JP2005320403A - Cyclic polymer compound and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a cyclic polymer compound excellent in thermal stability and a method for producing the same. <P>SOLUTION: This cyclic polymer compound is characterized by forming covalent bonds between both ends of a polymer main chain and both ends of a low molecular chain and has ≥4,000 molecular weight, and the both ends of the low molecular chain form covalent bonds with a part of the monomer constituting the polymer main chain. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a cyclic polymer compound having excellent thermal stability and a method for producing the same.

  In general, a high molecular compound has a high molecular weight main chain in which several hundred to several tens of thousands of atoms are connected by a covalent bond, and this main chain has both ends.

  In contrast, if a so-called cyclic polymer compound having no terminal in the main chain can be synthesized, various properties such as mechanical properties and processability can be expressed in the polymer compound having a terminal in the main chain. It is possible to provide a material that exhibits no new characteristics. However, a method for producing a cyclic polymer compound on a scale that can be used industrially has not been established yet.

Therefore, the present inventor has heretofore introduced, for example, as shown in Patent Document 1, an aliphatic cyclic amine introduced into both ends of a polymer main chain of a high molecular compound and a carboxyl group introduced into both ends of a low molecular compound. And forming an ion bond between the cyclic amine and the carboxyl group to form a cyclic polymer compound. Have developed a method.
JP 2004-107311 A

  However, in the method shown in Patent Document 1, an amino ester is formed between both ends of the polymer chain and both ends of the low molecular weight compound by opening the cyclic amines at both ends of the polymer main chain. The obtained cyclic polymer compound has a problem that its thermal stability is lower than that of a carboxylic acid ester type, for example.

  The present invention has been made in view of the above-described conventional problems, and an object thereof is to provide a cyclic polymer compound excellent in thermal stability and a method for producing the same.

  In order to solve the above problems, a cyclic polymer compound according to an embodiment of the present invention is a cyclic polymer compound having a molecular weight of 4000 or more, wherein both ends of a polymer main chain and both ends of a low molecular chain are covalently bonded. Thus, both ends of the low molecular chain form the covalent bond with a part of the monomer constituting the polymer main chain.

  The polymer main chain may be a linear polymer chain having no branched chain.

  The polymer main chain may be a polymer chain having a branched chain.

  The covalent bond may be an ester bond.

  The cyclic polymer compound may include an ester bond only between both ends of the polymer main chain and both ends of the low molecular chain.

（式（２）中、Ｒ１は、分岐鎖を有し、又は分岐鎖を有さない分子量４０００以上のポリマー鎖であり、Ｒ２は、直鎖状、分岐状、又は環状の低分子鎖である。） The cyclic polymer compound may be a cyclic polymer compound having a molecular weight of 4000 or more represented by the following general formula (2).

(In the formula (2), R1 is a polymer chain having a molecular weight of 4000 or more which has a branched chain or no branched chain, and R2 is a linear, branched or cyclic low molecular chain. .)

  The method for producing a cyclic polymer compound according to an embodiment of the present invention includes a precursor polymer compound having a first ionic functional group at both ends of a polymer main chain, and the first polymer compound at both ends of a low molecular chain. A low molecular compound having a second ionic functional group having a charge opposite to that of the one ionic functional group, and the first ionic functional group is prepared from the precursor polymer compound and the low molecular compound. An ionic bond is formed between the group and the second ionic functional group to produce a polymer complex composed of the precursor polymer compound and the low molecular compound, and A cyclic polymer compound in which one ionic functional group is eliminated to form a covalent bond between the second ionic functional group and a part of the monomer constituting the polymer main chain of the precursor polymer compound Is generated.

  Moreover, in the said cyclic polymer compound manufacturing method, the said covalent bond is good also as an ester bond.

  In the method for producing a cyclic polymer compound, the first ionic functional group may be an aliphatic cyclic amine.

  In the cyclic polymer compound manufacturing method, the second ionic functional group may be a carboxyl group.

  A cyclic polymer compound having excellent thermal stability and a method for producing the same can be provided.

  Hereinafter, an embodiment of the present invention will be described. The cyclic polymer compound according to this embodiment includes a polymer compound having an ionic functional group at both ends of the polymer main chain (hereinafter referred to as precursor polymer compound A), and both ends of the precursor polymer compound A. A low molecular compound B having an ionic functional group having a charge opposite to that of the ionic functional group at both ends of the low molecular chain. Here, hereinafter, for the purpose of distinction, the ionic functional groups introduced into both ends of the precursor polymer compound are referred to as first ionic functional groups X, and the ionic functional groups introduced into both ends of the low molecular compound The group is called the second ionic functional group Y.

The precursor polymer compound A is represented by the following general formula (3).

  Here, in the formula (3), R1 is a polymer main chain of the precursor polymer compound A. For example, polyethers such as polytetrahydrofuran and polyalkylene oxide, polyethylene, polypropylene, polyisobutylene, polybutadiene, polyisoprene, polystyrene Polyolefins and derivatives thereof, polyacrylic acid esters, polymethacrylic acid and derivatives thereof, polyvinyl acetate, polysiloxanes, polyesters, polyamides, polyurethanes, etc., and copolymers containing these as components And block polymers. The polymer main chain R1 may be a linear polymer chain having no branched chain, or may be a polymer chain having a branched chain formed by graft polymerization or the like.

In Formula (3), X is a first ionic functional group introduced into both ends of the polymer main chain R1, which contains a nitrogen atom or a sulfur atom, and an anionic portion in which the atom portion is ionized. Or it is a cationic functional group. Among those used as the first ionic functional group X, as an anionic one, for example, a five-membered sulfonium base, and as a cationic one, for example, an azetidinium group, a pyrrolidinium group, a piperidinium group, a quinuclidinium group , Tetrahydrothiophenium groups, and 4- to 7-membered aliphatic cyclic amines such as derivatives thereof, and more specifically, for example, N— represented by the following structural formula (4) Examples thereof include phenylhexamethyleneimine, N-phenylpentamethyleneimine represented by the following structural formula (5), N-phenylpyrrolidinium represented by the following structural formula (6), and the like.

  The first ionic functional group X is introduced into the polymer main chain R1 by the following method, for example. That is, first, an anion such as a sulfonic acid derivative is added to the monomer as an initiator to perform cation living polymerization of the monomer, and then the first ion is used as a cation terminal terminator of the polymer main chain R1 synthesized by the polymerization reaction. By adding the functional group X, the first ionic functional group X is introduced into both ends of the polymer main chain R1. In this case, the precursor polymer compound A represented by the formula (3) is produced by ionic bonding of the anion used as the initiator as a counter ion to the first ionic functional group X at both ends. The

  Further, the method is not limited to the method in which the first ionic functional group X is directly introduced into the polymer main chain R1 as in this case, and the low molecular compound or the high molecular compound having the first ionic functional group X is used as the polymer main chain The first ionic functional group X can also be introduced into the polymer main chain R1 by performing a reaction for bonding to both ends of R1.

The low molecular compound B is represented by the following general formula (7).

  Here, in the formula (7), R2 is a low molecular chain containing a linear, branched, or cyclic aliphatic or aromatic hydrocarbon chain, such as an alkyl group such as an ethyl group or a butyl group. , A phenyl group, a biphenyl group, and the like, and the molecular weight thereof is not particularly limited, but is, for example, about several hundreds, preferably 200 or less. This is because if a low molecular weight compound B having a low molecular weight with a molecular weight in this range is used, the operation of introducing it as a counter anion of the first ionic functional group X of the precursor polymer compound A is easy. This is because the formation of a covalent bond with the chain R1 easily proceeds.

  In Formula (7), Y is a second ionic functional group introduced into both ends of the low molecular chain R2, and has an anionic or cationic property having a charge opposite to that of the first ionic functional group X. Is a functional group of Of those used as the second ionic functional group Y, examples of the anionic one include a carboxyl group, a sulfonic acid group, and a hydroxyl group.

  In the low molecular compound B represented by the general formula (7), the second ionic functional group Y is introduced into the low molecular chain R2 in the same manner as in the case of the first ionic functional group X. For example, commercially available dicarboxylic acids such as terephthalic acid, biphenyldicarboxylic acid, maleic acid, fumaric acid, and adipic acid, and derivatives thereof may be used.

  The molecular weight of the cyclic polymer compound produced from these precursor polymer compound A and low molecular compound B is preferably 4000 or more. This is because when the molecular weight of the cyclic polymer compound is less than 4000, for example, the glass transition temperature thereof is low, so that the moldability to a film or the like is lowered.

  Next, the manufacturing method of the cyclic polymer compound concerning this embodiment is demonstrated. The method for producing a cyclic polymer compound according to the present embodiment includes two steps performed in stages. That is, first, in the first step, from the precursor polymer compound A and the low molecular compound B, both the first ionic functional group X at both ends of the precursor polymer compound A and the low molecular compound B By forming an ionic bond with the terminal second ionic functional group Y, a polymer composite C composed of the precursor polymer compound A and the low molecular compound B is generated.

  Specifically, in the first step, for example, as shown in FIG. 1, a first ionic functional group X (here, cationic) having an anion Z ion-bonded as a counter ion to both ends of the polymer main chain R1. ) Is added dropwise to water containing a low molecular compound B having a second ionic functional group Y (here anionic) at both ends of the low molecular chain R2, and precipitated, Alternatively, the precursor polymer compound A and the low-molecular compound B in which the ionic group concentrations (concentrations of the first ionic functional group X and the second ionic functional group Y) at both ends are adjusted to an equivalent amount in water or other By co-precipitation in a suitable solvent (aqueous alcohol, alcohol, etc.) to exchange the counter ion from the anion Z to the second ionic functional group Y (exchange of the counter anion), and the resulting precipitate Suitable Diluting with a solvent, for example, as shown in the literature (J. Am. Chem. Soc., 122, 9592 (2000)), an intramolecular reaction is advantageous over an intermolecular reaction. More preferably, by selecting the conditions of 1 g / L or less, both ends of the precursor polymer compound A are temporarily fixed by the low molecular compound B (that is, both ends of the precursor polymer compound A are low molecular compounds) A polymer composite C (connected through B) is produced.

  Here, in this first step, the precursor polymer compound A and the low molecular compound B are usually used in equimolar amounts, but the present invention is not limited to this, and the first ionic functional group X and the second ionic functional group are used. Any one of them may be used in excess as long as the group Y can form a counter ion. For example, 0.5 to 10 mol of the low molecular compound B with respect to 1 mol of the precursor polymer compound A, Preferably, it is used at a ratio of about 5 mol.

  Next, the second process performed after the first process will be described. In this second step, the polymer composite C produced in the first step is subjected to a treatment such as heating and light irradiation, so that both ends of the precursor polymer compound A constituting the polymer composite C are treated. The first ionic functional group X is desorbed, the second ionic functional group Y at both ends of the low molecular compound B, which has temporarily fixed both ends of the precursor polymer compound A, and the precursor height A monocyclic polymer compound D is produced by forming a covalent bond with a part of the monomer constituting the polymer chain R1 of the molecular compound A.

  Specifically, in this second step, for example, as shown in FIG. 2, the polymer composite C produced in the first step is dissolved at a low concentration in a solvent such as toluene, and this polymer composite solution In addition, for example, by performing heat treatment in a temperature range of about 40 ° C. to 150 ° C., a part of the monomers near both ends of the polymer main chain R1 constituting the precursor polymer compound A and both ends of the low molecular compound B And the second ionic functional group Y form a covalent bond, and a monocyclic polymer compound D in which both ends of the polymer main chain R1 are connected via the low molecular chain R2 is generated.

  Note that the concentration of the polymer complex C in the polymer complex solution used in the second step may be appropriately adjusted according to the type and molecular weight of the precursor polymer compound A constituting the polymer complex C. However, for example, a range of about 0.1 g / L to 50 g / L is preferably used. In addition, the covalent bond forming reaction between the precursor polymer compound A and the low molecular compound B in the second step is not limited to the heat treatment, and can be performed by, for example, light irradiation treatment.

  The cyclic polymer compound D produced in the second step has a unique topological structure in which the polymer main chain R1 does not have an end, and thus has a polymer main chain such as melting point, solubility, and film formability. The properties that are not easily affected by end groups are almost the same as those of conventional polymer compounds having terminal ends in the polymer main chain. The physical or mechanical properties that are easily affected can be expected to exhibit novel properties that could not be expressed by conventional general polymer compounds. That is, the cyclic polymer compound D is useful as, for example, a resin, a film, a fiber, a rubber material, various modified materials, and various additive materials.

In the second step, the first ionic functional groups X at both ends of the precursor polymer compound A are eliminated in the polymer complex C, and the polymer main chain R1 of the precursor polymer compound A and For example, when a carboxyl group is used as the second ionic functional group Y, the second ionic functional group Y at both ends of the low molecular compound B directly forms a covalent bond. Cyclic polymer compound D represented by the following general formula (8), which is cyclized by formation and excellent in thermal stability, can be produced.

  Next, examples of the present invention will be described. The present invention is not limited to the present embodiment.

[Raw material preparation 1: Synthesis of first ionic functional group]
In this example, N-phenylhexamethyleneimine synthesized by the following method was used as the first ionic functional group X. That is, sodium amide (25.1 g, 6.39 × 10 ⁻¹ mol, manufactured by Kanto Chemical Co., Ltd.) and hexamethyleneimine (160.2 g, 1.60 mol, manufactured by Aldrich) were mixed and heated under reflux for 30 minutes in a nitrogen atmosphere. Bromobenzene (51.0 g, 3.20 × 10 ⁻¹ mol, manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise thereto over 2 hours, and the mixture was further stirred under reflux for 2 hours. Next, H ₂ O (50 ml) was added to the reaction mixture while cooling with ice, extracted several times with toluene (100 ml), and the extracted solution was washed 5 times with H ₂ O. Then, the solvent was distilled off, and N-phenylhexamethyleneimine was isolated by distillation under reduced pressure (yield: 38.4 g, 2.19 × 10 ⁻¹ mol, yield: 68.4%).

[Preparation of raw materials 2: Production of precursor polymer compound]
In this example, precursor polymer compound A was synthesized using tetrahydrofuran (hereinafter referred to as THF) (manufactured by Kanto Chemical Co., Inc.) as a monomer. That is, 50 ml of THF was stirred at 25 ° C. for a predetermined time in a nitrogen atmosphere, and then trifluoromethanesulfonic anhydride (127.3 ml, 5.94 × 10 ⁻⁴ mol, manufactured by Aldrich) was added as an initiator. Cationic polymerization reaction was started, and after 11 minutes and 30 seconds, N-phenylhexamethyleneimine (910.4 mg, 4.76 × 10 ^-3 mol) synthesized by the above method was added as a cation terminal terminator to stop the reaction. . After distilling off the solvent, 9 ml of THF was added and dissolved, and this solution was added dropwise to 350 ml of cold petroleum ether. After stirring for 30 minutes, the precipitated product was collected by filtration and dried under reduced pressure to isolate the product (yield: 1.97 g, 4.53 × 10 ⁻⁴ mol).

Using this product, FT-IR (Fourier Transform Infrared Spectroscopy) (JASCO FT / IR-410, manufactured by JASCO) and ¹ H-NMR (Proton Nuclear Magnetic Resonance) (JEOL-AL300, manufactured by JEOL) The analysis results are shown in FIGS. 3 and 4, respectively.

As shown in FIG. 3, in the IR spectrum, absorption from triflate anion (trifluoromethanesulfonic acid anion) is, 638cm ^-1 (CS stretching vibration), 1030 cm ^-1 (SO ₃ ^- symmetric stretching vibration), 1257Cm ^-1 (CF vibration) was detected respectively.

Moreover, as shown in FIG. 4, in the ¹ H-NMR spectrum, the peaks derived from methylene of the hexamethylene iminium ring contained in N-phenylhexamethyleneimine are 4.16 ppm (peak d) and 2.16 ppm (peak e). Respectively.

From these results of FIG. 3 and FIG. 4, the first monomer has a poly THF chain (hereinafter referred to as PTHF chain) as a polymer main chain R1 by living polymerization of a THF monomer, and a trifluoromethanesulfonate ion is bound as a counter anion. It was confirmed that the precursor polymer compound A represented by the following structural formula (9) in which N-phenylhexamethyleneimine as the ionic functional group X of the compound was introduced at both ends was synthesized.

[First step: Formation of polymer composite]
In this example, sodium 4,4′-biphenyldicarboxylate was used as the low molecular compound B. This sodium 4,4′-biphenyldicarboxylate was synthesized by reacting 4,4′-biphenyldicarboxylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) with an equivalent amount of sodium hydroxide in water.

Next, distilled water in which the synthesized sodium 4,4′-biphenyldicarboxylate was dissolved in 10-fold molar amount (306.6 mg, 1.07 mmol) of N-phenylhexamethyleneimine groups at both ends of the precursor polymer compound A ( 250 ml) was prepared and cooled to 5 ° C. or lower, and while stirring vigorously, precursor polymer compound A (466.6 mg, 1.07 × 10 ⁻¹ mmol) dissolved in THF (2 ml) was slowly added dropwise thereto. . After stirring for 1 hour, the precipitated product was collected by filtration and dried under reduced pressure to obtain a product (hereinafter referred to as the first step product). In order to completely exchange the counter anion of the precursor polymer compound A from the trifluoromethanesulfonate anion to the biphenyldicarboxylate anion, this operation was repeated twice (yield: 395.6 mg).

The results of analyzing the obtained first step product using FT-IR and ¹ H-NMR are shown in FIGS. 5 and 6, respectively. As shown in FIG. 5, in the IR spectrum, the absorption derived from the triflate anion detected before the counter anion exchange (see FIG. 3) disappeared, and the absorption derived from the carboxylate anion was detected at 1590 cm ⁻¹ . . That is, it was confirmed that the counter anion was exchanged from the trifluoromethanesulfonate anion to the biphenyldicarboxylate anion.

Further, as shown in FIG. 6, in the ¹ H-NMR spectrum, a peak derived from 4,4′-biphenyldicarboxylate anion that was not detected before the counter anion exchange (see FIG. 4) was 8.19 ppm (peak h ) And 7.73 ppm (peak i), respectively.

From the results shown in FIG. 5 and FIG. 6, in the first step, the second ionicity of both ends of N-phenylhexamethyleneimine and 4,4′-biphenyldicarboxylic acid at both ends of the precursor polymer compound A is obtained. The carboxylic acid anion which is the functional group Y forms an ionic bond, thereby comprising the precursor polymer compound A and the 4,4′-biphenyldicarboxylic acid, which is represented by the following structural formula (10). It was confirmed that the molecular complex C was produced as the first step product.

[Second step: Production of cyclic polymer compound]
Next, the polymer composite C (59.6 mg) produced in the first step was dissolved in toluene (200 ml) and heated to reflux for 12 hours. After distilling off the solvent, the obtained product (46.0 mg) was prepared by adding 500 ml of water to silica gel thin layer chromatography (200 g of Silicagel 60 PF ₂₅₄ MERCK, stirring, and applying to a glass plate. ). As a developing solvent, acetone: hexane was used at a ratio of 1: 2, and a portion showing UV absorption (R _f = 0.5 to 0.6) was selectively recovered and extracted with acetone (50 ml) for 30 minutes. The silica gel was filtered, and the solvent of the filtrate was distilled off, followed by drying under reduced pressure to obtain the final product (hereinafter referred to as the second step product) (yield: 40.3 mg).

Further, in the first step and the second step, by using tetra-n-butylammonium benzoate instead of 4,4′-biphenyldicarboxylic acid, a polymer compound having a non-cyclic end (hereinafter referred to as a control product) Called). As a result of analyzing this control product using FT-IR and ¹ H-NMR, it was confirmed that the polymer was a polymer compound in which benzoic acid groups were covalently bonded to both ends of the PTHF chain (analysis result not shown). ).

FIG. 7 shows the results of analyzing the second step product and the control product using SEC (Size Exclusion Chromatography). The results of analysis of the second step product using FT-IR, ¹ H-NMR, and MALDI-TOF-MS (Matrix Assisted Laser Desorption Ionization Time Of Fright Mass Spectrometry) are shown in FIGS. It shows in FIG. The SEC analysis was performed using a GPC unit equipped with dual pump CCPS, TSK gel column G3000HXL, differential refractometer RI-8020, UV-visible detector UV-8020, and conductivity detector CM-8010 (elution solvent THF = 1.0 ml / min). , Column temperature 40 ° C, manufactured by Tosoh Corporation), the molecular weight of the second step product and control product is calculated by multiplying the polystyrene equivalent molecular weight by the conversion coefficient 0.556 from the peak position on the chromatogram. did. In addition, MALDI-TOF-MS analysis uses SHIMADZU AXIMA-CFR (nitrogen laser beam λ = 337 nm, acceleration voltage = 20 kv, manufactured by Shimadzu Corp.), sample (second step product or control product) solution (sample / THF = 1 mg / 1 ml) and 50 μl of a mixed solution of a matrix solution (disranol / sodium trifluoroacetate / THF = 10 mg · 1 mg / 1 ml) 50 μl.

FIG. 7 (a) and FIG. 7 (b) are SEC chromatograms showing the results of SEC analysis for the control product and the second step product, respectively. From the results shown in FIG. 7A, the number average molecular weight _Mn of the control product was calculated as 6510, and the ratio _Mw / _Mn between the weight average molecular weight _Mw and the number average molecular weight _Mn was calculated as 1.09. Further, from the result shown in FIG. 7B, the number average molecular weight M _n of the second step product was calculated to be 5000, and the ratio M _w / M _n of the weight average molecular weight M _w to the number average molecular weight was calculated to be 1.23. .

  Further, the molecular weight corresponding to the peak position (m) of the molecular weight distribution of the second step product shown in FIG. 7 (b) and the peak position (l) of the molecular weight distribution of the control product shown in FIG. 7 (a). The ratio of the molecular weight to be calculated was 0.76. This apparent molecular weight ratio is determined by using SEC in the literature (Macromolecules, 34, 6592 (2001)) for PTHF having the same molecular weight and having an end in the main chain and cyclic PTHF in the molecular weight range of 3100 to 300300. Since it agreed with the apparent molecular weight ratio (0.75 to 0.87) in the analysis result, it was confirmed that the product of the second step was a cyclic polymer compound.

Further, as shown in FIG. 8, in the IR spectrum, the absorption derived from the carboxylate anion detected before the heating in the second step (see FIG. 5) disappears, and the absorption derived from the ester bond instead of 1718 cm ⁻ Detected at ¹ (C = O stretching vibration).

Further, as shown in FIG. 9, in the ¹ H-NMR spectrum, a signal derived from methylene of the hexamethylene iminium ring detected before heating in the second step (see FIG. 6) (peak d in FIG. 6, All of the peaks e) disappeared, and the peak of methylene adjacent to the ester was detected at 4.35 ppm (peak k), confirming the formation of an ester bond.

  From the results shown in FIG. 8 and FIG. 9, in the second step, both N-phenylhexamethyleneimine and 4,4′-biphenyldicarboxylic acid at both ends of the precursor polymer compound A constituting the polymer composite C are obtained. It was confirmed that the ionic bond between the terminal carboxyl group disappeared and a second step product having an ester bond was produced.

  Moreover, as shown in FIG. 10, two types of peak distributions were detected in the MALDI-TOF-MS spectrum, and it was confirmed that the product of the second step contains two types of cyclic polymer compounds. Here, for the sake of distinction, the peak distribution with a smaller peak height in FIG. 10 will be referred to as a first peak distribution, and the peak distribution with a larger peak height in FIG. 10 will be referred to as a second peak distribution.

  The molecular weight difference between adjacent peaks in the first peak distribution and the molecular weight difference between adjacent peaks in the second peak distribution are all equivalent to the molecular weight 72 of the repeating unit (THF monomer) of the PTHF chain. The value to show. That is, it was confirmed that each peak detected adjacently in each peak distribution indicates a product having a different degree of polymerization of THF.

  Furthermore, the molecular weight indicated by each peak position in the first peak distribution shown in FIG. 10 is the same as that of a part of the THF monomer constituting the PTHF chain and N-phenylhexamethyleneimine at both ends of the PTHF chain is eliminated. The molecular weight of the cyclic polymer was almost the same as that assumed when 4'-biphenyldicarboxylic acid was formed by forming an ester bond.

That is, for example, with respect to the 60-mer, the molecular weight of the cyclic polymer compound assuming that both N-phenylhexamethyleneimines are generated by elimination is (C ₄ H ₈ O) × 60 + C ₄ H ₈ + ( COO + C ₆ H ₄ ) × 2 = 4645.749, but the peak p was detected at a position corresponding to the molecular weight 4465.67 in the first peak distribution of FIG. Such a coincidence was confirmed even when the degree of polymerization was other than 60.

  Further, for each peak in the second peak distribution shown in FIG. 10, the molecular weight indicated by each peak position is determined by removing one N-phenylhexamethyleneimine from the N-phenylhexamethyleneimine at both ends of the PTHF chain. It was almost the same as the molecular weight of the cyclic polymer when it was assumed that the ring was released and the other was ring-opened.

That is, for example, the molecular weight of the 60-mer is calculated as (C ₄ H ₈ O) × 60 + C ₄ H ₈ + (COO + C ₆ H ₄ ) × 2 + N + C ₆ H ₅ + C ₆ H ₁₂ = 4821.024. In the second peak distribution, a peak q was detected at a position corresponding to a molecular weight of 4802.76. Such a coincidence was confirmed even when the degree of polymerization was other than 60.

  Further, the molecular weight difference between the peak p in the first peak distribution and the peak q in the second peak distribution in FIG. 10 is 175.09, which is very close to the molecular weight 175 of one N-phenylhexamethyleneiminium ring. Met.

  From the analysis results using MALDI-TOF-MS shown in FIG. 10, in the second step, the first ionic functional groups X at both ends of the precursor polymer compound A constituting the polymer complex C are eliminated. It was confirmed that a cyclic polymer compound was produced by a cyclization reaction involving the formation of an ester bond between the polymer main chain R1 and the second ionic functional group Y.

  In other words, in this second step, the polymer complex C composed of the precursor polymer compound A and the low-molecular compound B represented by the structural formula shown in FIG. As shown in FIG. 11 (b) in which the vicinity of N-phenylhexamethyleneimine and a carboxyl group surrounded by a solid line L in FIG. 11B is enlarged, nucleophilicity by 4,4′-biphenyldicarboxylate anion Since the attack was performed on the methylene (position I) of the THF monomer constituting the PHTF chain, together with the elimination reaction of the N-phenylhexamethyleneiminium ring, the carbon atom at the position I constituting the THF monomer Formation of an ester bond with a carboxyl group occurs, and a cyclic polymer compound represented by the structural formula shown in FIG. 11C detected as the first peak distribution in FIG. That it has been has been confirmed.

  In addition, for a part of the polymer complex C used in the second step, a nucleophilic attack by 4,4′-biphenyldicarboxylate anion is caused by the THF monomer constituting one end of the PHTF chain. In each of the ends of the methylene (position I) and the adjacent methylene (position II) of the amine of the N-phenylhexamethyleneiminium ring at the other end of the PTHF chain, Along with the elimination reaction of the N-phenylhexamethyleneiminium ring, an ester bond is formed between the carbon atom at position I and the carboxyl group, and the N-phenylhexamethyleneiminium ring is opened at the other end. FIG. 11 (d) is detected as the second peak distribution of FIG. 10 by the formation of an ester bond between the carbon atom at position II and the carboxyl group with reaction. It was also confirmed that a cyclic polymer compound represented by the structural formula shown in FIG.

  Thus, in this example, the ring-opening reactivity of N-phenylhexamethyleneimine used as the first ionic functional group is relatively low. The elimination reaction of N-phenylhexamethyleneimine occurred, and a cyclic polymer compound excellent in thermal stability was produced.

It is explanatory drawing about the production | generation reaction of the polymer composite_body | complex in one Embodiment of this invention. It is explanatory drawing about the production | generation reaction of the cyclic polymer compound in one Embodiment of this invention. It is a spectrum figure which shows the FT-IR analysis result about the precursor polymer compound in one Embodiment of this invention. It is a spectrum diagram showing the ¹ H-NMR analysis results for the precursor polymer compound in an embodiment of the present invention. It is a spectrum figure which shows the FT-IR analysis result about the polymer composite_body | complex in one Embodiment of this invention. It is a spectrum diagram showing the ¹ H-NMR analysis results for the polymer composite in an embodiment of the present invention. It is a chromatogram which shows the SEC analysis result about the cyclic | annular polymeric compound and control product in one Embodiment of this invention. It is a spectrum figure which shows the FT-IR analysis result about the cyclic polymer compound in one Embodiment of this invention. It is a spectrum diagram showing the ¹ H-NMR analysis results for the cyclic macromolecular compound in an embodiment of the present invention. It is a spectrum figure which shows the MALDI-TOF-MS analysis result about the cyclic polymer compound in one Embodiment of this invention. It is explanatory drawing which shows the process of the production | generation reaction of the cyclic polymer compound in one Embodiment of this invention.

Claims (10)

A cyclic polymer having a molecular weight of 4000 or more, wherein both ends of a polymer main chain and both ends of a low molecular chain are covalently bonded,
A cyclic polymer compound, wherein both ends of the low molecular chain form the covalent bond with a part of a monomer constituting the polymer main chain.   The cyclic polymer compound according to claim 1, wherein the polymer main chain is a linear polymer chain having no branched chain.   The cyclic polymer compound according to claim 1, wherein the polymer main chain is a polymer chain having a branched chain.   The cyclic polymer compound according to any one of claims 1 to 3, wherein the covalent bond is an ester bond.   The cyclic polymer compound according to claim 4, comprising an ester bond only between both ends of the polymer main chain and both ends of the low molecular chain. A cyclic polymer compound having a molecular weight of 4000 or more, represented by the following general formula (1):

(In the formula (1), R1 is a polymer chain having a branched chain or not having a branched chain, and R2 is a linear, branched, or cyclic low molecular chain.) A precursor polymer compound having a first ionic functional group at both ends of the polymer main chain;
A low molecular compound having a second ionic functional group having a charge opposite to that of the first ionic functional group at both ends of the low molecular chain, and
An ionic bond is formed between the first ionic functional group and the second ionic functional group from the precursor polymer compound and the low molecular compound, and the precursor polymer compound and the low molecule Producing a polymer composite comprising the compound,
The first ionic functional group is eliminated from the polymer complex, and is shared between the second ionic functional group and a part of the monomer constituting the polymer main chain of the precursor polymer compound. Producing a cyclic polymer compound in which a bond is formed;
A method for producing a cyclic polymer.   The cyclic polymer production method according to claim 7, wherein the covalent bond is an ester bond.   9. The method for producing a cyclic polymer according to claim 7, wherein the first ionic functional group is an aliphatic cyclic amine. The method for producing a cyclic polymer according to any one of claims 7 to 9, wherein the second ionic functional group is a carboxyl group.

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