JP2001323058A - Method for ring-opening polymerization of cyclic ether - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for the efficient ring-opening polymerization of a scarcely stained cyclic ether monomer. SOLUTION: This method for the ring-opening polymerization of a cyclic ether, characterized by performing the ring-opening polymerization of the cyclic ether in the presence of a promoter represented by formula (I), (II) or (III) [(p) is 0 or 1; R1 to R6, R11, R12, R31, R32, Rq+12, and Rq+19 are each H, an alkyl, an aryl or the like; (q) is 1 to 7; Z is O or S; provided that when (q) is 1, R11 and R12 may be bound to each other to form =C(R27)(R28) (R27 and R28 are each H, an alkyl, an aryl or the like)] and an initiator represented by formula (IV) [X1 to X4 are each H, a halogen, nitro, cyano, an alkyl or the like; M is boron atom or the like; Y1 and Y2 are each H, a halogen, an alkyl, an aryl or the like; (n) is 0 or 1].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for producing a polymer by ring-opening polymerization of a cyclic ether and a promoter for use in the method.

[0002]

2. Description of the Related Art Cationic, anionic, and coordinating anionic polymerizations are widely known as polymerization systems used in the ring-opening polymerization of cyclic ethers. The polymerization of these cyclic ethers has the problem that, except for some living polymerization systems, the formation of cyclic oligomers occurs, and when a monomer having a substituent is used, proton extraction is likely to occur. This is a polymerization system in which a problem that a polymer having a high molecular weight cannot be obtained or a molecular weight distribution is widened easily occurs. Further, when the strain of the cyclic ether monomer becomes small or when a certain kind of substituent is attached, the polymerizability is lowered and the polymerization becomes difficult.

[0003] Particularly, tetrahydrofuran, which is a five-membered ring, is known to have low ring distortion, so that polymerization does not proceed unless the system generates strong cations such as a strong acid. And it is difficult to control the terminal groups. The polymerization of tetrahydrofuran, as an initiator, for example (such as HClO ₄₎ strong, strong acid anhydride _{((CF 3 SO 2) 2} O , etc.), triethyl oxonium ion (Et ₃ O ⁺ PbCl ₆ ^-, etc.), photolatent Initiator (p-Cl
_{^{-Ph-N = N + PF 5}} - , etc.), etc. are used, they susceptible to chain transfer reaction and termination reaction is a known initiator system, a polymer having a low molecular weight and broad molecular weight distribution only give I couldn't.

On the other hand, the boron-based initiator BF ₃ : THF-EO initiator system has high stability of a counter anion with respect to a polymerization active species, so that a termination reaction hardly occurs, and a polymer having a high molecular weight and a narrow molecular weight distribution can be obtained. Cheap. However, since this polymerization system has a slow initiation reaction and hardly progresses alone, it is essential to add a promoter (promoter). For example, although the initiator efficiency is improved by the addition of acetic anhydride, the conversion is about 10%, which is not satisfactory from a practical viewpoint. Although the conversion of promoters such as oxiranes improves the efficiency of the initiator, it takes 2 days at 0 ° C. and bulk polymerization to reach a conversion of 80%, which is also a practically satisfactory method. is not.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing a polymer by ring-opening polymerization of a cyclic ether. More specifically, a cyclic ether monomer having less distortion is produced. It is an object of the present invention to provide a polymerization method capable of efficiently producing a ring-opened polymer even when used. Another object of the present invention is to provide a method for efficiently producing a polymer having a high molecular weight and a narrow molecular weight distribution while suppressing a termination mechanism and a chain transfer mechanism.

[0006]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above problems, and as a result, by using a promoter containing the following specific compound in combination with a specific initiator, the cyclic ether can be efficiently used. It has been found that a desired polymer can be produced by a specific polymerization, and that even a cyclic ether having a small distortion can be efficiently subjected to ring-opening polymerization. The present invention has been completed based on the above findings.

That is, the present invention relates to a method for producing a polymer by ring-opening polymerization of a cyclic ether, comprising the following general formula:
(I), general formula (II), and general formula (III):

Embedded image [In the formula (I), p represents 0 or 1; R ¹ , R ² , R ³ ,
R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted arylalkyl group, a halogen atom, an alkoxy group, a substituted or unsubstituted aryloxy Group, cyano group,
And a substituent selected from the group consisting of mono- or dialkylamino groups, wherein R ¹ and R ³ are bonded to each other to form a group represented by the formula (I)
A 4- to 10-membered substituted or unsubstituted cyclic ether may be formed together with the oxygen atom therein. In the formula (II), q represents an integer of 1 to 7; Z represents an oxygen atom or a sulfur atom;
¹¹ and R ¹² are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted arylalkyl group, a halogen atom, an alkoxy group,
A substituted or unsubstituted aryloxy group, a cyano group, and a substituent selected from the group consisting of a mono- or dialkylamino group, wherein R ¹¹ and R ¹² may be bonded to each other to represent an oxygen atom; In the case of 1, R ¹¹ and R ¹² are bonded to each other to form ＝ C (R ²⁷ ) (R ²⁸ ) (R ²⁷ and R ²⁸ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, Represents a substituent selected from the group consisting of a substituted or unsubstituted arylalkyl group, a halogen atom, an alkoxy group, a substituted or unsubstituted aryloxy group, a cyano group, and a mono- or dialkylamino group) R ^{q + 12} and R ^{q + 19} each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted arylalkyl group, a halogen atom, an alkoxy group; A substituent selected from the group consisting of a group, a substituted or unsubstituted aryloxy group, a cyano group, and a mono- or dialkylamino group. In the formula (III), R ³¹ and R ³² each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted arylalkyl group, a halogen atom, an alkoxy group, a substituted or unsubstituted It represents a substituent selected from the group consisting of an aryloxy group, a cyano group, and a mono- or dialkylamino group. And a promoter containing a compound selected from the group consisting of the following general formula (IV):

Embedded image (Wherein X ¹ , X ² , X ³ , and X ⁴ each independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkyl group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted arylalkyl group A substituent selected from the group consisting of X ¹ , X ² , X ³ , and X ⁴
One is a substituent selected from the group consisting of halogen, nitro and cyano; M is an atom selected from the group consisting of boron, aluminum, titanium, zirconium, gallium and indium. Y ¹ and Y ² each independently represent a hydrogen atom, a halogen atom, an alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted arylalkyl group, an alkoxy group, a substituted or unsubstituted arylalkyloxy group, a substituted or unsubstituted A substituent selected from the group consisting of a substituted aryloxy group, a mono- or dialkylamino group, a substituted or unsubstituted arylamino group, an alkylthio group, and a substituted or unsubstituted arylthio group; n represents 0 or 1) Performed in the presence of an initiator containing the compound to be prepared.

According to a preferred embodiment of the above invention, there is provided the above method, wherein M is a boron atom. From still another viewpoint, a promoter used together with an initiator containing a compound represented by the above general formula (IV) to produce a polymer by ring-opening polymerization of a cyclic ether, wherein the above-mentioned general formula The present invention provides a promoter comprising a compound selected from the group consisting of (I), general formula (II), and general formula (III).

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The terms used in the present specification have the following meanings. The alkyl moiety of an alkyl group or a substituent having an alkyl moiety (eg, an alkylaryl group, an alkoxy group, an alkylthio group, etc.)
It may be linear, branched, cyclic, or a combination thereof, and has 1 to 12, preferably 1 to 10, more preferably 1 to 8, more preferably 1 to 6, particularly preferably 1 to 6, carbon atoms. It is about 1 to 4. Examples of the alkyl group include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a cyclopropyl group, a n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group,
Examples thereof include a cyclobutyl group, a cyclopropylmethyl group, an n-pentyl group, and an n-hexyl group.
It is not limited to these.

The halogen atom may be any of a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, but is preferably a fluorine atom, a chlorine atom or a bromine atom. When "substituted or unsubstituted" is used for the aryl moiety of an aryl group or a substituent having an aryl moiety (eg, an arylalkyl group), the aryl ring may have one or more substituents on the ring. Means that. The position of the substituent present on the aryl ring is not particularly limited, and when two or more substituents are present,
They may be the same or different. Examples of the aryl group include a phenyl group or a naphthyl group, and more preferably a phenyl group.

[0011] Examples of the substituted aryl group include an alkyl-substituted aryl group, more preferably an alkyl-substituted phenyl group. More specifically, examples of the substituted aryl group include a p-toluyl group, a p-ethylphenyl group, and a xylyl group. Examples of the arylalkyl group include a benzyl group, a phenethyl group, and a naphthylmethyl group, and a benzyl group is preferable.

In the general formula (I), when p is 0,
Is R¹And R^TwoIs a carbon to which R^ThreeAnd R^FourJoin
An oxirane ring is formed by carbon and oxygen atoms, and p
Is 1 then R^FiveAnd R⁶Is bonded to carbon
An oxetane ring is formed with the atoms. For example, if p is
0 and R¹Is a chloromethyl group, and R^Two, R^Three,
And R^FourIs a hydrogen atom, the compound represented by the formula (I)
The thing is epichlorohydrin. R¹And R^ThreeAre connected to each other
4 to 10 membered substituents together with the oxygen atom in formula (I)
Alternatively, an unsubstituted cyclic ether may be formed. like this
A good example is R ¹And R^ThreeAre 6 to 8 members joined together
It is preferred to form a cyclic ether of
Is preferred. R¹And R^Three
P is 0 when bonded to each other to form a ring
Preferably, the representative compound is cyclohexene
Oxide.

In the formula (II), Z is preferably an oxygen atom.
New R¹¹And R¹²Are bonded to each other to represent an oxygen atom
In such a case, Z is preferably oxygen. When q is 1
R ¹¹And R¹²Are bonded to each other and = C (R²⁷) (R²⁸)
(R²⁷And R²⁸Are each independently a hydrogen atom, an alkyl
Group, substituted or unsubstituted aryl group, substituted or unsubstituted aryl
Alkyl, halogen, alkoxy, and mono
Or a substituent selected from the group consisting of dialkylamino groups
Represents a group). In this case, Z
If it is an oxygen atom, the compound of formula (II) is substituted or unsubstituted
Equivalent to diketene.

In the general formulas (I) to (III), R ¹ ,
R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ¹¹ , R ¹² , R ²⁷ , R ²⁸ ,
As the alkyl group represented by R ^{q + 12} , R ^{q + 19} , R ³¹ and R ³² , for example, an alkyl group having 1 to 12 carbon atoms can be used, and more specifically, a methyl group, an ethyl group , N-
Preferred are propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-hexyl and the like.
^{R 1, R 2, R 3} , R 4, R 5, R 6, R 11, R 12, R 27, R
^{28, R q + 12, R} q + 19, R 31, and R ³² represents an aryl group, the alkylaryl group or arylalkyl group, each phenyl group, a tolyl group, or a benzyl group and the like. R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ¹¹ ,
Examples of the substituted alkyl group represented by R ¹² , R ²⁷ , R ²⁸ , R ^{q + 12} , R ^{q + 19} , R ³¹ and R ³² include a halogen-substituted alkyl group having 1 to 20 carbon atoms, for example, chloromethyl group, bromomethyl A chloroethyl group; a hydroxy-substituted alkyl group having 1 to 20 carbon atoms, such as a hydroxymethyl group;
Preferred are 20 aryloxy-substituted alkyl groups such as a phenoxymethyl group; alkylsilyloxy-substituted alkyl groups such as a trimethylsilyloxymethyl group.

R¹, R^Two, R^Three, R^Four, R^Five, R⁶, R¹¹, R
¹², R²⁷, R²⁸, R^{q + 12}, R^{q + 19}, R ³¹, And R³²Shows
Examples of the alkoxy group include a methoxy group and an ethoxy group.
And propoxy groups. R¹,
R^Two, R^Three, R^Four, R^Five, R⁶, R¹¹, R¹², R²⁷, R²⁸,
R^{q + 12}, R^{q + 19}, R³¹, And R³²Aryloxy
Examples of the group include a phenoxy group and the like.
Wear. R¹, R^Two, R^Three, R^Four, R^Five, R⁶, R¹¹, R¹², R
²⁷, R²⁸, R^{q + 12}, R^{q + 19}, R³¹, And R³²Things that indicate
Examples of the alkylamino group or the dialkylamino group include, for example,
For example, monomethylamino group, dimethylamino group, monoethyl
And amino group, diethylamino and the like.
You.

Specific examples of the compounds represented by the formulas (I) to (III) include ethylene oxide, propylene oxide, isobutylene oxide, cis-1,2-butylene oxide, trans-1,2-butylene. Oxide, styrene oxide, cyclopentene oxide, cyclohexene oxide, epichlorohydrin, glycidol, glycidyl phenyl ether, oxetane, 2-methyloxetane, 2,2-dimethyloxetane, 2-chloromethyloxetane, 3,3-dimethyloxetane,
3-methyl-3-chloromethyloxetane, 3,3-bis (chloromethyl) oxetane, 3- (trimethylsilyloxymethyl) oxetane, β-propiolactone,
γ-butyrolactone, diketene, acetic anhydride, propionic anhydride, lacnic anhydride, isolanic anhydride, trimethylacetic anhydride, acrylic acid, crotonic anhydride, methacrylic anhydride, phenylacetic anhydride, fluoroacetic anhydride, chloroacetic anhydride, anhydrous Bromoacetic acid, iodoacetic anhydride, dichloroacetic anhydride, trichloroacetic anhydride, oxalic anhydride, malonic anhydride, succinic anhydride, maleic anhydride, glutaric anhydride, adipic anhydride, and phthalic anhydride. Of these, preferred are ethylene oxide, propylene oxide, cyclohexene oxide, epichlorohydrin, β
-Propiolactone, diketene, acetic anhydride.

The compounds represented by the general formulas (I) to (III) are known per se or can be easily produced by known methods. In addition, typical compounds are commercially available and easily available. Incidentally, the compounds represented by the above general formulas (I) to (III) may have one type depending on the type of the substituent.
Alternatively, the compound may have two or more asymmetric carbon atoms, and may have a stereoisomer such as an optically active substance or a diastereoisomer. As the promoter of the present invention, in addition to stereoisomers in pure form, any substance such as any mixture of stereoisomers and racemate may be used. In addition, hydrates or solvates of the compounds represented by the above general formulas (I) to (III) or salts thereof can also be used as the promoter.

In the compound represented by the general formula (IV), M
Is an atom selected from a boron atom, an aluminum atom, a titanium atom, a zirconium atom, a gallium atom, and an indium atom, and is preferably a boron atom. n represents 0 or 1 depending on the valence of the metal represented by M. Y ¹
Or an alkoxy group represented by Y ² includes a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group and the like, and an arylalkyloxy group includes a benzyloxy group and the like; Examples of the group include a phenoxy group. Examples of the mono or dialkylamino group represented by Y ¹ or Y ² include a monomethylamino group, a dimethylamino group, a monoethylamino group, an ethylmethylamino group, a mono-n-propylamino group, and the like. When they have groups, they may be the same or different. The arylamino group represented by Y ¹ or Y ² includes a phenylamino group, the alkylthio group includes a methylthio group and an ethylthio group, and the arylthio group includes a phenylthio group. As Y ¹ or Y ² , a methoxy group, an ethoxy group, an n-propoxy group, n
-Alkoxy groups such as butoxy groups, aryloxy groups such as phenoxy groups, and arylalkyl groups such as benzyl groups are preferred. Further, Y ¹ and Y ² are preferably groups other than a hydrogen atom.

Specific examples of the compound represented by the general formula (IV) include, for example, 3,4,5,6-tetrafluorocatecholborane, 3,4,5-trifluorocatecholborane, 3,4,4 6-trifluorocatechol borane,
3,4-difluorocatechol borane, 3,5-difluorocatechol borane, 3,6-difluorocatechol borane, 3-fluorocatechol borane, 4-fluorocatechol borane, and a fluorine atom (in these compounds, two or more fluorine atoms Compounds in which some or all of them have been replaced by chlorine or bromine atoms if present);

3,4,5,6-tetrachlorocatecholbutoxyborane, 3,4,5-trichlorocatecholbutoxyborane, 3,4,6-trichlorocatecholbutoxyborane, 3,4-dichlorocatecholbutoxyborane, 3, 5-dichlorocatechol butoxyborane, 3,
6-dichlorocatecholbutoxyborane, 3-chlorocatecholbutoxyborane, 4-chlorocatecholbutoxyborane, and the fluorine atom (part or all of them when two or more chlorine atoms are present) of these compounds A compound in which a butoxy group is replaced by an alkoxy group, an alkylamino group, or an alkylthio group;

3,4,5,6-tetracyanocatechol borane, 3,4,5-tricyanocatechol borane,
3,4,6-tricyanocatechol borane, 3,4-dicyanocatechol borane, 3,5-dicyanocatechol borane, 3,6-dicyanocatechol borane, 3-cyanocatechol borane, 4-cyanocatechol borane, and these A compound in which a hydrogen atom on a boron atom of a compound is replaced with an alkyl group, an alkoxy group, an alkylamino group, or an alkylthio group;

3,4,5,6-tetranitrocatechol borane, 3,4,5-trinitrocatechol borane,
3,4,6-trinitrocatechol borane, 3,4-dinitrocatechol borane, 3,5-dinitrocatechol borane, 3,6-dinitrocatechol borane, 3-nitrocatechol borane, 4-nitrocatechol borane, and these A compound in which a hydrogen atom on a boron atom of a compound is replaced with an alkyl group, an alkoxy group, an alkylamino group, or an alkylthio group; and a compound in which the boron atom of all the above compounds is replaced with an aluminum atom, a titanium atom, or a zirconium atom And the like.

Of these, preferred are tetrachlorocatechol borane and its alkoxy derivative, and tetrabromocatechol borane and its alkoxy derivative. However, the compound represented by the general formula (IV) is not limited to the compounds exemplified above.

The compound represented by the general formula (IV) can be produced, for example, by reacting catechol with a corresponding metal hydride, alkoxy compound, amide compound or alkylthio compound. Specific examples thereof are specifically shown in Examples of the present specification, and those skilled in the art refer to the methods described in the Examples, and by appropriately selecting starting compounds, reaction reagents, reaction conditions, and the like, The above general formula (IV)
Can be produced.

The compound represented by the above general formula (IV) may have one or more asymmetric carbons depending on the kind of the substituent, and the stereoisomer such as an optically active substance or a diastereoisomer may be present. May be present. As the initiator of the present invention, in addition to stereoisomers in a pure form, any substance such as an arbitrary mixture of stereoisomers and a racemate may be used.
When the compound represented by the general formula (IV) forms a salt, a salt-form substance may be used as the initiator. In addition, a hydrate or a solvate of the compound represented by the above general formula (IV) or a salt thereof can also be used as an initiator. As the initiator, the compound represented by the general formula (IV) may be used alone, or two or more compounds may be used in combination.

According to the method of the present invention, the above general formula (I)
Or a promoter represented by (III), and the above general formula
A polymer can be produced by ring-opening polymerization of a cyclic ether monomer using the initiator represented by (IV). As the cyclic ether monomer, a 3- to 11-membered cyclic ether containing one oxygen atom as a ring-constituting atom can be used. One or more substituents may be present on the carbon atoms constituting the ring, and when two or more substituents are present, they may be the same or different. As the substituent on the ring, for example, an alkyl group having 1 to 12 carbon atoms (methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, hexyl group, etc.) A halogen-substituted alkyl group having 1 to 20 carbon atoms (eg, chloromethyl group, bromomethyl group, chloroethyl group, etc.), an aryl group (eg, phenyl group), an arylalkyl group (eg, benzyl group), an alkylaryl group (eg, tolyl group) ), An aryloxy group (such as a phenoxy group), a halogen atom, an alkoxy group (such as a methoxy group, an ethoxy group, and a propoxy group), a dialkylamino group (such as a dimethylamino group and a diethylamino group), and a cyano group.

Specific examples of the cyclic ether monomer include ethylene oxide, propylene oxide, isobutylene oxide, cis-1,2-butylene oxide, trans-1,2-butylene oxide, styrene oxide,
Cyclopentene oxide, cyclohexene oxide, epichlorohydrin, glycidol, glycidyl phenyl ether, oxetane, 2-methyloxetane, 2,2
-Dimethyl oxetane, 2-chloromethyl oxetane,
3,3-dimethyloxetane, 3-methyl-3-chloromethyloxetane, 3,3-bis (chloromethyl) oxetane, 3- (trimethylsilyloxymethyl) oxetane, tetrahydrofuran, 2-methyl-tetrahydrofuran, 3-methyl-tetrahydrofuran 2,5-dimethoxytetrahydrofuran, 2-ethoxytetrahydrofuran, methyltetrahydrofurfuryl ether,
2,3-dihydrobenzofuran, 2,3-dihydrofuran, 2,5-dihydrofuran, tetrahydrofuran acetic acid ethyl ester, tetrahydrofurfuryl chloride, tetrahydrofurfuryl acetate, tetrahydrofurfuryl propionate, tetrahydrofurfuryl n- Butyrate, tetrahydrofurfuryl methacrylate and the like can be mentioned. Of these, ethylene oxide, propylene oxide, oxetane, and tetrahydrofuran are preferred. One kind of the cyclic ether monomer may be used alone, or two or more kinds of the cyclic ether monomers may be copolymerized.

As the promoter, it is desirable to use a compound having a larger strain than the monomer to be polymerized. In particular, when polymerizing a cyclic ether monomer having low polymerization activity such as tetrahydrofuran, among the cyclic ether compounds represented by the general formula (I),
Those having high distortion are preferably used. For example, a compound having an oxirane ring is preferable. As the promoter, a compound selected from the compounds represented by formulas (I) to (III) may be used alone, or two or more compounds may be used in combination.

The ring-opening polymerization method in the present invention is not particularly limited, and may be any of conventional polymerization methods such as a slurry polymerization method, a gas phase polymerization method, a bulk polymerization method, a solution polymerization method and a suspension polymerization method. May be used. Of these,
Slurry polymerization, solution polymerization and bulk polymerization are preferred. Further, a batch method or a continuous method may be used. General formula (I)
The method for introducing the promoter represented by the general formula (III), and the initiator represented by the general formula (IV) into the polymerization system is not particularly limited, and an appropriate method can be employed depending on the purpose. . For example, an initiator and a promoter may be added in the presence and / or absence of a monomer. Alternatively, a raw material compound for producing the compound represented by the formula (IV) may be introduced into the polymerization system to generate an initiator in the polymerization system, and a promoter may be added thereto. In that case,
The order of the raw material compounds added to the polymerization system is not particularly limited. Usually, a raw material compound (usually a catechol and a metal hydride, an alkoxy compound, an amide compound, an alkylthio compound, etc.) for producing the above-mentioned initiator is introduced into an inert solvent under an inert gas atmosphere, and The initiator can be generated in the polymerization system by bringing the compounds into contact with each other, and it is desirable to add a promoter into the system.

The polymerization temperature can be appropriately selected, but is usually in the range of -78 to 150 ° C, preferably -30 to 110 ° C. The amounts of the initiator and promoter used are not particularly limited, and can be appropriately selected according to various conditions such as the type of the cyclic ether monomer, the type of the reaction, the reaction temperature, and the polymerization time. For example, in the case of a solution polymerization system, the amount of the initiator used is preferably in the range of 10 ^-6 to 10 mol / l, particularly preferably in the range of 10 ^-4 to 1 mol / l. The ratio of the monomer and initiator (monomer / initiator (mol / mol)), for example, 1 to 10 ^6, preferably is preferably in the range such that 10 to 10 ^5. The ratio of monomer to promoter (monomer / promoter (mol / mol)) is 4 to
10 ⁵ , preferably 4 to 10 ³ . If the polymerization is performed at a ratio outside this range, the molecular weight distribution may be widened and a desired polymer may not be obtained.

In the case of polymerization using a polymerization solvent, a solvent generally used for ring-opening polymerization can be used.
Halogenated hydrocarbons such as methylene chloride and 1,2-dichloroethane; aliphatic hydrocarbons such as pentane, hexane, heptane and octane; alicyclic hydrocarbons such as cyclopentane and cyclohexane; and aromatics such as benzene, toluene and xylene Petroleum fractions such as hydrocarbons, gasoline, kerosene, light oil, etc.
Further, a mixed solvent thereof can be used.

The molecular weight of the polymer can be controlled by appropriately selecting various conditions such as the type of initiator and promoter, the type of cyclic ether monomer, the type of reaction, the reaction temperature, and the polymerization time. The polymerization degree (n) of the polymer obtained by the ring-opening polymerization method of the present invention is usually 10
~ 3000. The polymer obtained by the method of the present invention has a feature that the molecular weight distribution is narrow. For example,
When performing ring-opening polymerization of tetrahydrofuran, the ratio of the number average molecular weight (Mn) to the weight average molecular weight (Mw) Mw / M
n (= Q value) is 1.0 to 3.5, preferably 1.0 to 3.5
It is possible to produce about 2.5 polymers.

[0033]

EXAMPLES The present invention will be described more specifically with reference to the following examples, but the scope of the present invention is not limited to the following examples. In the examples, Mw and Mw / Mn are as follows:
It was calculated by permeation chromatography (GPC) in terms of polystyrene using tetrahydrofuran (THF) as a solvent. The initiator efficiency is expressed as yield (g) / Mn
(G / mol) / initiator amount (mol) × 100
(%) = Initiator efficiency (%). The identification of the borane compound was performed by mass spectrometry (MS: FinniganMa).
(measured by TSQ-700 manufactured by T Co.). For quantification of the terminal group, the sample was dissolved in CDCl ₃ and NM
It was calculated from the integrated value of the R spectrum (270 MHz, measured by JEOL Ltd.).

Example 1 Synthesis of (3,4,5,6-tetrachlorocatechol) butoxyborane 0.62 g (2.5 mmol) of tetrachlorocatechol was placed in a two-necked eggplant flask purged with nitrogen, and toluene 20 was added.
Dissolved in ml. Tributoxy borane (2.5mmo
l) Addition was allowed to react and toluene was distilled. The remaining toluene was distilled off under reduced pressure to give a pale yellow solid (3,3).
0.83 g (2.5 mmol) of 4,5,6-tetrachlorocatechol) butoxyborane was obtained. As a result of mass spectrometry, a molecular ion peak m / z: 328 (M ⁺ ·) was observed.

Example 2 2.5 mmol of (3,4,5,6-tetrachlorocatechol) butoxyborane synthesized in Example 1 was placed in a two-necked flask and purged with nitrogen. Here, THF20ml (246m
mol) and 1.3 ml of cyclohexene oxide (12.
(5 mmol) was added to initiate polymerization. Stirring was continued for 1 hour while maintaining the temperature at room temperature, and 10 ml of water was added to terminate the polymerization. 400 ml of the reaction mixture in ether
, And washed twice with 50 ml of 0.025 N NaOH aqueous solution, twice with 50 ml of water, and 0.01 N HCl aqueous solution, and the solvent was distilled off under reduced pressure. Yield 12.5 g (conversion 70%), Mn = 9700, M
w / Mn = 1.7 Initiator efficiency 51%

Example 3 1.3 ml of cyclohexene oxaside (12.5 mmol
The reaction was carried out in the same manner as in Example 2, except that l) was changed to 0.8 ml (12.5 mmol) of oxetane. Yield 11.8 g (conversion 65%), Mn = 8020, M
w / Mn = 1.75 Initiator efficiency 58%

Example 4 1.3 ml of cyclohexene oxide (12.5 mmol
l) with epichlorohydrin 0.2 ml (2.5 mmo)
The reaction was carried out in the same manner as in Example 2, except for changing to l). Yield 13.0 g (conversion 73%), Mn = 6300, M
w / Mn = 2.0 Initiator efficiency 83%

Example 5 (Comparative Example) The reaction was carried out in the same manner as in Example 2, except that no cyclohexene oxide was used. Yield 11.6 g (conversion 65%), Mn = 28500,
Mw / Mn = 1.87 Initiator efficiency 16%

Example 6 (Comparative Example) (3,4,5,6-Tetrachlorocatechol) Polymerization was carried out in the same manner as in Example 2 except that butoxyborane was changed to catecholbutoxyborane. Polymerization did not proceed.

Example 7 2.5 mmol of (3,4,5,6-tetrachlorocatechol) butoxyborane synthesized in Example 1 was placed in a two-necked flask and purged with nitrogen. Here, THF20ml (246m
(mol) and 0.23 ml (2.5 mmol) of acetic anhydride, and the polymerization was started. Stirring was continued for 1 hour while maintaining the temperature at room temperature, and 10 ml of water was added to terminate the polymerization. The reaction mixture was dissolved in 200 ml of ether and
After adding 5 ml of 2N NaOH aqueous solution and stirring vigorously,
Only the ether layer was purified through a column of silica gel 10 g. The solvent was distilled off under reduced pressure to obtain a polymer. Yield 12.1 g (conversion 68%), Mn = 15800,
Mw / Mn = 1.67 Initiator efficiency 51%

Example 8 1.3 ml of cyclohexene oxide (12.5 mmol)
l) with 0.16 ml of β-propiolactone (2.5 mm
ol), except that the reaction was carried out in the same manner as in Example 2. Yield 11.5 g (conversion 64%), Mn = 8360, M
w / Mn = 2.0 Initiator efficiency 55%

Example 9: Synthesis of tetrachlorocatechol borane 0.62 g (2.5 mmol) of tetrachlorocatechol was placed in a two-necked eggplant flask purged with nitrogen, and toluene 20 was added.
Dissolved in ml. Borane dimethyl sulfide 0.24
ml (2.5 mmol) and add 110 with stirring.
Heated to ° C. The solvent was distilled off under reduced pressure to obtain 0.64 g of white solid tetrachlorocatechol borane. As a result of mass spectrometry, molecular ion peak m / z: 256 (M
⁺・) Was observed.

Example 10: Synthesis of tetrachlorocatechol isopropoxyborane Tetrachlorocatechol borane synthesized in Example 9 0.64
g (2.5 mmol) was placed in a two-necked eggplant flask purged with nitrogen, and dissolved in 20 ml of toluene. 0.15 ml (2.5 mmol) of isopropanol was added to this solution to cause a reaction. After reacting for 24 hours, toluene was distilled off under reduced pressure to obtain 0.79 g (2.5 mmol) of white solid tetrachlorocatechol isopropoxyborane. As a result of mass spectrometry, molecular ion peak m / z: 31
4 (M ⁺ ·) was observed.

Example 11: Synthesis of tetrachlorocatechol phenoxyborane 0.24 g of phenol instead of isopropanol
(2.5 mmol) in the same manner as in Example 11, except that 0.87 of white solid tetrachlorocatechol borane was used.
g (2.5 mmol) were obtained. As a result of mass spectrometry, a molecular ion peak m / z: 348 (M ⁺ ·) was observed.

[0045]

According to the present invention, a polymer having a high molecular weight and a narrow molecular weight distribution can be efficiently produced by polymerizing a cyclic ether using an initiator and a promoter.

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Claims (3)

[Claims] A method for producing a polymer by ring-opening polymerization of a cyclic ether, comprising the following general formula (I), general formula (II),
And the general formula (III): [In the formula (I), p represents 0 or 1; R ¹ , R ² , R ³ ,
R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted arylalkyl group, a halogen atom, an alkoxy group, a substituted or unsubstituted aryloxy Group, cyano group,
And a substituent selected from the group consisting of mono- or dialkylamino groups, wherein R ¹ and R ³ are bonded to each other to form a group represented by the formula (I)
A 4- to 10-membered substituted or unsubstituted cyclic ether may be formed together with the oxygen atom therein. In the formula (II), q represents an integer of 1 to 7; Z represents an oxygen atom or a sulfur atom;
¹¹ and R ¹² are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted arylalkyl group, a halogen atom, an alkoxy group,
A substituted or unsubstituted aryloxy group, a cyano group, and a substituent selected from the group consisting of a mono- or dialkylamino group, wherein R ¹¹ and R ¹² may be bonded to each other to represent an oxygen atom; In the case of 1, R ¹¹ and R ¹² are bonded to each other to form ＝ C (R ²⁷ ) (R ²⁸ ) (R ²⁷ and R ²⁸ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, Represents a substituent selected from the group consisting of a substituted or unsubstituted arylalkyl group, a halogen atom, an alkoxy group, a substituted or unsubstituted aryloxy group, a cyano group, and a mono- or dialkylamino group) R ^{q + 12} and R ^{q + 19} each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted arylalkyl group, a halogen atom, an alkoxy group; And a substituent selected from the group consisting of a group, a substituted or unsubstituted aryloxy group, a cyano group, and a mono- or dialkylamino group. In the formula (III), R ³¹ and R ³² each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted arylalkyl group, a halogen atom, an alkoxy group, a substituted or unsubstituted And a substituent selected from the group consisting of an aryloxy group, a cyano group, and a mono- or dialkylamino group. And a promoter containing a compound selected from the group consisting of the following general formula (IV): (Wherein X ¹ , X ² , X ³ , and X ⁴ each independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkyl group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted arylalkyl group A substituent selected from the group consisting of X ¹ , X ² , X ³ , and X ⁴
One is a substituent selected from the group consisting of halogen, nitro, and cyano; M is an atom selected from the group consisting of boron, aluminum, titanium, zirconium, gallium, and indium. Y ¹ and Y ² each independently represent a hydrogen atom, a halogen atom, an alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted arylalkyl group, an alkoxy group, a substituted or unsubstituted arylalkyloxy group, a substituted or unsubstituted A substituent selected from the group consisting of a substituted aryloxy group, a mono- or dialkylamino group, a substituted or unsubstituted arylamino group, an alkylthio group, and a substituted or unsubstituted arylthio group; n represents 0 or 1) Carried out in the presence of an initiator containing the compound to be prepared. 2. The method according to claim 1, wherein M is a boron atom. 3. A promoter used together with an initiator containing a compound represented by the general formula (IV) according to claim 2 to produce a polymer by ring-opening polymerization of a cyclic ether. 2. A promoter comprising a compound selected from the group consisting of the general formulas (I), (II) and (III) according to 1.