JP2001122950A - Compound having functional group at both ends and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a compound having alicyclic or heterocyclic structures as the main chain and functional groups at both the ends, capable of giving the compound having the alicyclic or heterocyclic structures as the main chain and the functional groups at both the ends, even when water or another compound, such as a raw material having a specific functional group, exists, and to provide the compound having the alicyclic or heterocyclic structures as the main chain and the functional groups at both the ends through the above method. SOLUTION: This compound having the functional groups at both the ends is obtained by adding an unsaturated cyclic compound to a mixture of an unsaturated chain compound having the functional groups at both the ends and a catalyst containing ruthenium or osmium in such a manner that the unsaturated cyclic compound is added little by little in a partial or full amount, then polymerizing the mixture to form the compound having the alicyclic or heterocyclic structures as the main chain and the functional groups at both the ends.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel compound having both functional groups at both ends and a method for producing the same, and more particularly to an alicyclic structure or a heterocyclic ring useful as a raw material for a resin modifier, a plasticizer and a condensation polymer. The present invention relates to a compound having both ends functional groups having a structure in the main chain.

[0002]

2. Description of the Related Art Both terminal functional compounds can be used as raw materials for plasticizers and polycondensation polymers. As a method for producing a compound having functional groups at both terminals having an alicyclic structure or a heterocyclic structure in the main chain, a cyclic unsaturated compound such as norbornene and a chain having a functional group at both terminals such as 1,4-diacetoxy-2-butene are known. A method has been reported in which ring-opening polymerization is carried out from unsaturated unsaturated compounds using a catalyst comprising tungsten chloride and a tin compound (Henri Cramail et al., J. Mol. Ca.
t., Vol. 65, 193 (1991)). In addition, Tokuhyo Hei 9-5128
No. 28 discloses 1,5-cyclooctadiene and 1,4
Disclosed is a method for producing a polybutadiene having both ends functionalized from diacetoxy-2-butene by ring-opening polymerization using a ruthenium carbene complex.

[0003]

A process for producing a compound having both terminal functional groups having an alicyclic structure or a heterocyclic structure in the main chain thereof by ring-opening polymerization using a catalyst comprising tungsten chloride and a tin compound has been proposed. In some cases, the catalyst is deactivated due to the influence of compounds such as water or raw materials, and a compound having a functional group at both ends may not be obtained. For example, when 1,4-dihydroxy-2-butene is used as a chain unsaturated compound having a functional group at both terminals, a compound having a functional compound at both terminals cannot be obtained.

[0004] Japanese Patent Publication No. Hei 9-512828 discloses that
5-cyclooctadiene is converted to 1,4-diacetoxy-2-
A method for producing a polybutadiene having both ends functionalized by ring-opening polymerization with a ruthenium carbene complex in the presence of butene is disclosed. According to this method, norbornene, 1,4
-When a ruthenium carbene complex is added to a solution in which diacetoxy-2-butene and a solvent are mixed to produce a compound having both terminal functional groups having an alicyclic structure in the main chain, the polymerization reaction proceeds rapidly, An oligomer having a molecular weight and a functional group at both terminals cannot be obtained.

An object of the present invention is to solve the above-mentioned problems of the prior art. More specifically, a production method capable of obtaining a both-end functional compound having an alicyclic structure or a heterocyclic structure in the main chain even in the presence of a compound such as water or a raw material having a specific functional group, and a production method obtained by the method. It is an object of the present invention to provide a terminal-functional compound having an alicyclic structure or a heterocyclic structure in its main chain.

[0006]

Means for Solving the Problems As a result of intensive studies on the above problems, the present inventors have found that an alicyclic structure or an alicyclic structure is obtained by subjecting a catalyst containing ruthenium or osmium to ring-opening polymerization under specific production conditions. The present inventors have succeeded in obtaining a compound having a functional group at both ends having a heterocyclic structure in the main chain, and have reached the present invention. That is, the present invention relates to a compound having a functional group at both ends represented by the following (1) to (9) and a method for producing the same. (1) Both terminal functional compounds represented by the general formula (I).

[0007]

Embedded image[Wherein X is independently OR, COOR or OCOR (R
Represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
You. ), P represents an integer of 1 to 1000, m and
n represents the integer of 0-5 independently. When X = OR, R
¹~ R⁸Has independently a halogen atom, a hydrogen atom and a substituent
An optionally substituted hydrocarbon group having 1 to 20 carbon atoms (R ^ThreeAnd R^Four,
R^FiveAnd R⁶Is independently divalent in each group.
May be a Japanese hydrocarbon group;¹~ R⁸Two or more of are connected
A ring may be formed. ), Cyano group, hydroxyl group, alcohol
Xyl group, acyl group, formyl group, carboxyl group (D
Form acid anhydride from stel or two carboxyl groups
May be. ) Or a silyl group. X = COOR
Or OCOR, R¹~ R⁸Is independently a halogen source
And a hydrocarbon having 1 to 20 carbon atoms which may have a substituent
Base group (R^ThreeAnd R^Four, R^FiveAnd R⁶Are independent of each other,
May be a divalent unsaturated hydrocarbon group.¹~ R⁸Horse
Two or more may be linked to form a ring. ), Cyano
Group, hydroxyl group, alkoxyl group, acyl group, formyl group,
Carboxyl group (ester or two carboxyl groups
To form an acid anhydride. ) Or a silyl group
Represent. ]

(2) When R ^{1 to} R ^{8 in} the general formula (I) are independently X = OR, a hydrogen atom or a C ¹ to C 20
Hydrocarbon groups (R ³ and R ^4, R ⁵ and R ⁶ are independently in each set, together may be a divalent unsaturated hydrocarbon group, R ¹
Two or more of R ⁸ to R ⁸ may be linked to form a ring. )
And when X = COOR or OCOR, a hydrocarbon group having 1 to 20 carbon atoms (R ³ and R ⁴ , and R ⁵ and R ⁶ independently represent a divalent unsaturated hydrocarbon in each group. Or two or more of R ^{1 to} R ⁸ may be linked to form a ring.). (3) Both terminals are each represented by the general formula (II), and between them, (a) the repeating unit represented by the general formula (III) and (b) one double bond of the cyclic unsaturated compound And a repeating unit represented by a ring-opened structure upon cleavage. _{X- (CH 2) m -CH =} , X- (CH 2) n -CH = (II) wherein, X is OR independently, COOR or OCOR (R
Represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. ), And m and n independently represent an integer of 0 to 5. ]

[0009]

Embedded image [Wherein, R ^{1 to} R ⁸ are each independently a halogen atom, a hydrogen atom, or an optionally substituted hydrocarbon group having 1 to 20 carbon atoms (R ³ and R ⁴ , R ⁵ and R ⁶ are each May be independently a divalent unsaturated hydrocarbon group, and two of R ^{1 to} R ⁸
Two or more may be linked to form a ring. ), A cyano group, a hydroxyl group, an alkoxyl group, an acyl group, a formyl group, a carboxyl group (an acid anhydride may be formed from an ester or two carboxyl groups), or a silyl group. ]

(4) R ^{1 to} R ^{8 in} the general formula (III) are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms (R ³ and R ⁴ , R ⁵ and R ⁶ are And independently may be a divalent unsaturated hydrocarbon group, and two of R ^{1 to} R ⁸
Two or more may be linked to form a ring. ) The compound at both ends functionalized according to (3) above. (5) (b) A cyclic unit having a ring-opened structure of a cycloalkene having 4 to 12 carbon atoms, wherein the repeating unit represented by the structure opened by cleavage of one double bond of the cyclic unsaturated compound is (3). Or the both-end functional compound according to (4). (6) A catalyst containing ruthenium or osmium is used from (A) a cyclic unsaturated compound and (B) a chain unsaturated compound having a functional group at both ends to form an alicyclic structure or a heterocyclic structure in the main chain. In the method for producing a compound having a functional group at both ends, the compound (B) comprises a mixture of a chain unsaturated compound having a functional group at both terminals and a catalyst containing ruthenium or osmium, which is cleaved by a ring-opening polymerization reaction. The two-center energy of the heavy bond is larger than -23.2 eV (A)
Add part or all of the cyclic unsaturated compound little by little,
A method for producing a compound having both functional groups, characterized by polymerizing. (7) (B) a linear unsaturated compound having a functional group at both ends is represented by the general formula (IV):

[0011]

Embedded image [Wherein, m and n are independently an integer of 0 to 5, X is independently O
R, COOR or OCOR (R represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms). [6] The method for producing a compound having functional groups at both ends according to (6). (8) The method for producing a compound having functional groups at both ends according to (6) or (7), wherein the catalyst is a carbene complex of ruthenium or osmium. (9) The number-average molecular weight of the compound having functional groups at both ends is 300 to 3
The method for producing a compound having both ends functionalized according to any one of (6) to (8), wherein the compound is 0000.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described below. According to the invention, the general formula (I):

[0013]

Embedded image[Wherein X is independently OR, COOR or OCOR (R
Represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
You. ), P represents an integer of 1 to 1000, m and
n represents the integer of 0-5 independently. When X = OR, R
¹~ R⁸Has independently a halogen atom, a hydrogen atom and a substituent
An optionally substituted hydrocarbon group having 1 to 20 carbon atoms (R ^ThreeAnd R^Four,
R^FiveAnd R⁶Is independently divalent in each group.
May be a Japanese hydrocarbon group;¹~ R⁸Two or more of are connected
A ring may be formed. ), Cyano group, hydroxyl group, alcohol
Xyl group, acyl group, formyl group, carboxyl group (D
Form acid anhydride from stel or two carboxyl groups
May be. ) Or a silyl group. X = COOR
Or OCOR, R¹~ R⁸Is independently a halogen source
And a hydrocarbon having 1 to 20 carbon atoms which may have a substituent
Base group (R^ThreeAnd R^Four, R^FiveAnd R⁶Are independent of each other,
May be a divalent unsaturated hydrocarbon group.¹~ R⁸Horse
Two or more may be linked to form a ring. ), Cyano
Group, hydroxyl group, alkoxyl group, acyl group, formyl group,
Carboxyl group (ester or two carboxyl groups
To form an acid anhydride. ) Or a silyl group
Represent. ] Is provided.

Specifically, R is a hydrogen atom; methyl, ethyl, propyl, isopropyl, butyl, isobutyl,
C 1-6 such as tert-butyl, amyl, hexyl, etc.
And an aryl group such as phenyl, tolyl, mesityl, and naphthyl. Also, more specifically, X
Examples thereof include alkoxyl groups such as methoxy, ethoxy, propoxy, isobutoxy and tert-butoxy; acyloxy groups such as acetoxy and propionyloxy; aroyloxy groups such as benzoyl and toluoyloxy; hydroxyl groups; and carboxyl groups. Of these, a hydroxyl group and an acyloxy group are preferred, and a hydroxyl group and an acetoxyl group are more preferred.

R ^{1 to} R ⁸ in the general formula (I) will be described below with specific examples. Examples of the halogen atom include a fluorine atom, a chlorine atom and a bromine atom. Examples of the hydrocarbon group having 1 to 20 carbon atoms which may have a substituent include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, amyl, hexyl, octyl, decyl, dodecyl, octadecyl and the like. An alkyl group, a cycloalkyl group such as cyclopentyl and cyclohexyl, an aryl group such as phenyl, tolyl, mesityl, and naphthyl; a divalent unsaturated formed independently from each set of R ³ and R ⁴ , and R ⁵ and R ⁶ Examples of the hydrocarbon group include an alkylidene group such as ethylidene, propylidene and isopropylidene; and a ring in which two or more of R ^{1 to} R ⁸ are linked.
A 3- to 6-membered spiro ring in which R ¹ and R ² , R ³ and R ^4, or R ⁵ and R ⁶ are linked to each other, which is bonded to one common carbon atom, α in the general formula (I) , Β, a condensed 5-8 membered ring sharing a carbon atom, and substituted alkyl groups such as hydroxymethyl, hydroxyethyl, chloromethyl, methoxymethyl, and acetoxymethyl.

A cyano group; a hydroxyl group; an alkoxyl group such as methoxy, ethoxy, propoxy, isobutoxy and tert-butoxy; an acyl group such as acetoxy and propionyloxy; a formyl group; a carboxyl group or its methyl, ethyl, propyl, butyl, Esters such as phenyl or an acid anhydride formed from two carboxyl groups; silyl groups such as trimethylsilyl and the like. Of these R ^{1 to} R ⁸ , preferably, when X = OR, a hydrogen atom, a hydrocarbon group, a hydroxyl group, and when X = COOR or OCOR, a hydrocarbon group, a hydroxyl group, and more preferably, X = When OR, it is a hydrogen atom or a hydrocarbon group, and when X = COOR or OCOR, it is a hydrocarbon group.

More specifically, examples of the monomer compound forming a repeating unit of the both-terminal functional compound represented by the general formula (I) include norbornene, 2,5-norbornadiene,
5-ethylidene-2-norbornene, 2-methyl-5
Norbornene, 2-hexyl-5-norbornene, 2-
Norbornenes formed only from hydrocarbons such as cyclohexyl-5-norbornene, dicyclopentadiene, and benzonorbornadiene; 5-norbornene-2-carbonitrile; 5-norbornene-2-carbaldehyde;
5-norbornene-2,3-dicarboxylic anhydride, 2-
Trimethylsilyl-5-norbornene, 2-chloro-5
Norbornenes having a substituent other than a hydrocarbon group such as -norbornene, 2-methoxycarbonyl-5-norbornene, 2-methyl-5-norbornene-3-carbaldehyde, 2-methyl-5-norbornene-3-methanol, 8-ethylidenetetracyclo [4.4.0.
^12.5 . 1 ^{7, 10]} -3-dodecene, 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^{2, 5.
Examples} thereof include norbornene-based compounds such as norbornenes having a condensed ring such as [ ^1,7,10 ] -3-dodecene. These norbornene compounds may be used alone or in combination of two or more. Among these norbornene-based compounds, norbornenes formed preferably of only hydrocarbons are used.

Further, according to the present invention, both terminals are represented by the general formula (II), and between them, (a) the general formula (II)
A double-ended functional type comprising: a repeating unit represented by I); and (b) a repeating unit represented by a ring-opened structure obtained by cleavage of one double bond of a cyclic unsaturated compound. Compounds are provided.

X- (CH ₂ ) _m -CH =, X- (CH ₂ ) _n -CH = (II) wherein X is independently OR, COOR or OCOR (R
Represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. ), And m and n independently represent an integer of 0 to 5. ]

[0020]

Embedded image [Wherein, R ^{1 to} R ⁸ are each independently a halogen atom, a hydrogen atom, or an optionally substituted hydrocarbon group having 1 to 20 carbon atoms (R ³ and R ⁴ , R ⁵ and R ⁶ are each May be independently a divalent unsaturated hydrocarbon group, and two of R ^{1 to} R ⁸
Two or more may be linked to form a ring. ), A cyano group, a hydroxyl group, an alkoxyl group, an acyl group, a formyl group, a carboxyl group (an acid anhydride may be formed from an ester or two carboxyl groups), or a silyl group. ]

Specifically, R is a hydrogen atom; methyl, ethyl, propyl, isopropyl, butyl, isobutyl,
C 1-6 such as tert-butyl, amyl, hexyl, etc.
And an aryl group such as phenyl, tolyl, mesityl, and naphthyl. Also, more specifically, X
Examples thereof include alkoxyl groups such as methoxy, ethoxy, propoxy, isobutoxy and tert-butoxy; acyloxy groups such as acetoxy and propionyloxy; aroyloxy groups such as benzoyl and toluoyloxy; hydroxyl groups; and carboxyl groups. Of these, a hydroxyl group and an acyloxy group are preferred, and a hydroxyl group and an acetoxyl group are more preferred.

(A) R in the general formula (III)¹~ R⁸
Will be described below with specific examples. As a halogen atom
Include fluorine, chlorine, bromine, etc.
You. Hydrocarbons having 1 to 20 carbon atoms which may have a substituent
Basic groups include methyl, ethyl, propyl, isopropyl
Butyl, isobutyl, tert-butyl, amyl,
Hexyl, octyl, decyl, dodecyl, octadecyl
Alkyl groups such as cyclopentyl, cyclohexyl, etc.
Cycloalkyl group, phenyl, tolyl, mesityl, naph
An aryl group such as tyl, R^ThreeAnd R^Four, R^FiveAnd R⁶Each of
As a divalent unsaturated hydrocarbon group formed independently from the group
Means ethylidene, propylidene, isopropylidene, etc.
Alkylidene group, R¹~ R⁸A ring in which two or more of
Substituents attached to one common carbon atom
That is, R¹And R^Two, R^ThreeAnd R^FourOr R ^FiveAnd R⁶3 linked
A 6-membered spiro ring represented by α and β in the general formula (I)
5- to 8-membered condensed ring sharing a carbon atom,
Methyl, hydroxyethyl, chloromethyl, methoxymeth
And substituted alkyl groups such as tyl and acetoxymethyl.
It is.

A cyano group; a hydroxyl group; an alkoxyl group such as methoxy, ethoxy, propoxy, isobutoxy and tert-butoxy; an acyl group such as acetoxy and propionyloxy; a formyl group; a carboxyl group or its methyl, ethyl, propyl, butyl, Esters such as phenyl or an acid anhydride formed from two carboxyl groups; silyl groups such as trimethylsilyl and the like. Among these R ^{1 to} R ^8, a hydrogen atom, a hydrocarbon group and a hydroxyl group are preferable, and a hydrogen atom and a hydrocarbon group are more preferable.

More specifically, the monomer compounds forming the repeating unit represented by the general formula (III) include norbornene, 2,5-norbornadiene, 5-ethylidene-
2-norbornene, 2-methyl-5-norbornene, 2
-Hexyl-5-norbornene, 2-cyclohexyl-
Norbornenes formed only from hydrocarbons such as 5-norbornene, dicyclopentadiene, and benzonorbornadiene; 5-norbornene-2-carbonitrile;
Norbornene-2-carbaldehyde, 5-norbornene-2,3-dicarboxylic anhydride, 2-trimethylsilyl-5-norbornene, 2-chloro-5-norbornene,
Norbornenes having a substituent other than a hydrocarbon group, such as 2-methoxycarbonyl-5-norbornene, 2-methyl-5-norbornene-3-carbaldehyde, 2-methyl-5-norbornene-3-methanol, 8-ethylidene Tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10] -3-dodecene, 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^{2, 5. Examples} thereof include norbornene-based compounds such as norbornenes having a condensed ring such as [ ^1,7,10 ] -3-dodecene. These norbornene compounds are
One kind may be used alone, or two or more kinds may be used in combination. Of these norbornene-based compounds, preferred are norbornenes formed of only hydrocarbons, and more preferred are norbornene and 5-ethylidene-2-norbornene.

(B) Monomers which form a repeating unit represented by a ring-opened structure by cleavage of one double bond of a cyclic unsaturated compound include cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene and cyclooctene. Cycloalkenes such as cyclononene and cyclodecene; substituted cycloalkenes such as 4-methyl-1-cyclohexene; cycloalkadienes such as cyclopentadiene, methylcyclopentadiene and 1,5-cyclooctadiene; 3-cyclohexene-1- Methanol, 3-cyclohexene-1,1-dimethanol, 6-methyl-3
And cyclic unsaturated compounds such as cycloalkenes having a hydroxyl group such as -cyclohexene-1,1-dimethanol and halogenated cycloalkenes such as 3-bromocyclohexene. These cyclic unsaturated compounds may be used alone or in combination of two or more. Of these cyclic unsaturated compounds, preferred are cycloalkenes.

The method for producing a compound having a functional group at both ends according to the present invention is characterized in that a mixture of a chain unsaturated compound having a functional group at both ends and a catalyst containing ruthenium or osmium is prepared by adding a part or all of the cyclic unsaturated compound to the mixture. It is characterized by being added little by little and polymerized. More specifically, the reaction is started by adding a catalyst to a mixture containing a chain unsaturated compound having a functional group at both terminals and a solvent, or optionally also a part of the cyclic unsaturated compound, and then starting the reaction. This is a production method in which part or all of an unsaturated compound is gradually added to the mixture to cause a reaction. In other words, the production method is characterized in that the polymerization is carried out while adding at least a part of the cyclic unsaturated compound into the system during the reaction little by little.
The addition of the cyclic unsaturated compound to the mixture after the start of the reaction may be carried out relatively quickly, but in order to obtain a compound having both ends functionalized with a more controlled structure such as molecular weight, it is necessary to supply the compound by a liquid feed pump. It is preferred to add and polymerize at a controlled rate using a method such as dropping. The time required to complete the addition of all the cyclic unsaturated compounds varies depending on the cyclic unsaturated compound, a chain unsaturated compound having a functional group at both terminals, a catalyst, a solvent, a reaction temperature, a desired molecular weight, and the like. It is about 10 minutes to 10 hours.

The alicyclic compound of the cyclic unsaturated compound used in the method for producing a compound having both terminal functional groups according to the present invention is represented by the general formula (V):

[0028]

Embedded image [Wherein, R ^{1 to} R ⁸ are each independently a halogen atom, a hydrogen atom, or an optionally substituted hydrocarbon group having 1 to 20 carbon atoms (R ³ and R ⁴ , R ⁵ and R ⁶ are each May be independently a divalent unsaturated hydrocarbon group, and two of R ^{1 to} R ⁸
Two or more may be linked to form a ring. ), A cyano group, a hydroxyl group, an alkoxyl group, an acyl group, a formyl group, a carboxyl group (an acid anhydride may be formed from an ester or two carboxyl groups), or a silyl group. Represented by the following formulas], cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclononene, cycloalkene such as cyclodecene, substituted cycloalkene such as 4-methyl-1-cyclohexene, cyclopentadiene, methylcyclopentadiene, Cycloalkadienes such as 3,5-cyclooctadiene, 3-cyclohexene-1-methanol, 3
And cycloalkenes having a hydroxyl group such as -cyclohexene-1,1-dimethanol and 6-methyl-3-cyclohexene-1,1-dimethanol, and halogenated cycloalkenes such as 3-bromocyclohexene.

R ^{1 to} R ⁸ in the general formula (V) will be described below with specific examples. Examples of the halogen atom include a fluorine atom, a chlorine atom and a bromine atom. Examples of the hydrocarbon group having 1 to 20 carbon atoms which may have a substituent include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, amyl, hexyl, octyl, decyl, dodecyl, octadecyl and the like. An alkyl group, a cycloalkyl group such as cyclopentyl and cyclohexyl, an aryl group such as phenyl, tolyl, mesityl, and naphthyl; a divalent unsaturated formed independently from each set of R ³ and R ⁴ , and R ⁵ and R ⁶ Examples of the hydrocarbon group include an alkylidene group such as ethylidene, propylidene and isopropylidene; and a ring in which two or more of R ^{1 to} R ⁸ are linked.
A substituent bonded to one common carbon atom, that is, a 3- to 6-membered spiro ring in which R ¹ and R ² , R ³ and R ⁴ or R ⁵ and R ⁶ are linked, α in the general formula (V) , Β, a condensed 5-8 membered ring sharing a carbon atom, and substituted alkyl groups such as hydroxymethyl, hydroxyethyl, chloromethyl, methoxymethyl, and acetoxymethyl.

A cyano group; a hydroxyl group; an alkoxyl group such as methoxy, ethoxy, propoxy, isobutoxy and tert-butoxy; an acyl group such as acetoxy and propionyloxy; a formyl group; a carboxyl group or its methyl, ethyl, propyl, butyl, Esters such as phenyl or an acid anhydride formed from two carboxyl groups; silyl groups such as trimethylsilyl and the like. Of these R ^{1 to} R ⁸ , preferred are a hydrogen atom, a hydrocarbon group, a hydroxyl group, and more preferred are a hydrogen atom and a hydrocarbon group.

More specifically, the norbornene compounds represented by the general formula (V) include norbornene, 2,5-norbornadiene, 5-ethylidene-2-norbornene,
2-methyl-5-norbornene, 2-hexyl-5-norbornene, 2-cyclohexyl-5-norbornene,
Norbornenes formed only with hydrocarbons such as dicyclopentadiene and benzonorbornadiene, 5-norbornene-2-carbonitrile, 5-norbornene-2-carbaldehyde, 5-norbornene-2,3-dicarboxylic anhydride, 2 -Trimethylsilyl-5-norbornene,
Substituents other than hydrocarbon such as 2-chloro-5-norbornene, 2-methoxycarbonyl-5-norbornene, 2-methyl-5-norbornene-3-carbaldehyde, 2-methyl-5-norbornene-3-methanol Having norbornene, 8-ethylidenetetracyclo [4.4.
0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-methyl-8
- methoxycarbonyltetracyclo [4.4.0.1 ^2,
5 ． Norbornenes having a condensed ring such as [ ^17,10 ] -3-dodecene.

As the heterocyclic compound, benzooxanorbornadiene, 2,3-bis (methoxymethyl)
And oxonorbornenes such as -7-oxa-5-norbornene and 2,3-trifluoromethyl-7-oxa-5-norbornene.

These cyclic unsaturated compounds can be used alone or in combination of two or more. Among these, a cyclic unsaturated compound formed preferably of only a hydrocarbon, and more preferably a norbornene formed of only a hydrocarbon is used. Further, other copolymerizable components can be used in combination within a range not to impair the gist of the present invention.

From the above-mentioned cyclic unsaturated compound and a chain unsaturated compound having a functional group at both terminals, a catalyst is used to produce a compound with both terminals having an alicyclic structure or a heterocyclic structure in the main chain. In the method, it has been found that a compound having functional groups at both ends using a specific cyclic unsaturated compound as a raw material can be produced by a polymerization reaction under specific conditions. That is, a mixture of a chain unsaturated compound having a functional group at both terminals and a catalyst containing ruthenium or osmium is added with a reactive carbon-carbon double bond 2
By adding a part or the whole amount of the cyclic unsaturated compound having a central energy of more than −23.2 eV little by little and polymerizing the compound, a compound having a desired specific structure at both ends can be obtained. 2 center energy is -2
Compounds having a carbon double bond of 3.2 eV or less can be reacted without addition. The two-center energy is a measure of the strength of the bond. Use the semi-empirical molecular orbital method calculation program, MOPAC, to perform a structure optimization calculation, and use ENPART as a keyword when optimizing the molecular structure in the input file. Is most preferable.

Examples of the cyclic unsaturated compound which is preferably polymerized by adding the compound are shown below. The value in parentheses after the compound name is the value of the two-center energy of the reactive carbon-carbon double bond cleaved by the polymerization reaction, and the unit is eV. Cyclobutene (-22.44), 8-ethylidenetetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene (-22.94), norbornene (-23.0)
0), 5-norbornene-2,3-dicarboxylic anhydride (-23.00), 5-norbornene-2-carbonitrile (-23.01), dicyclopentadiene (-2
3.02), 5-ethylidene-2-norbornene (-2
3.02), 7-oxa-5-norbornene (-23.
04), 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ] -3-dodecene (-23.04), cyclopentene (-23.12) and the like. Some of these compounds have a substituent
Although there are endo- and exo-stereoisomers, there is almost no effect on the two-center energy of the double bond cleaved by the polymerization reaction, and no problem occurs.

Examples of the cyclic unsaturated compound which may be mixed with the catalyst at the start of the reaction, as described above, are as follows. Cyclohexene (-23.34), 1,5-cyclooctadiene (-23.38), cyclopentene (-2
3.34), cyclooctene (-23.41) and the like.

The chain unsaturated compound having a functional group at both terminals used in the method for producing a compound having both terminals functional groups of the present invention is represented by the general formula (IV):

[0038]

Embedded image [Wherein, m and n are independently an integer of 0 to 5, X is independently O
R, COOR or OCOR (R represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms). And a compound for introducing a functional group into both terminals as well as a molecular weight regulator.

Specifically, R is a hydrogen atom; methyl, ethyl, propyl, isopropyl, butyl, isobutyl,
C 1-6 such as tert-butyl, amyl, hexyl, etc.
And an aryl group such as phenyl, tolyl, mesityl, and naphthyl. Also, more specifically, X
Examples thereof include alkoxyl groups such as methoxy, ethoxy, propoxy, isobutoxy and tert-butoxy; acyloxy groups such as acetoxy and propionyloxy; aroyloxy groups such as benzoyl and toluoyloxy; hydroxyl groups; and carboxyl groups. Of these, a hydroxyl group and an acyloxy group are preferred, and a hydroxyl group and an acetoxyl group are more preferred.

More specifically, examples of the chain unsaturated compound represented by the general formula (IV) include 1,4-dihydroxy-2
-Butene, 1,6-dihydroxy-3-hexene, 1,
Both terminal diol compounds such as 8-dihydroxy-4-octene, 1,4-diacetoxy-2-butene, 1,6-diacetoxy-3-hexene, 1,8-diacetoxy-4
-Carboxylic acid ester compounds of diols at both terminals such as octene, carboxylic acid compounds of both terminals such as maleic acid and fumaric acid, carboxylic acid ester compounds of both terminals such as dimethyl maleate, diethyl maleate, dimethyl fumarate and diethyl fumarate, etc. Is mentioned. Of these, preferably used are diol compounds at both ends and carboxylic acid ester compounds of diols at both ends, and more preferably 1,4-dihydroxy-2-butene and 1,4-diacetoxy-2-butene.

The amount of the chain unsaturated compound having a functional group at both terminals is 0.1 mol per mol of the cyclic unsaturated compound.
Desirably, it is 100. The molar ratio may be reduced when a high molecular weight bifunctional compound is desired, and the molar ratio may be increased when a low molecular weight bifunctional compound is desired.

The catalyst used in the present invention is ruthenium or ruthenium.
Or a catalyst containing osmium,
The reaction can proceed. The catalyst is
Body-borne or complex catalysts can be used, but are preferred.
Or a complex catalyst, more preferably a carbene complex
It is. As a specific example, (In each of the following formulas, Me is
Represents a ruthenium or osmium atom. ), Cl_Two
[P (iso-C_ThreeH₇)_Three]_TwoMe = CH-C₆H_Five, Br
Cl [P (iso-C_ThreeH₇)_Three]_TwoMe = CH-C₆H_Five,
Cl_Two[P (iso-C_ThreeH₇)_Three]_TwoMe = CH- [C₆H
_Four(CH_Three)], Cl_Two[P (iso-C_ThreeH₇)_Three]_TwoMe
= CH- [C₆H_Four(Ter-C_FourH₉)], BrCl [P
(Iso-C_ThreeH₇)_Three]_TwoMe = CH-CH_TwoC₆H_Five, C
l_Two[P (sec-C_FourH₉)_Three]_TwoMe = CH-C₆H_Fiveetc
Having a ligand in which an alkyl group is bonded to a phosphorus atom of
Ben complex, Cl_Two[P (C_FiveH₉)_Three]_TwoMe = CH_Two, Cl
_Two[P (C_FiveH₉)_Three]_TwoMe = CH-CH_Three, Br_Two[P
(C_FiveH₉)_Three]_TwoMe = CH-iso-C_ThreeH₇, Cl
_Two[P (C_FiveH₉)_Three]_TwoMe = CH-n-C_FourH₉, Cl
_Two[P (C_FiveH₉)_Three]_TwoMe = CH-C_FiveH₉, Cl_Two[P
(C_FiveH₉)_Three]_TwoMe = CH-C₆H ₁₁, F_Two[P (C
_FiveH₉)_Three]_TwoMe = CH-C₆H_Five, Cl_Two[P (C
_FiveH₉)_Three]_TwoMe = CH-C₆H_Five, Br_Two[P (C
_FiveH₉)_Three]_TwoMe = CH-C₆H_Five, Br_Two[P (C
_FiveH₉)_Three]_TwoMe = CH- (C₆H_Four-OC_TwoH_Five), Cl_Two
[P (C_FiveH₉)_Three]_TwoMe = CH- (C₆H_Four-Br), C
l_Two[P (C_FiveH₉)_Three]_TwoMe = CH- [C₆H_Three− (C
H_Three)_Two], F_Two[P (C_FiveH₉)_Three]_TwoMe = CH- [C₆H
_Three− (CH_Three)_Two], Br_Two[P (C_FiveH₉)_Three]_TwoMe = CH
-CH_TwoC₆H_FiveCyclopentyl group is bonded to phosphorus atom such as
Complex with a modified ligand, Cl_Two[P (C
₆H₁₁)_Two-CH_TwoCH_Two−P (C₆H₁₁)_Two] Me = CH-
C₆H_Five, Cl_Two[P (C₆H₁₁)_Three]_TwoMe = CH_Two, Cl_Two
[P (C₆H₁₁)_Three]_TwoMe = CH-CH_Three, Cl_Two[P
(C₆H₁₁)_Three]_TwoMe = CH-n-C_FourH₉, Cl_Two[P
(C₆H₁₁)_Three]_TwoMe = CH-ter-C_FourH₉, Cl
_Two[P (C₆H₁₁)_Three]_TwoMe = CH-C_TenH₉, F_Two[P
(C₆H₁₁)_Three]_TwoMe = CH-C₆H_Five, Cl_Two[P (C₆
H₁₁)_Three]_TwoMe = CH-C₆H_Five, Br_Two[P (C₆H₁₁)
_Three]_TwoMe = CH-C₆H_Five, Cl_Two[P (C₆H₁₁)_Three]_TwoM
e = CH (C₆H_Four-CH_Three), Cl_Two[P (C₆H₁₁)_Three]
_TwoMe = CH-C₆H_Four-CH (CH_Three)_Two, Cl_Two[P (C
₆H₁₁)_Three]_TwoMe = CH- [C₆H_Four(Ter-C
_FourH₉)], Br_Two[P (C₆H₁₁)_Three]_TwoMe = CH-C₆
H_Two− (CH_Three)_Three, Cl_Two[P (C₆H₁₁)_Three]_TwoMe = C
HC₆H_Four-OCH_Three, Br_Two[P (C₆H₁₁)_Three]_TwoMe
= CH- (C₆H_Four-NO_Two), Cl_Two[P (C₆H₁₁)_Three]
_TwoMe = CH- (C₆H_Four-Cl), BrCl [P (C₆H
₁₁)_Three]_TwoMe = CH-CH_TwoC₆H_Five, BrCl [P (C₆
H₁₁)_Three]_TwoMe = CH-CH_TwoC₆H_Five, Cl_Two[P (C₆
H₁₁)_Two(C (CH_TwoCH_Two)_TwoN (CH_Three)_TwoCl)]_TwoM
e = CH-C₆H_Five, Cl_Two[P (C₆H₁₁)_Two(CH_TwoCH
_TwoSO_ThreeNa)]_TwoMe = CH-C₆H_Five, Cl_Two[P (C₆
H₁₁)_Two(CH_TwoCH_TwoN (CH_Three)_ThreeCl)]_TwoMe = CH
-C₆H_FiveWith a cyclohexyl group bonded to a phosphorus atom such as
Carbene complex with ligand, Cl_Two[P (C₆H_Five)_Three]_Two
Me = CH-C₆H_Five, Cl_Two[P (C₆H_Four-CH_Three)_Three]_Two
Me = CH-C₆H_Five, Br_Two[P (C₆H_Three− (C
H_Three)_Two)_Three]_TwoMe = CH-C₆H_Five, Cl_Two[P (C₆H_Two
− (CH_Three)_Three)_Three]_TwoMe = CH-C₆H_FiveSuch as phosphorus atom
Carbene complex having a ligand to which an aromatic group is bonded, WO
 98/21214 of ruthenium and osmium
Carbene complexes, Thomas Weskamp et al., Angew. Chem. Int.
 Ed., Vol. 37, 2490 (1998)
-Dialkyl-imidazoline-2-ylidene coordinated
Carbene complexes and the like. These catalysts are used alone
Or a combination of two or more. this
Of these, a complex having a ruthenium atom is preferred.
And more preferably a complex having a ruthenium atom.
Such as cyclopentyl and cyclohexyl groups
Has a phosphorus compound ligand bound to a cycloalkyl group
Carbene complexes are used.

The amount of the catalyst used is 1 to 0.00001, preferably 0.1 to 0.
0001, more preferably in the range of 0.01 to 0.0002. If it exceeds 1, the cost increases, and if it is too small, the reaction rate may decrease, which is not preferable.

The both-terminal functional compound obtained according to the present invention is useful as a resin modifier, a plasticizer and a raw material for polycondensation.
In these applications in which a compound having both terminal functional groups is used as a reaction raw material, a compound having both terminal functional groups having a molecular weight in a so-called oligomer region, as typified by polybutadiene polyol, is preferable. In such a case, gel permeation chromatography (hereinafter referred to as gel permeation chromatography) The number average molecular weight in terms of polystyrene measured by GPC is 300 to
It is about 30,000. The preferred number average molecular weight is about 300 to 28,000, more preferably 30 to 30.
0 to 25000.

Although the reaction mode of the present invention is not particularly limited, it is preferable to carry out the reaction in a homogeneous system. The homogeneous reaction may be a solventless reaction, but is preferably performed in a solvent. There are no particular restrictions on the use of the solvent, but preferred solvents include methanol, ethanol, n-propanol, isopropanol, n-butanol and se.
Alcohols such as c-butanol, ter-butanol, isobutanol, cyclohexanol, propylene glycol monomethyl ether, pentane, hexane, heptane, octane, nonane, cyclohexane, cycloheptane, cyclooctane and other aliphatic hydrocarbons, benzene, Toluene, xylene, ethylbenzene,
Aromatic hydrocarbons such as cumene, halogenated hydrocarbons such as chlorobutane, bromohexane, methylene chloride, chloroform, dichloroethane, chlorobenzene, and dichlorobenzene, and halogenated aromatic hydrocarbons, ethyl acetate, isopropyl acetate, and n-butyl acetate , Methyl propionate, propylene glycol monomethyl ether acetate, ethyl lactate, saturated carboxylic esters such as methyl 3-methoxypropionate, diethyl ether,
Dibutyl ether, tetrahydrofuran, dioxane,
Ethers such as dimethoxyethane, ketones such as acetone and methyl ethyl ketone, dimethylformamide,
Aprotic polar solvents such as dimethylacetamide, N-methylpyrrolidone, and dimethylsulfoxide; These can be used alone or in combination of two or more. These solvents do not necessarily need to be used after being dehydrated and purified, and can be reacted in the presence of water. For example, in the catalyst system of the present invention, emulsion polymerization can be carried out in an aqueous solution in the presence of a surfactant, or in a mixed system of water and a solvent such as methylene chloride or toluene, which is impossible with a conventional tungsten-based catalyst or the like. Although the dissolution of oxygen in the solvent does not cause a serious problem, if the reaction time is long, the catalyst may be gradually deactivated.

In the method for producing a compound having both ends functionalized according to the present invention, the reaction can be carried out at a reaction temperature of 0 to 200 ° C. Desirably, it is 15 to 100 ° C. The reaction is generally carried out at normal pressure, but may be carried out under reduced pressure or under a pressure of 5 MPa or less.

The method for recovering a compound having both terminal functional groups from the reaction solution produced by the method of the present invention is not particularly limited. For example, the reaction solution can be precipitated by dropping it into a poor solvent, and the compound having functional groups at both ends can be recovered by filtration or the like. The method for removing the catalyst is not particularly limited. For example, in a method of recovering a compound having both terminal functional groups by dropping a reaction solution into a poor solvent, the compound having both terminal functional groups is insoluble as a poor solvent, but if a solvent that dissolves a catalyst is used, the compound having both terminal functional groups is used. At the stage of recovering the catalyst, the catalyst can be removed at the same time.

The compound having a functional group at both ends obtained by the present invention may be a known antioxidant such as hydroquinone, methoxyphenol, 2,6-di-tert-butyl-4-methylphenol, 2,2'-dioxy- 3,3'-di-t
phenol-based antioxidants such as er-butyl 5,5'-dimethyldiphenylmethane; sulfur-based antioxidants such as dilauryl 3,3'-thiodipropionate and dimyristyl 3,3'-thiodipropionate; A neighboring antioxidant such as phyte and diphenylisodecyl phosphite can be added and stabilized by a known method, and a known ultraviolet absorber, for example, 2,4-dihydroxybenzophenone, 2-hydroxy-4- Stabilization can also be achieved by adding methoxybenzophenone or the like.

[0049]

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

The calculation of the two central energies is performed by assembling the molecular structure with Editor, which is a program of CAChe (Oxford Molecular, UK) system, and then MOPAC (version 9), a semi-empirical molecular orbital calculation program.
According to 4.10), the structure optimization calculation is performed using the AM1 method,
The two-center energy was calculated by using the keyword ENPART based on the obtained structure having the minimum energy. The machine used for the calculation was a Macintosh (Pow
erMacintosh8500 / 120).

The reagents and solvents used were degassed and replaced with an inert gas. However, the reagents were used as purchased without any purification such as dehydration. Was. GPC Using tetrahydrofuran as a solvent, the number average molecular weight (Mn) and the molecular weight distribution (Mw / Mn) in terms of polystyrene were measured. -Nuclear magnetic resonance spectrum (NMR) The structure and functional groups at both terminals were confirmed and quantified by proton NMR in deuterated chloroform. -Vapor pressure osmotic pressure measurement (VPO) The number average molecular weight (Mn) was measured in chloroform.

Example 1 A 300 ml three-necked flask equipped with a cooling tube and a dropping funnel was purged with argon, and 20.64 g of 1,4-diacetoxy-2-butene (120 mmol)
l), 70 ml of toluene was added. The catalyst (Cl
₂ [P (C ₆ H ₁₁ ) ₃ ] ₂ Ru = CH-C ₆ H ₅ ) 0.3 g
(0.35 mmol) was dissolved and stirred with a mechanical stirrer. Place the flask in the oil bath and set the bath temperature to 5
Raise to 5 ° C and adjust separately 28.2g of norbornene
(300 mmol) dissolved in 70 ml of toluene was added dropwise from a dropping funnel over 5 hours. After dropping 5
The reaction was performed at 5 ° C. for 2 hours. Thereafter, 1 ml of ethyl vinyl ether was added dropwise and stirred for 30 minutes to complete the reaction. The solution after the reaction was cooled to room temperature, and methanol 1000m
The mixture was dropped into 1 to precipitate a solid. The obtained solid was dissolved in 200 ml of toluene, and 1000 ml of methanol was dissolved.
The solid was precipitated and purified. This purification operation was further repeated twice, followed by filtration and vacuum drying. Yield 28 g.

When GPC was measured, Mn in terms of polystyrene was 6,300, and Mw / Mn was 2.26. As a result of VPO measurement, Mn was 3,200. As a result of proton NMR measurement, it was found that the polymer was structurally obtained by ring-opening polymerization of norbornene. No terminal group other than an acetoxyl group was observed. From the ratio of the integral value of the proton attached to the methylene group adjacent to the acetoxyl group and the double bond and the Mn obtained by VPO, the ratio (Fn) of the acetoxyl group attached to both terminals was calculated. As a result, F
n = 1.94 (100% introduction at Fn = 2), and it was confirmed that an acetoxyl group was introduced at both ends without fail within the range of analysis error. That is, it has the following structure.

[0054]

Embedded image When Fn = 2, the molecular weight Mn calculated from proton NMR was 3,300, which was in good agreement with the VPO measurement result.

Example 2 As a cyclic unsaturated compound,
1,5-Cyclooctadiene and norbornene were used. The two central energies of the double bond are respectively -2
Since 3.38 eV and -233.00 eV, 1,
The reaction was carried out by charging 5-cyclooctadiene simultaneously with the catalyst and adding norbornene.

A 300 ml three-necked flask equipped with a cooling tube and a dropping funnel was replaced with argon, and 1,4-diacetoxy-
4.13 g (24 mmol) of 2-butene, toluene 30
ml and 25.92 g of 1,5-cyclooctadiene (2
40 mmol) was added. A catalyst (Cl ₂ [P
_{(C 6 H 11) 3]} 2 Ru = CH-C 6 H 5) 0.12g
(0.14 mmol) was dissolved and stirred with a magnetic stirrer. The flask was placed in an oil bath, the bath temperature was raised to 55 ° C, and norbornene 11.2 adjusted separately was used.
A solution of 8 g (120 mmol) dissolved in 45 ml of toluene was added dropwise from a dropping funnel over 5 hours. After the completion of the dropwise addition, the reaction was carried out at 55 ° C for 2 hours. Thereafter, 1 ml of ethyl vinyl ether was added dropwise and stirred for 30 minutes to complete the reaction. The solution after the reaction was cooled to room temperature, and methanol 100
A solid was precipitated by dropping into 0 ml. The obtained solid was dissolved in 100 ml of toluene, and 500 ml of methanol was dissolved.
The solid was precipitated and purified by reprecipitation in l. This purification operation was further repeated twice, followed by filtration and vacuum drying.
A viscous solid was obtained. Yield 13 g.

As a result of GPC measurement, M
n was 3300 and Mw / Mn was 11. VP
As a result of O measurement, Mn was 3,600. Proton NM
As a result of R measurement, it was found that the polymer was structurally ring-opening copolymerized with norbornene and 1,5-cyclooctadiene. The molar ratio of norbornene to 1,5-cyclooctadiene in the copolymer was norbornene / 1,5-cyclooctadiene = 1.4. When the molecular weight Mn was calculated from the proton NMR at Fn = 1.95,
00.

From the results of Example 1 and the results, the compound prepared by the method of the present invention has functional groups at both ends,
It was confirmed that molecular weight Mn can be calculated by proton NMR measurement. Thereafter, the molecular weight M
n was calculated.

(Example 3) A 200 ml three-necked flask equipped with a cooling tube and a dropping funnel was replaced with nitrogen, and 10.32 g (60 mmol) of 1,4-diacetoxy-2-butene and 30 ml of toluene were added. A catalyst (Cl ₂ [P
_{(C 6 H 11) 3]} 2 Ru = CH-C 6 H 5) 0.1g (0.
11 mmol) was dissolved and stirred with a mechanical stirrer. The flask was placed in an oil bath, the bath temperature was raised to 55 ° C, and 14.1 g (150
(mmol) in 35 ml of toluene was added dropwise from a dropping funnel over 2 hours. After dropping, 2 at 55 ° C
Reacted for hours. Thereafter, 1 ml of ethyl vinyl ether was added dropwise and stirred for 30 minutes to complete the reaction. The solution after the reaction was cooled to room temperature and dropped into 500 ml of methanol to precipitate a solid. The obtained solid is dissolved in toluene 1
It was dissolved in 00 ml and reprecipitated in 500 ml of methanol to precipitate and purify a solid. This purification operation was further repeated twice, followed by filtration and vacuum drying. Yield 14 g.

When GPC was measured, Mn in terms of polystyrene was 11,300, and Mw / Mn was 3.3. The molecular weight Mn calculated from proton NMR is 70
00.

Example 4 1,4-dihydroxy-2-
The reaction was carried out in the same manner as in Example 3, except that 5.28 g (60 mmol) of butene was used instead of 1,4-diacetoxy-2-butene.

When GPC of the product was measured, Mn in terms of polystyrene was 13000, and Mw / Mn was 2.6. Proton NMR was measured and hydrogen bonded to the 5-membered ring was found to be 0.9 to 2.9 ppm, 5.0, respectively.
Hydrogen bonded to a double bond at ~ 5.8 ppm;
At 4.3 ppm, a signal of hydrogen bonded to the allyl position adjacent to the terminal hydroxyl group was observed. That is, it has the following structure.

[0063]

Embedded image FIG. 1 shows a proton NMR spectrum chart. The molecular weight Mn calculated from proton NMR was 7,500.

A compound having a hydroxy functional group which did not react at all with a tungsten-based catalyst also reacted without any problem.

Example 5 A 200 ml three-necked flask equipped with a cooling tube and a dropping funnel was replaced with nitrogen, and 10.32 g (60 mmol) of 1,4-diacetoxy-2-butene, 5 ml of toluene and 30 ml of water were added. The catalyst (C
0.1 g of l ₂ [P (C ₆ H ₁₁ ) ₃ ] ₂ Ru = CH-C ₆ H ₅ )
(0.11 mmol) was dissolved and stirred with a mechanical stirrer. The solution was emulsified. The flask was placed in an oil bath, the bath temperature was raised to 55 ° C., and 14.1 g (150 mmol) of norbornene separately prepared in 35 ml of toluene
Was dropped from the dropping funnel over 2 hours. After completion of the dropwise addition, the mixture was stirred at 55 ° C. for 2 hours. The viscosity increased while the solution remained emulsified. Thereafter, 1 ml of ethyl vinyl ether was added dropwise and stirred for 30 minutes to complete the reaction. The solution after the reaction was cooled to room temperature, and methanol 500m
The mixture was dropped into 1 to precipitate a solid. The obtained solid was dissolved in 100 ml of toluene, and reprecipitated in 500 ml of methanol to precipitate and purify the solid. This purification operation was further repeated twice, followed by filtration and vacuum drying. Yield 14 g.

When GPC was measured, Mn in terms of polystyrene was 19,200 and Mw / Mn was 3.9. The molecular weight Mn calculated from proton NMR is 16
400.

(Example 6) A 100 ml three-necked flask equipped with a cooling tube and a dropping funnel was replaced with argon, and 5.16 g (30 mmol) of 1,4-diacetoxy-2-butene and 20 ml of toluene were added thereto, followed by degassing while stirring. Was replaced with argon. While flowing a small amount of argon, the catalyst (C
l ₂ [P (C ₆ H ₁₁ ) ₃ ] ₂ Ru = CH-C ₆ H ₅ ) 0.05
g (0.06 mmol) was dissolved, and the temperature of the oil bath was raised to 55 ° C. 9.0 g (75 mmol) of 2-ethylidene-5-norbornene and 20 ml of toluene were degassed,
The solution, which had been purged with argon, was placed in a dropping funnel and dropped over 3 hours. After completion of the dropwise addition, the mixture was stirred at 55 ° C. for 2 hours to complete the reaction. The solution after the reaction was dropped into methanol to precipitate a solid. The operation of dissolving the obtained solid in toluene and precipitating with methanol was repeated twice to purify.

From the result of the proton NMR measurement, it was confirmed that there was no terminal other than the acetoxy group. Proton N
The molecular weight Mn calculated from MR was 8,900.

Comparative Example 1 A 200 ml three-necked flask equipped with a cooling tube and a dropping funnel was purged with nitrogen, and 10.32 g (60 mmol) of 1,4-diacetoxy-2-butene, 14.1 g (150 mmol) of norbornene, and toluene 7
5 ml was added. The reactor was flushed with nitrogen and the catalyst (Cl ₂ [P (C
_{6 H 11) 3] 2 Ru} = CH-C 6 H 5) 0.1g (0.11
mmol) was added as a powder. The solution instantly increased in viscosity and generated heat. After stirring for 30 minutes, 0.5 ml of ethyl vinyl ether was added dropwise and stirred for 30 minutes to complete the reaction. A part of the solution after the reaction was dropped into methanol to precipitate a solid. The obtained solid was dissolved in a small amount of toluene, and reprecipitated in methanol to precipitate and purify the solid. This purification operation was further repeated twice, followed by filtration and vacuum drying.

The GPC was measured, and the Mn in terms of polystyrene was 39000. Proton NMR of this solid did not confirm that acetoxyl groups were present at both ends.

It can be understood that a compound having a functional group at both terminals having an alicyclic structure in the main chain can be produced only by reacting a norbornene compound in a mixture of a catalyst and 1,4-diacetoxy-2-butene, for example, dropwise. .

[0072]

Industrial Applicability The present invention provides a compound having both terminal functional groups having an alicyclic structure or a heterocyclic structure in the main chain and a novel method for producing the same. Can be used in a wide range of fields such as resin modifiers, plasticizers and polycondensation polymer raw materials.

[0073]

[Brief description of the drawings]

FIG. 1 is a proton NMR spectrum chart of a compound having functional groups at both ends produced in Example 4 of the present invention.

Claims (9)

[Claims] 1. A compound having a functional group at both ends represented by the general formula (I)
object. Embedded image[Wherein X is independently OR, COOR or OCOR (R
Represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
You. ), P represents an integer of 1 to 1000, m and
n represents the integer of 0-5 independently. When X = OR, R
¹~ R⁸Has independently a halogen atom, a hydrogen atom and a substituent
An optionally substituted hydrocarbon group having 1 to 20 carbon atoms (R ^ThreeAnd R^Four,
R^FiveAnd R⁶Is independently divalent in each group.
May be a Japanese hydrocarbon group;¹~ R⁸Two or more of are connected
A ring may be formed. ), Cyano group, hydroxyl group, alcohol
Xyl group, acyl group, formyl group, carboxyl group (D
Form acid anhydride from stel or two carboxyl groups
May be. ) Or a silyl group. X = COOR
Or OCOR, R¹~ R⁸Is independently a halogen source
And a hydrocarbon having 1 to 20 carbon atoms which may have a substituent
Base group (R^ThreeAnd R^Four, R^FiveAnd R⁶Are independent of each other,
May be a divalent unsaturated hydrocarbon group.¹~ R⁸Horse
Two or more may be linked to form a ring. ), Cyano
Group, hydroxyl group, alkoxyl group, acyl group, formyl group,
Carboxyl group (ester or two carboxyl groups
To form an acid anhydride. ) Or a silyl group
Represent. ] 2. The compound of the formula (I) wherein R ^{1 to} R ⁸ are independently X
When ＯＲOR, a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms (R ³ and R ⁴ , R ⁵ and R ⁶ are independently
In addition, it may be a divalent unsaturated hydrocarbon group, and two or more of R ^{1 to} R ⁸ may be linked to form a ring. )
When X = COOR or OCOR, C 1-20
Hydrocarbon groups (R ³ and R ^4, R ⁵ and R ⁶ are independently in each set, together may be a divalent unsaturated hydrocarbon group, R ¹
Two or more of R ⁸ to R ⁸ may be linked to form a ring. )
The compound having both functional groups at both ends according to claim 1, which is: 3. Both ends are each represented by the general formula (II), between which (a) a repeating unit represented by the general formula (III) and (b) one double of a cyclic unsaturated compound A compound having both ends functionalized, comprising a repeating unit represented by a ring-opened structure by cleavage of a bond. _{X- (CH 2) m -CH =} , X- (CH 2) n -CH = (II) wherein, X is OR independently, COOR or OCOR (R
Represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. ), And m and n independently represent an integer of 0 to 5. [Chemical formula 2] [Wherein, R ^{1 to} R ⁸ are each independently a halogen atom, a hydrogen atom, or an optionally substituted hydrocarbon group having 1 to 20 carbon atoms (R ³ and R ⁴ , R ⁵ and R ⁶ are each May be independently a divalent unsaturated hydrocarbon group, and two of R ^{1 to} R ⁸
Two or more may be linked to form a ring. ), A cyano group, a hydroxyl group, an alkoxyl group, an acyl group, a formyl group, a carboxyl group (an acid anhydride may be formed from an ester or two carboxyl groups), or a silyl group. ] 4. A compound according to claim 1, wherein R ^{1 to} R ^{8 in} the general formula (III) are independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms (R ³
And R ⁴ , and R ⁵ and R ⁶ are each independently 2
It may be a monovalent unsaturated hydrocarbon group, and two or more of R ^{1 to} R ⁸ may be linked to form a ring. )), The compound having both functional groups at both ends according to claim 3. 5. The repeating unit represented by (b) a ring-opened structure in which one double bond of the cyclic unsaturated compound is cleaved is a ring-opened product of a cycloalkene having 4 to 12 carbon atoms. Item 6. A compound having both ends functionalized according to Item 3 or 4. 6. An alicyclic structure or a heterocyclic structure mainly comprising a catalyst containing ruthenium or osmium from (A) a cyclic unsaturated compound and (B) a chain unsaturated compound having functional groups at both ends. In the method for producing a compound having both functional groups at both ends of a chain, (B) a mixture of a chain unsaturated compound having a functional group at both ends and a catalyst containing ruthenium or osmium is carbon-cleavable by a ring-opening polymerization reaction. A method for producing a compound having both terminal functional groups, wherein a part or all of the (A) cyclic unsaturated compound in which the two-center energy of the carbon double bond is larger than -23.2 eV is added little by little and polymerized. (B) A chain unsaturated compound having a functional group at both ends is represented by the general formula (IV): [Wherein, m and n are independently an integer of 0 to 5, X is independently O
R, COOR or OCOR (R represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms). ] The method for producing a compound having functional groups at both ends according to claim 6, which is represented by the formula: 8. The method according to claim 6, wherein the catalyst is a carbene complex of ruthenium or osmium. 9. The compound having a functional group at both ends having a number average molecular weight of 30.
9. The method for producing a compound having functional groups at both ends according to any one of claims 6 to 8, wherein the compound number is from 0 to 30,000.