JP2001288255A - Cleavage method, polymer production method and polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for preferentially cleaving one of at least two aliphatically unsaturated bonds differing from each other in reactivity, a method for producing a polymer by using the method for cleavage as an elementary reaction, and a polymer produced thereby. SOLUTION: Provided is a method for preferentially cleaving one of at least two aliphatically unsaturated bonds present in the same molecule and different from each other in reactivity.

Description

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to a cleavage method for preferentially cleaving one or more kinds of aliphatic unsaturated bonds having different reactivities, a method for producing a polymer using the cleavage method as an elementary reaction, and a polymer. .

[0002]

2. Description of the Related Art When a polymer is produced from a compound having two or more kinds of aliphatic unsaturated bonds having different reactivities as monomers, two or more kinds of aliphatic unsaturated bonds are cleaved randomly to form an unsaturated compound. Upon re-formation of the bond, the resulting polymer becomes highly branched. Using a compound having two or more aliphatic unsaturated bonds having different reactivity as a monomer, one of the two or more aliphatic unsaturated bonds is selected in order to form a linear polymer. It is necessary to cleave it. However, up to now, selective cleavage of any aliphatic unsaturated bond in a compound having two or more aliphatic unsaturated bonds having different reactivities has not been achieved efficiently.

[0003] As a reaction for cleaving an aliphatic unsaturated bond, a metathesis reaction is known. However, a metathesis reaction using a carbene complex causes
There has been no report yet of a high probability of selectively cleaving any one or more aliphatic unsaturated bonds. Although there are some reports on polymerization using a metathesis reaction in a solution system or the like, linear polymerization using a compound having two or more kinds of aliphatic unsaturated bonds having different reactivities as a monomer. It has been difficult to efficiently form coalescence.

[0004]

SUMMARY OF THE INVENTION In view of the above circumstances, the present invention provides a cleavage method and a cleavage method for preferentially cleaving one of two or more aliphatic unsaturated bonds having different reactivities. An object of the present invention is to provide a method for producing a polymer used as a reaction and a polymer.

[0005]

SUMMARY OF THE INVENTION The present invention is a cleavage method for preferentially cleaving one or more aliphatic unsaturated bonds having different reactivities in the same molecule. Hereinafter, the present invention will be described in detail.

The compound having two or more kinds of aliphatic unsaturated bonds having different reactivities is not particularly limited, but is preferably a cyclic compound, more preferably a bicyclic compound,
It is a polycyclic norbornene compound having three or more rings.

As polycyclic norbornene compounds having two or more aliphatic unsaturated bonds having different reactivities, for example, dicyclopentadiene, tricyclopentadiene,
Examples include tetracyclopentadiene, cyclohexenylnorbornene, and derivatives thereof. Among them, dicyclopentadiene and its derivatives are preferably used because of their excellent selectivity for the cleavage reaction.

The above derivatives include, for example, alkyl-substituted, alkylidene-substituted and aryl-substituted products. Examples of the alkyl substituent include methyl,
Ethyl, propyl and butyl substituents are exemplified. Examples of the alkylidene-substituted product include an ethylidene-substituted product. Examples of the aryl substituent include phenyl, tolyl, and naphthyl substituents. Tricyclic or higher polycyclic norbornene compounds can also be obtained by heat-treating dicyclopentadiene.

The above-mentioned polycyclic norbornene compounds having two or more kinds of aliphatic unsaturated bonds having different reactivities do not necessarily have to have a double bond in the ring. A substituted norbornene-based compound may be used. As the substituted norbornene-based compound, for example, 5-vinyl-2-norbornene and the like are suitably used.

[0010] The cleavage method of the present invention is preferably performed by adding a carbene complex to the reaction system and performing a metathesis reaction. The metathesis reaction refers to a reaction in which an alkylidene group of an olefin is exchanged.

The above carbene complex means a complex having a structure of M = CRR '. M represents a metal atom. The carbene complex may be a low-valent complex containing a hetero atom (shroke type) or a complex not containing a hetero atom (Fischer type).

The metal atoms constituting the carbene complex are not particularly restricted but include, for example, ruthenium, titanium, molybdenum, tungsten, zirconium, vanadium,
Niobium, tantalum, chromium, technitium, rhenium,
Examples include cobalt, osmium, and iron. Among them, ruthenium, tungsten, titanium, zirconium, vanadium, niobium, tantalum, chromium, technitium, rhenium, cobalt, and osmium are preferable, and ruthenium is more preferable from the viewpoint of the stability of the complex. The carbene complex may be generated in a reaction system using a complex precursor.

The ruthenium carbene complex using ruthenium as a metal atom constituting the carbene complex includes a ruthenium alkylidene complex and a ruthenium vinylidene complex. Among them, the following general formula (1):
A Fischer-type ruthenium complex represented by (2), (2 ′) or (2 ″) is preferred.

[0014]

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In the formula, Y ¹ and Y ² are the same or different and represent a sulfur atom, an oxygen atom, or a selenium atom, and R ¹ and R ² are the same or different and are a hydrogen atom, a carbon atom having 2 to 20 carbon atoms.
Alkenyl group, an alkyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkyl group having 1 to 5 carbon atoms, a halogen atom, and a phenyl group substituted by an alkoxyl group having 1 to 5 carbon atoms. A carboxylate having 2 to 20 carbon atoms, an alkoxyl group having 2 to 20 carbon atoms, an alkenyloxy group having 2 to 20 carbon atoms, an aryloxy group, an alkoxycarbonyl having 2 to 20 carbon atoms which may be substituted according to A group, an alkylthio group having 2 to 20 carbon atoms, or a ferrocene derivative, wherein X ¹ and X ² are
The same or different and represents an anionic ligand; L ¹ and L ² represent the same or different and represent a neutral electron donor;
Two or three of ¹ , X ² , L ¹ and L ² may together form a polydentate chelating ligand.

[0016]

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In the formula, 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 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms, and a carbon atom having 6 to 20 carbon atoms. An aryl group, an alkyl group having 1 to 5 carbon atoms, a halogen atom,
A carboxylate having 2 to 20 carbon atoms, an alkoxyl group having 2 to 20 carbon atoms, an alkoxyl group having 2 to 20 carbon atoms, which may be optionally substituted by a phenyl group substituted by an alkoxyl group having 1 to 5 carbon atoms; Alkenyloxy group,
Represents an aryloxy group, an alkoxycarbonyl group having 2 to 20 carbon atoms, an alkylthio group having 2 to 20 carbon atoms, or a ferrocene derivative, or R ¹ and R ³ , R ² and R
⁴ together represent a heterocycle with the N atom to which they are attached. X ¹ and X ² are the same or different and represent an anionic ligand; L ¹ and L ² are the same or different and represent a neutral electron donor; X ¹ , X ² , L ¹ and L ^Two
Two or three of may form together a polydentate chelating ligand.

In the ruthenium carbene complex represented by the above general formula (1) or (2), Y ¹ and Y ² each represent a sulfur atom, and R ¹ and R ² are the same or different and are each a hydrogen atom, methyl 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; X ¹ and X ² are the same or different; , B
R is the same or different, and L ¹ and L ² are the same or different and are preferably ruthenium carbene complexes that represent trimethylphosphine, triethylphosphine, triisopropylphosphine, triphenylphosphine or tricyclohexylphosphine.

In the cleavage method of the present invention, when the metathesis reaction is performed using the carbene complex, the complex itself may be further used in an equivalent amount as a partner of the metathesis reaction, that is, the double bond exchange reaction.

In the cleavage method of the present invention, it is preferable to further add a compound having a metathesis-reactive unsaturated bond to the reaction system. When a compound having a metathesis-reactive unsaturated bond is added to the reaction system, this compound acts as a partner of the double bond exchange reaction.

The compound having a metathesis-reactive unsaturated bond is at least one selected from the group consisting of an aromatic ring, a sulfur element, an oxygen element, a selenium element and a nitrogen element in order to cleave the unsaturated bond with high selectivity. It is preferable to have one in the molecule. Examples of the compound having a metathesis-reactive unsaturated bond and having an aromatic ring in the molecule include styrene and 1,4-divinylbenzene.

The compounds having a metathesis-reactive unsaturated bond and having a sulfur element, an oxygen element, and a selenium element in the molecule include compounds represented by the following general formulas (3) to (1).
The compound represented by 2) is preferably used.

[0023]

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In the formula, Y ¹ , Y ² , Y ³ and Y ⁴ are the same or different and represent a sulfur atom, an oxygen atom or a selenium atom;
R ³ , R ⁴ , R ⁵ and R ⁶ 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, 1 to
10 alkoxyl groups, carboxyl group having 2 to 10 carbon atoms, alkenyloxy group having 2 to 10 carbon atoms, 6 to 1 carbon atoms
0 represents an aryloxy group, a C2 to C10 alkoxycarbonyl group, a C1 to C10 alkylthio group, an acetyl group, or a thioacetyl group. Of these, phenylvinyl sulfide, benzylvinyl sulfide, and allyl acetate are preferred from the viewpoint of cost and reactivity.

As the above-mentioned compound having a metathesis-reactive unsaturated bond and having a nitrogen element in the molecule, compounds represented by the following general formulas (13) to (22) are preferably used.

[0026]

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Wherein R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R
⁸ , R ⁹ and R ¹⁰ are the same or different and each 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,
Represents an alkylthio group, an acetyl group, or a thioacetyl group having 1 to 10 carbon atoms.

The cleavage method of the present invention may be any of a bulk reaction, a solvent reaction, a suspension reaction, and an emulsification reaction, but is preferably a bulk reaction. The bulk reaction refers to performing the reaction without solvent, but DCP
When a catalyst insoluble in a monomer such as D is used, a minimum amount of a solvent may be used to dissolve the catalyst. According to the bulk reaction, the reaction can proceed efficiently.

The above-mentioned bulk reaction is preferably carried out in an inert gas atmosphere, but may be carried out in the air when a stable catalyst such as the above-mentioned ruthenium carbene complex or ruthenium vilinidene complex is used.

Using the cleavage method of the present invention as an elementary reaction,
Polymers can also be produced. When a polymer is produced using the cleavage method of the present invention as an elementary reaction, a linear polymer can be obtained efficiently. The present invention also relates to a method for producing a polymer obtained by repeating an elementary reaction, wherein the elementary reaction is a method for producing a polymer comprising the cleavage method of the present invention. The monomer used in the method for producing a polymer of the present invention is not particularly limited as long as it has two or more aliphatic unsaturated bonds having different reactivities in the same molecule, and is a cyclic compound. May be a non-cyclic compound, but a cyclic compound having two or more aliphatic unsaturated bonds having different reactivities is preferable.

Examples of the cyclic compound having two or more types of aliphatic unsaturated bonds having different reactivities include polycyclic norbornene compounds having two or more rings and three or more rings. As the polycyclic norbornene-based compound having two or more kinds of aliphatic unsaturated bonds having different reactivities, the compound used in the above-described cleavage method of the present invention can be used.

These compounds having two or more kinds of aliphatic unsaturated bonds having different reactivities may be used alone or in combination.
More than one species may be used in combination. Further, in the method for producing a polymer of the present invention, a polymerizable compound other than a compound having two or more kinds of aliphatic unsaturated bonds having different reactivities as a monomer may be used in combination. In the method for producing the polymer of the present invention, it is not always necessary to repeat only the metathesis reaction as an elementary reaction, and may include another elementary reaction in some cases.

The process for producing the polymer of the present invention comprises a bulk reaction,
Any of a solvent reaction, a suspension reaction, and an emulsification reaction may be used.However, considering the gel effect of the produced polymer, the solvent reaction is preferred in that a polymer can be obtained with high yield. preferable.

The amount of the carbene complex used in the production method of the present invention depends on its activity, but is preferably 1/5 to 1 / 500,000 molar equivalents with respect to all monomers. If it exceeds 1/5 molar equivalent, the molecular weight of the obtained polymer will not increase, and if it is less than 1 / 500,000 molar equivalent, the polymerization rate will decrease. More preferably, it is 1/30 to 1/200000 molar equivalent.

In the production method of the present invention, the polymerization temperature is-
The temperature is preferably from 30 to 150 ° C. If the temperature is lower than −30 ° C., the reactivity of the monomer is low, and the polymerization hardly proceeds. When the polymerization temperature exceeds 150 ° C., the carbene complex may be decomposed. The temperature is more preferably 0 to 100 ° C. Also,
In order to efficiently polymerize a compound having two or more types of aliphatic unsaturated bonds having different reactivities, it is preferable to suppress the heat generation during the polymerization, but the polymerization temperature is lowered by lowering the polymerization temperature as the polymerization proceeds. Heat generation at the time can be suppressed.

The polymer produced by the method for producing a polymer of the present invention is also one of the present invention. The polymer of the present invention preferably has a gel fraction of 20% by weight or less. When the gel fraction is 20% by weight or less, it can be said that the obtained polymer is almost linear. If the gel fraction exceeds 20% by weight, the fluidity 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.

The polymer of the present invention has a number average molecular weight of 600
Preferably, it is ３30,000. When the number average molecular weight is less than 600, the ratio of the compound having a metathesis-reactive unsaturated bond in the obtained polymer becomes large, so that physical properties such as impact resistance and heat resistance originally expected become insufficient. Not preferred. If it exceeds 30,000, the obtained polymer has low fluidity in a molten state, which is not preferable in the process. It is more preferably from 800 to 20,000, further preferably from 900 to 15,000, particularly preferably from 1,000 to 20,000.
~ 10,000.

The polymer of the present invention comprises an antioxidant, a filler,
The properties of the polymer may be modified by blending various additives such as a reinforcing material, a foaming agent, a pigment, a colorant, an elastomer, and a dicyclopentadiene-based thermopolymer resin.

Examples of the filler include inorganic fillers such as glass, carbon black, talc, calcium carbonate, mica, and clay such as montmorillonite. Examples of the reinforcing material include fibrous fillers such as glass fiber, carbon fiber, and organic fiber.

Examples of the elastomer include natural rubber, polybutadiene, polyisoprene, styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, EPDM, ethylene-vinyl acetate copolymer and hydrogenated hydrogen thereof. And the like.

Since the polymer of the present invention has little branching and is excellent in adhesiveness, heat resistance, chemical resistance, etc., it is used for various applications such as electric and electronic parts, bathtubs, combined septic tanks and the like which require these properties. can do.

The monomer component remaining when synthesizing the polymer of the present invention is obtained by dissolving the produced polymer in a good solvent,
It can be removed by reprecipitation purification by adding a poor solvent. It can also be removed by drying under reduced pressure.
In order to remove residual monomers efficiently by drying under reduced pressure, it is preferable to heat the polymer within a range where the polymer is not decomposed. Preferably it is in the range of 30 to 120 ° C. In order to lower the polymer viscosity when removing the residual monomer by drying under reduced pressure, an inert solvent in which the polymer is dissolved may be added.

[0043]

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 1.0 mmol of the following ruthenium complex (1) (1/1000 equivalent of dicyclopentadiene) was added to a mixed solution of 1.0 mol of dicyclopentadiene and 1.0 mol of p-tolylvinyl sulfide. Was. After stirring at room temperature for 83 hours, the reaction solution was separated by a silica gel column, and then N 2
When analyzed by MR, as shown in the following formula (23), only the compound in which the aliphatic unsaturated bond in the norbornene skeleton of dicyclopentadiene was preferentially cleaved and substituted with phenylvinyl sulfide was quantitatively determined. Was obtained.

[0045]

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Example 2 To a mixed solution of 1.0 mol of dicyclopentadiene and 1.0 mol of phenylvinyl sulfide, 1.0 mmol of the following ruthenium complex (2) (1/1000 equivalent of dicyclopentadiene) was added. After stirring at 60 ° C. for 48 hours, the reaction solution was separated by a silica gel column, and then N 2
When analyzed by MR, as shown in the following formula (24), only 20% of the compound in which the aliphatic unsaturated bond in the norbornene skeleton of dicyclopentadiene was preferentially cleaved and substituted with phenylvinyl sulfide was obtained. It was found that it was obtained in yield.

[0047]

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Example 3 Ruthenium catalyst (3) 3.1 represented by the following formula (25)
mg (1 / 100,000 molar equivalent of dicyclopentadiene),
2 g of benzyl vinyl sulfide was dissolved in 50 g of dicyclopentadiene. After stirring at room temperature for 2 hours, 50 ° C
The residue was dried under reduced pressure to remove residual monomers. The amount of the obtained polymer was 46 g. 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 obtained polymer had a gel fraction of 8% as measured by GPC, and a number average molecular weight of 8,000 in terms of standard polystyrene.

[0049]

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Example 4 50 g of dicyclopentadiene was dissolved in 150 g of toluene, and a ruthenium catalyst (4) represented by the following formula (26) was dissolved.
15.4 mg (dicyclopentadiene 1/20000 molar equivalent) and 500 mg of allyl acetate were added, and the mixture was added at 8 ° C at 30 ° C.
After stirring for an hour, methanol was added to reprecipitate the oligomer. The obtained polymer was 48 g. The obtained polymer was immersed in xylene at 100 ° C.
The gel fraction was determined by filtering through a 0 mesh and measuring the dry weight of the solids remaining on the mesh. The obtained polymer had a gel fraction of 2% as measured by GPC, and a number average molecular weight of 3,000 in terms of standard polystyrene.

[0051]

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[0052]

According to the present invention, one of two or more types of aliphatic unsaturated bonds having different reactivities, which could not be selectively cleaved with high probability, is caused to react preferentially. It becomes possible. This makes it possible to produce compounds that could not be synthesized by conventional techniques and polymers with excellent linearity.

Claims (8)

[Claims] 1. A method for cleaving one of two or more aliphatic unsaturated bonds having different reactivity in the same molecule preferentially. 2. The method according to claim 1, wherein a metathesis reaction is carried out by adding a carbene complex to the reaction system. 3. The method according to claim 2, further comprising adding a compound having a metathesis reactive unsaturated bond to the reaction system. 4. The method according to claim 1, wherein the cleavage is performed by a bulk reaction. 5. A method for producing a polymer by repeating elementary reactions, wherein the elementary reaction comprises the cleavage method according to claim 1, 2, 3, or 4. 6. A polymer produced by the method for producing a polymer according to claim 5. Description: 7. The polymer according to claim 6, wherein the gel fraction is 20% by weight or less. 8. The polymer according to claim 6, wherein the number average molecular weight is from 600 to 30,000.