JPH1180363A - New production of cyclic polymer and new cyclic polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for readily producing a cyclic polymer whose production in practical scale has been extremely difficult hitherto and obtain a new cyclic polymer. SOLUTION: (B) A bifunctional low molecular or polymer having charge opposite to that of the component A, e. g. a bifunctional carboxylic acid anion is introduced as a pair ion into (A) a linear polymer having functional groups capable of having charge at both ends, e. g. a linear polymer having cyclic ammonium bases having open ring reactivity at both ends and the ion bond is converted to a covalent bond.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel cyclic polymer and a method for producing the same, and more particularly, to two or more functional groups having a positive or negative charge introduced at both ends of a linear polymer. Mechanical and mechanical properties, melting properties, and moldability and processability obtained by introducing an ionic compound having the opposite charge as a counter ion and converting the ionic bond between them into a covalent bond The present invention relates to a cyclic polymer having novel physical properties such as lubricity and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, as a method for producing a cyclic polymer, a functional group introduced at both ends of a linear polymer and an equimolar amount of a bifunctional complementary reactive low-molecular compound are used. A method based on a two-molecule reaction in which the reaction is carried out for a long time under diluting conditions, or an intramolecular reaction between functional groups having complementary reactivity introduced at both ends of a linear polymer under high diluting conditions The former method is known, but in the former, 2 at a low concentration is used.
The extremely low efficiency of intermolecular reactions results in extremely low yields of cyclic polymers.In the latter case, the chemical reaction for introducing asymmetric complementary reactive functional groups at both ends of a linear polymer requires multiple steps. And the general scope of application is significantly limited. For this reason, a general method which can easily produce a cyclic polymer on a scale that can be used industrially has not been developed.

[0003]

SUMMARY OF THE INVENTION The present invention relates to a reactive functional group introduced at both ends of a linear polymer, and a complementary functional group which is required to proceed quantitatively by equimolar charging with the reactive functional group. In order to realize an efficient reaction with a compound having two or more functional groups having high reactivity, an ionic bond is formed by electrostatic interaction as a counter ion, and this is covalently bonded by an appropriate post-treatment. The present inventors have found a complementary functional group pair that can be converted into a cyclic polymer, which makes it possible to easily provide a cyclic polymer that has been extremely difficult to produce on a practical scale. Still another object of the present invention is to provide a method for producing a cyclic polymer in which the size of the ring and the type of the polymer chain constituting the ring structure can be arbitrarily selected, and a novel cyclic polymer obtained by the method. .

[0004]

SUMMARY OF THE INVENTION The present invention comprises two or more functional groups having opposite charges introduced as counterions to positive or negative ionic functional groups introduced at both ends of a linear polymer. An object of the present invention is to provide a polymer compound having a novel cyclic structure by a conversion reaction of an ionic bond into a covalent bond, which is carried out by an appropriate means, with respect to a compound, and a highly efficient method for producing a cyclic polymer compound.

That is, the present invention relates to a linear polymer (A) having a functional group capable of carrying a charge at both terminals and a terminal group of the linear polymer capable of having an opposite charge and having the opposite group. Is reacted with a low-molecular or high-molecular compound (B) having two or more functional groups capable of converting an ionic bond of a counter ion formed into a covalent bond to form the linear polymer (A) with the low-molecular compound. The present invention relates to a polymer compound having a cyclic structure composed of a molecule or a polymer compound (B). More specifically, the present invention provides the following general formula (1):

[0006]

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[0007] (wherein, R ₁ represents a divalent polymer chain, R ₂
And R ₃ represents an aliphatic hydrocarbon chain having 3 to 7 carbon atoms, R ₄ represents a hydrocarbon residue of dicarboxylic acid,
R ₅ and R ₆ each independently represent hydrogen or a lower alkyl group. The present invention relates to a polymer compound having a cyclic structure represented by the following formula: The present invention also provides a linear polymer (A) having a functional group capable of having an electric charge at both terminals and an end group of the linear polymer capable of having an opposite charge and having the opposite charge. Or high molecular compound (B) having two or more functional groups capable of converting an ionic bond of a counter ion into a covalent bond
And converting the ionic bond of the obtained cyclic counterion compound into a covalent bond, thereby producing a polymer compound having a cyclic structure. Further, the present invention is formed from a linear polymer (A) having a functional group capable of carrying a charge at both ends and an end group of the linear polymer capable of having an opposite charge. A low-molecular or high-molecular compound (B) having two or more functional groups capable of converting an ionic bond of a counter ion into a covalent bond with the linear polymer (A) and the low-molecular or high-molecular compound (B )) And a polymer counter ionic compound having a cyclic structure in which each charge is paired.

The present invention will be described in more detail below. The polymer compound having a cyclic structure of the present invention can be obtained by performing a binding reaction between functional groups at a low concentration. For this purpose, first, an ionic functional group that generates an electrostatic long-range attractive force between the functional groups is introduced into the terminal of the linear polymer. Next, as a counter ion of this terminal ionic group, a selective reaction occurs with the counter ion by appropriate post-treatment,
A substance capable of converting an ionic bond into a covalent bond is introduced. At this time, the ion-pair ion of the terminal group corresponds to one-to-one,
The stoichiometry for performing an efficient reaction can be satisfied. Finally, a cyclic polymer can be obtained in good yield by converting an ion pair into a covalent bond by heat treatment or the like under dilution conditions, if necessary.

The polymer compound having a cyclic structure according to the present invention is different from the linear polymer (A) having a functional group capable of carrying an electric charge at both terminals and the linear polymer (A) having the opposite charge and having the above-mentioned linear structure. It can be produced by reacting a low-molecular or high-molecular compound (B) having two or more functional groups capable of converting a ionic bond of a counter ion formed from a terminal group of the polymer into a covalent bond. The linear polymer (A) having a functional group capable of carrying a charge of the present invention at both ends.
Is obtained by introducing a functional group capable of having a charge into a linear polymer at both ends. The linear polymer compound is not particularly limited as long as it is linear and can introduce necessary functional groups at both ends thereof. For example, the following general formula (2)

HO-R ₁ -OH (2) (wherein, R ₁ has the same meaning as described above). In the formula (2), R ₁ represents a divalent polymer chain, for example, polyethers such as polytetrahydrofuran and polyalkylene oxide, polyethylene, polypropylene, polyisobutylene, porobutadiene, polyisoprene, polystyrene and the like. Derivatives, polyacrylic acid ester and polymethacrylic acid ester derivatives, poly (vinyl acetate), polysiloxanes, polyesters, polyamides, polyurethanes, and the like, and copolymers and block polymers containing these as components are exemplified. can do. The degree of polymerization of these polymer components is not particularly limited, but is 10 or more and 10,000 or more.
The following degree is preferable, and in terms of molecular weight, for example, about 200
To 1,000,000, preferably 1000 to 50
There are about ten thousand ones, and an appropriate size can be selected according to the application. For example, relatively high molecular weight materials are preferable for applications such as films and fibers, and relatively low molecular weight materials can be used for additives such as modifiers.

The functional group capable of having a charge to be introduced into both ends of the linear polymer, that is, the ionic functional group, contains a nitrogen atom or a sulfur atom, and the atom portion thereof is ionized. Preferred are a 5-membered ring group and a 5-membered ring group, for example, a quaternized 4-membered ammonium base, 5-membered ammonium base and 6-membered bicyclic ammonium having a nitrogen atom substituted by a lower alkyl group or a phenyl group. Bases and 5-membered ring sulfonium bases can be exemplified. More specifically, a pyrrolidinium group, a piperidinium group, an azetidinium group, a quinuclidinium group, a tetrahydrothiophenium group, and the like can be given. Further, the functional group capable of carrying a charge of the present invention, that is,
As the ionic functional group, not only a cationic functional group but also an anionic functional group such as a carboxylate can be used.

The method for introducing an ionic functional group into the linear polymer compound is not particularly limited, and it can be introduced by a usual method for introducing a functional group. The above-mentioned ionic functional group can also be directly introduced into the terminal of the linear polymer compound, but instead of directly introducing the ionic functional group, a low-molecular or high-molecular compound having an ionic functional group at the terminal And the above-mentioned linear polymer (A) can also be obtained by reacting with the linear polymer compound.

[0013] Further, according to the present invention, there is provided a low-molecular compound having two or more functional groups capable of converting the ionic bond of a counter ion formed with the terminal group of the linear polymer into a covalent bond. The molecule or polymer compound (B) is an ionic functional group having a charge opposite to that of the ionic functional group of the linear polymer (A), and is an ionic functional group of the linear polymer (A). The compound is not particularly limited as long as it is a compound having two or more, preferably two, functional groups capable of forming a counter ion with the functional functional group and converting the formed ionic bond into a covalent bond. Such ionic functional groups include, for example, carboxylate, sulfonate, alcoholate and the like, preferably carboxylate. When the ionic functional group of the linear polymer (A) is anionic, it may be a cationic functional group such as ammonium.

A low molecule or a low molecule having two or more functional groups capable of having the opposite charge of the present invention and capable of converting an ionic bond of a counter ion formed from the terminal group of the linear polymer into a covalent bond. as the polymer compound (B), for example, the following general formula ^{(3) Y + - OOC-} R 4 -COO - Y + (3) ( in the formula R ₄ are as defined above, Y is a cation The compound of the dicarboxylate dianion represented by the formula: The hydrocarbon residue of the dicarboxylic acid represented by R ₄ in the formula (3) represents a residue obtained by removing two carboxyl groups from the dicarboxylic acid, and may be any of an aliphatic group and an aromatic group. It may contain a heteroatom such as an oxygen atom or a nitrogen atom, and may be substituted with various functional groups which are inert under the reaction conditions of the synthesis reaction of the cyclic polymer of the present invention. The hydrocarbon residue R ₄ of the dicarboxylic acid is not particularly limited as long as it is a low-molecular or high-molecular compound as long as it can open the ring as a counter ion.
It is preferably about 00 or less. Specific examples of the dicarboxylic acid include low molecular dicarboxylic acid anions such as terephthalic acid, biphenyldicarboxylic acid, maleic acid, fumaric acid, and adipic acid, and high molecular dicarboxylic acids having a carboxylic acid group at both terminals.

[0015] The present invention relates to a method of forming the above-mentioned linear polymer (A) and a compound (B) having two or more functional groups to be paired with the linear polymer (A) by a chemical bond such as an ionic bond which can be relatively easily formed. The gist of the present invention is to preliminarily form a pre-stage of a target cyclic structure, and to form a covalent bond by an appropriate method. Such a pre-cyclic structure can be formed and the covalent bond can be formed. It will be apparent to those skilled in the art that any combination can be selected as the functional groups of the linear polymer (A) and the compound (B) as long as they can be converted. As such a combination, for example, a combination that can be easily introduced as a counter ion and that can convert an ionic bond into a covalent bond by a ring-opening reaction or the like by appropriate post-treatment, heating, or the like is selected. Examples of a preferable combination include a 5-membered ammonium salt group and biphenyldicarboxylic acid, and a 6-membered bicyclic ammonium salt group and terephthalic acid, but the selectable functional group is not limited to this combination.

As a method for producing the cyclic polymer according to the present invention, known methods (Y. Tezuka, EJ Goe) are used.
thals, Mcromol. Chem. , 18
8, 783, (1987); Tezuka, H .; l
mai, T .; Shiomi, Macromol. Che
m. Phys. , 198, 627 (1997); a linear polymer (A) having a distorted cyclic ammonium base at both ends synthesized by Japanese Patent Application No. 1-102356).
In a water containing a dicarboxylate (B), or by precipitation, or a linear polymer having a distorted cyclic ammonium base at both terminals and an ionic group concentration adjusted to an equal amount, and a dicarboxylate. Water or other suitable solvent,
For example, an ion exchange reaction is carried out by a method such as coprecipitation in a solvent such as aqueous alcohol or alcohol, and a cyclic polymer precursor having an ion pair having an appropriate combination of reactivity as a terminal group can be synthesized. it can. Then, after diluting this precursor with an appropriate solvent and selecting conditions under which the intramolecular reaction is advantageous for the intermolecular reaction, post-treatment such as heating at an appropriate temperature is performed to share ionic bonds. By converting into a bond, a cyclic polymer can be synthesized in high yield.

The proportion of the linear polymer (A) having a cyclic ammonium base and the dicarboxylate (B) used is such that a counter ion is formed. May be used in excess, and generally, the dicarboxylic acid salt (B) is used in an amount of 0.5 to 10 mol, preferably about 5 mol, per 1 mol of the linear polymer (A). Use in proportions. Although the concentration of the linear polymer (A) in the reaction solution varies depending on the type of the linear polymer used, it is not specified unconditionally, but usually 0.1 g of the linear polymer (A) is used. It is preferable to carry out the reaction in the range of about 50 g / l to 50 g / l. The conversion of the ionic bond thus formed into a covalent bond can be performed by a method such as heating or light irradiation, but is preferably performed by normal heating. The reaction temperature in the case of heating is about 30 ° C. to 150 ° C., preferably about 40 ° C. to 100 ° C.

The cyclic polymer compound of the present invention thus obtained, in particular, the cyclic polymer compound of the present invention formed into a cyclic structure using the low molecular compound (B) has a melting point, solubility,
Although it is almost the same as the raw material linear polymer (A) in properties that are not so affected by the polymer terminal groups such as film forming properties, it has a unique structure in which it has no terminal groups due to its cyclic structure. Since it has a topological structure, it is completely different from the raw material linear polymer (A) and has many polymer properties related by the presence of the terminal group, for example, physical or mechanical properties such as processability and surface properties. It can be used as a polymer material having novel physical properties that could not be expressed conventionally in various properties.
For example, the polymer compound having a cyclic structure of the present invention is used as a polymer material such as a resin, a film, a fiber, a rubber material, various modifying materials, and various additive materials. Modification materials to improve stability,
Useful as an additive material.

[0019]

EXAMPLES Next, the present invention will be described with reference to examples, but the present invention is not limited to these examples. Example 1 (Introduction of biphenyldicarboxylate anion as a counter anion into polytetrahydrofuran having a pyrrolidinium base at both ends and heat treatment of polytetrahydrofuran having a pyrrolidinium base at both ends with the obtained dicarboxylate anion as a counterion 0.52 g of polytetrahydrofuran (molecular weight 4500) having a pyrrolidinium base at both terminals having a trifluoromethanesulfonic acid anion as a counter ion is dissolved in 1.2 ml of tetrahydrofuran, and this is dissolved in sodium biphenyldicarboxylate. 200m with 0.16g dissolved
When dropped into 1 liter of cold water with stirring, a white precipitate (I) is formed. This was filtered and collected, yielding 0.48 g of reaction product. Then 0.20 of this product
g was dissolved in 200 ml of toluene, heated at 80 ° C. for 20 hours, insoluble matter was removed by filtration, toluene was distilled off, and then dissolved in a small amount of benzene and freeze-dried to obtain a white powdery product (II). 0.18 g was isolated.
The ¹ H-NMR and IR diagrams of (I) and (II) are shown in FIGS. 1 to 4, respectively, and the GPC diagram of (II) is shown in FIG. 5 together with that of linear polytetrahydrofuran having the same molecular weight. As a result of these analytical measurements, it was confirmed that (I) was a polytetrahydrofuran having a pyrrolidinium base at both ends with a dicarboxylate anion as a counter ion, and (II) was a cyclic polytetrahydrofuran.

Example 2 (Introduction of terephthalate anion as a counter anion into polytetrahydrofuran having a pyrrolidinium base at both terminals, and introduction of polytetrahydrofuran having a pyrrolidinium base at both terminals using the obtained terephthalate anion as a counter ion Synthesis of cyclic polytetrahydrofuran by heat treatment) 0.3 g of polytetrahydrofuran (molecular weight: 4500) having a pyrrolidinium base at both ends having a trifluoromethanesulfonate anion as a counter ion was dissolved in 0.8 ml of tetrahydrofuran, and this was dissolved in sodium terephthalate. A white precipitate is formed by dropping with stirring into 120 ml of cold water in which 0.07 g of a salt is dissolved. This is filtered, collected, dissolved again in 0.8 ml of tetrahydrofuran, and added dropwise with stirring to 120 ml of cold water in which 0.07 g of sodium terephthalate is dissolved, whereby a white precipitate (III) is formed. When this is filtered and collected,
0.22 g of the reaction product was obtained. Next, 0.02 g of this product was dissolved in 20 ml of toluene,
After heating for 0 hours, the toluene was distilled off, and the residue was dissolved in a small amount of benzene and freeze-dried.
016 g were isolated. ¹ H-N of (III) and (IV)
The MR and IR diagrams are shown in FIGS. 6 to 9 respectively, and the GP in (IV)
The C diagram is shown in FIG. 10 together with that of linear polytetrahydrofuran having the same molecular weight. As a result of these analytical measurements,
It was confirmed that (III) was a polytetrahydrofuran having a pyrrolidinium base at both ends with a terephthalate anion as a counter ion, and (IV) was a cyclic polytetrahydrofuran.

The polytetrahydrofuran having a pyrrolidinium base at both ends and having a trifluoromethanesulfonic acid anion as a counter ion used as a raw material in the present embodiment (molecular weight: 4200) is a tetrahydrofuran having a polymerization initiator of trifluoromethanesulfonic anhydride. It was synthesized by terminating the living polymerization with excess N-methylpyrrolidine.

[0022]

As described above, the present invention provides a high molecular compound having a cyclic structure and an efficient and industrial method for producing the same, comprising a resin, a film, a fiber, a rubber material, various modified materials, A novel polymer material useful as an additive material can be provided.

[Brief description of the drawings]

FIG. 1 is an NMR chart of a polymer compound having a counter ion structure of Example 1 of the present invention. (A) ~ in the figure
The peak in (h) assigns the corresponding hydrogen atom in the chemical structural formula.

FIG. 2 is a chart of infrared absorption (IR) of a polymer compound having a counter ionic structure of Example 1 of the present invention.

FIG. 3 is an NMR chart of a polymer compound having a cyclic structure of Example 1 of the present invention. (A) ~ in the figure
The peak in (h) assigns the corresponding hydrogen atom in the chemical structural formula.

FIG. 4 is a chart of infrared absorption (IR) of the polymer compound having a cyclic structure of Example 1 of the present invention.

FIG. 5 is a chart of gel permeation chromatography (GPC) of a polymer compound having a cyclic structure (cyclic) and a linear polymer compound (linear) as a raw material compound thereof according to Example 1 of the present invention. It is. The horizontal axis in the figure indicates the elution volume (ml).

FIG. 6 is an NMR chart of a polymer compound having a counter ion structure of Example 2 of the present invention. (A) ~ in the figure
The peak in (f) assigns the corresponding hydrogen atom in the chemical structural formula.

FIG. 7 is a chart of infrared absorption (IR) of a polymer compound having a counter ionic structure of Example 2 of the present invention.

FIG. 8 is an NMR chart of a polymer compound having a cyclic structure of Example 2 of the present invention. (A) ~ in the figure
The peak in (f) assigns the corresponding hydrogen atom in the chemical structural formula.

FIG. 9 is a chart of infrared absorption (IR) of a polymer having a cyclic structure according to Example 2 of the present invention.

FIG. 10 is a chart of gel permeation chromatography (GPC) of a polymer compound having a cyclic structure (cyclic) and a linear polymer compound (linear) as a raw material compound thereof in Example 2 of the present invention. It is. The horizontal axis in the figure indicates the elution volume (ml).

Claims (8)

[Claims] 1. A linear polymer (A) having a functional group capable of having an electric charge at both terminals and an end group of the linear polymer capable of having an opposite charge and being formed. The functional group capable of converting the ionic bond of the counter ion into a covalent bond is 2
A high molecular compound having a cyclic structure composed of the linear polymer (A) and the low molecular or high molecular compound (B) by reacting at least one low molecular or high molecular compound (B). 2. The polymer compound having a cyclic structure according to claim 1, wherein the functional group capable of having a charge of the linear polymer (A) is a cyclic amine or a cyclic ammonium salt. 3. A function capable of having the opposite charge of the low molecular weight or high molecular weight compound (B) and capable of converting the ionic bond of a counter ion formed from the terminal group of the linear polymer into a covalent bond. The polymer compound having a cyclic structure according to claim 1, wherein the group is a carboxyl group or a salt thereof. 4. The polymer compound having a cyclic structure according to claim 1, wherein the group formed by the reaction for forming the cyclic structure is an aminoester group. 5. The following general formula (1): (Wherein, R ₁ represents a divalent polymer chain, R ₂ and R ₃ represent an aliphatic hydrocarbon chain having 3 to 7 carbon atoms, and R ₄
Represents a hydrocarbon residue of a dicarboxylic acid, and R ₅ and R ₆ each independently represent hydrogen, a lower alkyl group or a phenyl group. The polymer compound having a cyclic structure according to any one of claims 1 to 4, wherein 6. A linear polymer (A) having a functional group capable of having a charge at both terminals and an end group of the linear polymer capable of having an opposite charge and being formed. The functional group capable of converting the ionic bond of the counter ion into a covalent bond is 2
A method for producing a high molecular compound having a cyclic structure, comprising mixing a low molecular or high molecular compound (B) having at least one compound and converting the ionic bond of the obtained cyclic counterion compound into a covalent bond. 7. The linear polymer (A) is a linear polymer having a cyclic ammonium base having ring-opening reactivity at both ends, and the low-molecular-weight or high-molecular-weight compound (B) is a dicarboxylic acid dianion. The method for producing a polymer compound having a cyclic structure according to claim 6, wherein 8. A linear polymer (A) having a functional group capable of having an electric charge at both ends and an end group of the linear polymer capable of having an opposite charge and being formed. The functional group capable of converting the ionic bond of the counter ion into a covalent bond is 2
And a low-molecular or high-molecular compound (B) having at least one low-molecular or high-molecular compound (B) such that the respective charges of the linear polymer (A) and the low-molecular or high-molecular compound (B) form a pair. Having a high molecular counter ion compound.