymerization in the air due to the process, the stable catalysts are represented by the following general formulas (21), (22) and (2).
Ruthenium carbene catalysts represented by 3) and (24) are preferred.

[0023]

Embedded image

(Wherein R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are the same or different and each represent a hydrogen atom, an alkenyl group having 2 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms, 20 aryl groups, carboxyl group having 2 to 20 carbon atoms, alkoxy group having 2 to 20 carbon atoms, alkenyloxy group having 2 to 20 carbon atoms, aryloxy group having 6 to 20 carbon atoms, alkoxy having 2 to 20 carbon atoms Represents a carbonyl group, an alkylthio group having 2 to 20 carbon atoms, or a ferrocene derivative, which is required by a phenyl group substituted by an alkyl group having 1 to 5 carbon atoms, a halogen atom, or an alkoxy group having 1 to 5 carbon atoms. Or R ⁹ and R ¹⁰ , R ^{11 in} general formulas (23) and (24).
And R ¹² together may represent a heterocyclic ring together with the N atom to which they are attached. X ¹ and X ² are the same or different and each represents an anionic ligand, Y ¹ and Y
² is the same or different and represents a sulfur atom or an oxygen atom,
L ¹ and L ² are the same or different and represent a neutral electron donor, and two or three of X ¹ , X ² , L ¹ and L ² together represent a multidentate chelating ligand May be formed. )

Among them, a more preferred structure of the metathesis polymerization catalyst is that, in the formulas (21) and (22), R ⁹ and R ¹⁰ are the same or different.
Represents a hydrogen atom, a methyl group, an ethyl group, a phenyl group, a ferrocenyl group, or a vinyl group optionally substituted by a methyl group, an ethyl group, a phenyl group or a ferrocenyl group, and X ¹ and X ² are the same or Differently, represents a chlorine atom, a bromine atom, Y ¹ and Y ² represent a sulfur atom, and L ¹ and L ² are the same or different and are trimethylphosphine, triethylphosphine, triphenylphosphine or tricyclohexyl. It is a ruthenium carbene complex that represents phosphine.

The amount of the metathesis polymerization catalyst varies depending on the activity of the catalyst.
/ 500,000 molar equivalents. If it exceeds 1/5 molar equivalent, the molecular weight of the obtained polymer does not increase, and
If it is less than / 500,000 molar equivalents, the polymerization rate decreases. More preferably, it is 1/30 to 1/200000 molar equivalent.

In the polymerization of the cyclic monomer having two or more aliphatic unsaturated bonds according to the present invention, a liquid component which does not participate in the metathesis polymerization reaction may be contained. The amount of the liquid component added during the above polymerization is not particularly limited, and is preferably 20% by weight or less of all the charged components. If it exceeds 20% by weight, a step of removing the solvent after the polymerization is required, which is not industrially preferable. In consideration of the polymer yield and processability, the content is preferably 10% by weight or less, more preferably 5% by weight or less. In this specification,
The expression "not involved in the polymerization reaction" means that the resin does not directly participate in the polymerization reaction as a reactant and does not participate in the promotion or suppression of the reaction. Further, in the present specification, the liquid component is a component that is liquid at a temperature of 60 ° C. or lower. Examples of the liquid that does not participate in the metathesis polymerization reaction include a reaction solvent and the like.
The reaction solvent is not particularly limited and includes, for example, toluene, xylene and the like.

In the polymerization of the cyclic monomer having two or more aliphatic unsaturated bonds according to the present invention, the temperature at which the monomer is polymerized is preferably from -30 to 150 ° C.
When the temperature is lower than −30 ° C., the reactivity of the monomer is low, and the polymerization hardly proceeds. If it exceeds 150 ° C., the metathesis polymerization catalyst may decompose. More preferably, 0-10
0 ° C. Further, in order to efficiently polymerize the monomer, it is preferable to suppress the heat generation during the polymerization. However, the heat generation during the polymerization can be suppressed by lowering the polymerization temperature as the polymerization proceeds.

The polymerization of the cyclic monomer having two or more aliphatic unsaturated bonds according to the present invention is preferably carried out in an inert gas atmosphere. However, a stable catalyst such as the aforementioned ruthenium carbene complex or ruthenium vilinidene complex may be used. In the case where is used, the polymerization can be carried out in the air.

Further, since the metathesis polymerization is an equilibrium reaction, there is usually a residual monomer after the polymerization, which limits the use of the molded product. However, the cyclic monomer having two or more aliphatic unsaturated bonds according to the present invention is used. In the polymerization of monomers, residual monomer components can be removed from the produced polymer. As a method for removing the residual monomer component, a method in which the produced polymer is dissolved in a good solvent and then removed by adding a poor solvent and reprecipitating and purifying, and the produced polymer is removed by drying under reduced pressure Method and the like. In order to remove residual monomers efficiently by drying under reduced pressure, it is preferable to heat at a temperature within a range where the produced polymer is not decomposed. The above temperature is preferably 30 to
120 ° C. When removing residual monomers by drying under reduced pressure, an inert solvent in which the polymer is soluble can be added to reduce the viscosity of the polymer.

The polymer produced by the method for polymerizing a cyclic monomer having two or more aliphatic unsaturated bonds according to the present invention and a molded article using the same are an antioxidant, a filler, a reinforcing material, a foaming agent and a pigment. By blending various additives such as a colorant, an elastomer, and a DCPD-based thermopolymerized resin, the properties can be improved.

The filler is not particularly restricted but includes, for example, inorganic fillers such as glass, carbon black, talc, calcium carbonate, mica and clay such as montmorillonite. The reinforcing agent is not particularly limited,
For example, fibrous fillers such as glass fiber, carbon fiber, and organic fiber can be used.

The elastomer is not particularly restricted but includes, for example, natural rubber, polybutadiene, polyisoprene, styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, EPDM, ethylene-vinyl acetate copolymer And hydrides thereof.

The method for polymerizing a cyclic monomer having two or more aliphatic unsaturated bonds according to the present invention has the above-mentioned constitution, and therefore has excellent adhesiveness, heat resistance and chemical resistance, and almost no residual monomer. The polymer which does not exist can be obtained in high yield.

A polymer produced by the method for polymerizing a cyclic monomer having two or more aliphatic unsaturated bonds according to the present invention is also one of the present invention.

The number average molecular weight of the polymer in the present invention is preferably from 600 to 30,000. When the number average molecular weight is less than 600, the impact resistance and heat resistance of the polymer may be insufficient. If it exceeds 30,000, the polymer has low fluidity in a molten state, which is not preferable in the process. It is more preferably 800 to 20,000, and still more preferably 900
To 15,000, particularly preferably 1,000 to 10,000.

The gel fraction of the polymer in the present invention is 20
It is preferable that the content be not more than weight%. If the content exceeds 20% by weight, the flowability of the polymer in the molten state is low, which is not preferable in the process. It is more preferably at most 10% by weight, further preferably at most 8% by weight.

Since the polymer of the present invention has the above-mentioned properties, a molded article produced using the polymer has adhesiveness,
Electric and electronic parts, bathtubs, etc. that require heat resistance, chemical resistance, etc.
It is suitably used for various purposes such as a combined septic tank.

[0039]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Example 1 3.1 mg of a Fischer-type ruthenium catalyst represented by the following structural formula (25) (DCPD
1 / 100,000 molar equivalent), benzyl vinyl sulfide 2
g was dissolved in 50 g of DCPD. After stirring at room temperature for 2 hours, the residue was dried at 50 ° C. under reduced pressure to remove residual monomers.
The obtained polymer weighed 46 g and had no monomer odor. The obtained polymer was immersed in xylene at 100 ° C.
After 4 hours, the mixture was filtered through 200 mesh, and the gel fraction was measured by measuring the dry weight of the solid content remaining on the mesh. The gel fraction was 8% by weight. When the number average molecular weight of the obtained polymer was measured by GPC, the number average molecular weight was 8,000 in terms of standard polystyrene.

[0041]

Embedded image

Example 2 3.1 mg of a Fischer-type ruthenium catalyst represented by the above structural formula (25) (DCPD
1 / 100,000 molar equivalent), phenylvinyl sulfide 2
g was dissolved in 50 g of DCPD. After stirring at room temperature for 2 hours, the residue was dried at 50 ° C. under reduced pressure to remove residual monomers.
The amount of the obtained polymer was 44 g, and there was no monomer odor. The obtained polymer was immersed in xylene at 100 ° C.
After 4 hours, the mixture was filtered through 200 mesh, and the gel fraction was measured by measuring the dry weight of the solid remaining on the mesh. The gel fraction was 12% by weight. By GPC,
When the number average molecular weight of the obtained polymer was measured, the number average molecular weight was 900 in terms of standard polystyrene.

The norbornene-based polymers obtained in Examples 1 and 2 have almost no residual monomers, have a number average molecular weight of 600 to 30,000 and a gel fraction of 20% by weight or less. It was excellent in post-crosslinkability while being melt-moldable.

Comparative Example 1 Benzyl vinyl sulfide 2
g was dissolved in 50 g of DCPD. Next, to this solution, 3.1 mg (1 / 100,000 molar equivalent of DCPD) of a shrock-type ruthenium catalyst represented by the following structural formula (26) was added, and a reaction was attempted at room temperature. . The obtained polymer was immersed in xylene at 100 ° C., filtered after 24 hours with 200 mesh, and the dry weight of the solid content remaining on the mesh was measured to determine the gel fraction. The gel fraction was 99% by weight and had lost thermoplasticity.

[0045]

Embedded image

[0046]

The method for polymerizing a cyclic monomer having two or more aliphatic unsaturated bonds according to the present invention has the above-mentioned structure, and therefore, the Fischer-type carbene complex, which has been considered to have no catalytic activity, can be converted into an intramolecular molecule. It has been found that the compound exhibits catalytic activity for cyclic monomers having two or more aliphatic unsaturated bonds. Further, by the polymerization method of the present invention, it is possible to produce a polymer having excellent heat resistance, mechanical strength, and the like and having no residual monomer. Therefore, the polymer of the present invention can be suitably used in fields where adhesiveness, chemical resistance and the like are required.

Claims (10)

[Claims] 1. A method for polymerizing a cyclic monomer having two or more aliphatic unsaturated bonds, wherein a Fischer-type carbene complex is used as a metathesis polymerization catalyst. 2. The polymerization method according to claim 1, wherein the polymerization of the cyclic monomer having two or more aliphatic unsaturated bonds is carried out in the presence of a monomer having a metathesis-reactive unsaturated bond. 3. The polymerization method according to claim 1, wherein the monomer having a metathesis-reactive unsaturated bond is a compound having an aromatic ring in the molecule. 4. The monomer having a metathesis-reactive unsaturated bond is a compound having at least one selected from a sulfur atom, an oxygen atom, a nitrogen atom, and a selenium atom in a molecule. 3. The polymerization method according to any one of 3. 5. The compound having at least one selected from the group consisting of a sulfur atom, an oxygen atom and a selenium atom in a molecule is at least one selected from the group consisting of compounds represented by the following general formulas (1) to (10). The polymerization method according to claim 4, wherein the polymerization method is a single compound. Embedded image ^{Wherein, Y 1, Y 2, Y} 3 and Y ⁴ are the same or different and each represents a sulfur atom, an oxygen atom and a selenium atom, R ^1,
R ² , R ³ and R ⁴ are the same or different and are each a hydrogen atom,
An alkenyl group having 2 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, 1 to 10 carbon atoms
An alkoxyl group, a carboxyl group having 2 to 10 carbon atoms,
An alkenyloxy group having 2 to 10 carbon atoms, 6 to 10 carbon atoms
Represents an aryloxy group, an alkoxycarbonyl group having 2 to 10 carbon atoms, or an alkylthio group, acetyl group, or thioacetyl group having 1 to 10 carbon atoms. 6. The compound having a nitrogen atom in the molecule is at least one compound selected from the group consisting of compounds represented by the following general formulas (11) to (20). Item 6. The polymerization method according to Item 4. Embedded image In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are the same or different and each represent a hydrogen atom, a carbon number of 2 to 10.
An alkenyl group, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, a carboxyl group having 2 to 10 carbon atoms, and 2 to 10 carbon atoms
An alkenyloxy group, an aryloxy group having 6 to 10 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, or an alkylthio group, acetyl group, or thioacetyl group having 1 to 10 carbon atoms. 7. The Fischer-type carbene complex used for the metathesis polymerization catalyst is at least one selected from the group consisting of compounds represented by the following general formulas (21) to (24).
The polymerization method according to any one of claims 1 to 6, which is a kind of compound. Embedded image (Wherein, R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are the same or different and each represent a hydrogen atom, an alkenyl group having 2 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms, an aryl having 6 to 20 carbon atoms) Group,
Carboxyl group having 2 to 20 carbon atoms, alkoxy group having 2 to 20 carbon atoms, alkenyloxy group having 2 to 20 carbon atoms, aryloxy group having 6 to 20 carbon atoms, alkoxycarbonyl group having 2 to 20 carbon atoms, carbon number Represents an alkylthio group having 2 to 20 or a ferrocene derivative, which is optionally substituted by a phenyl group substituted by an alkyl group having 1 to 5 carbon atoms, a halogen atom, or an alkoxy group having 1 to 5 carbon atoms. Or the general formula (2
In 3) and (24), R ⁹ and R ¹⁰ and R ¹¹ and R ¹² together represent a heterocyclic ring together with the N atom to which they are bonded. X1 and X2 are the same or different and represent an anionic ligand; Y1 and Y2 are the same or different and represent a sulfur atom or an oxygen atom; and L1 and L2 are the same or different and have a neutral electron donor. Body, and X1, X2, L1
And two or three of L2 may together form a multidentate chelating ligand. ) 8. A polymer obtained by the polymerization method according to any one of claims 1 to 7. 9. The polymer according to claim 8, wherein the gel fraction is 20% by weight or less. 10. The polymer according to claim 8, wherein the number average molecular weight is from 600 to 30,000.