JP2015525804A - Glycidyl-4-position-modified-1,2,3-triazole derivative polymer and synthesis method thereof - Google Patents

Abstract

Disclosed is a polymer material having a new function using a glycidyl azide polymer as a starting material. A glycidyl-4-position-modified-1,2,3-triazole derivative polymer obtained by converting all azide groups of a glycidyl azide polymer into a 4-position-modified triazole ring.

Description

  The present invention relates to a glycidyl-4-position-modified-1,2,3-triazole derivative polymer obtained by converting all azide groups of a glycidyl azide polymer into 4-position-modified-1,2,3-triazole groups.

  Click chemistry is the concept of creating new functional molecules using several reactions that create simple and stable bonds in the chemical field, and is used to search for useful compounds.

The azido-alkyne Fisgen cycloaddition reaction is one of the most known reactions in click chemistry. This reaction is a reaction in which a 1,2,3-triazole ring is formed by a 1,3-dipolar cycloaddition reaction between the carbon-carbon triple bond of an azide and an alkyne compound. From the combination of various azides and alkyne compounds, Many useful materials have been synthesized. (Non-Patent Documents 1 and 2).
There is also a report of modification of an azide-modified polymer by click reaction (Non-patent Document 3). However, an azide-modified polymer or its precursor is obtained from polymerization of monomers, and for this purpose, advanced polymer synthesis technology is used. Desired.
Glycidyl azide polymer is one of azide modified polymers and can be easily synthesized from commercially available polyepichlorohydrin. Glycidyl azide polymers have been studied as explosives and fuel propellants (Patent Document 1, Non-Patent Documents 4 and 5). There is also application research as a curing agent that solidifies the fuel propellant by chemically crosslinking the glycidyl azide polymer using the azide-alkyne Fisgen cycloaddition reaction. In this study, the cross-linked glycidyl azide polymer itself also acts as a fuel propellant, leaving most of the azide groups that are high energy functional groups unreacted. The explosive energy of glycidyl azide polymers is derived from high energy chemical bonds of azide groups. In the history of glycidyl azide polymer, no one has attempted chemical modification that completely crushes the azide group (Non-patent Documents 6 and 7). This is probably because glycidyl azide polymer was recognized as a high-energy material and could not be imagined for applications other than explosives.

JP 07-215790 A

Angewandte Chemie International Edition 2002, 41, 2596. Macromolecular Rapid Communications 2007,28,15. Macromolecules 2007,40,796. Defense Science Journal, 2008,58,86 Propellants Explosives, Pyrotechnics, 1991, 16,177. Journal of Applied Polymer Science, 2009, 114, 398. Propellants Explosives, Pyrotechnics, 2012, 37, 59.

  An object of the present invention is to provide a polymer material having a new function using a glycidyl azide polymer as a starting material.

  The glycidyl-4 position-modified 1,2,3-triazole derivative polymer of the present invention (hereinafter simply referred to as the polymer derivative of the present invention) is represented by the following general formula (1).

（１）

(1)

  In the formula, R is an alkyl group, a halogen group, a hydroxyl group, an aldehyde group, an amino group, a cyano group, a nitro group, a carboxyl group, a phosphoric acid group, a sulfo group, a thiol group, a vinyl group, or a cyclic group having 3 to 30 carbon atoms. A substituent selected from organic compounds, which is directly bonded to a triazole group, or an ester bond, an amide bond, an aliphatic hydrocarbon chain having 1 to 30 carbon atoms, a cyclic organic compound having 3 to 30 carbon atoms, It is bonded via one or more spacer units selected from oligoethylene glycol chains or alkyl ether chains having 2 to 10 repeats, n is the number of repeats, and the molecular weight of the polymer derivative of the present invention is 2, It is selected to fall within the range of 8 to 8 million.

  The method for synthesizing a polymer derivative of the present invention is a method of reacting a glycidyl azide polymer with at least one alkyne, wherein the molar ratio of alkyne compound / azide group is 1 or more, leaving no unreacted azide group, And it is made to react on the conditions which a reaction solution does not change to gel.

The polymer derivative of the present invention uses a glycidyl azide polymer as a synthesis starting material, and reacts with an alkyne to convert all azide groups of the glycidyl azide polymer into 4-position-modified 1,2,3-triazole groups. It is obtained by. Unlike the conventional glycidyl azide modified polymer, the polymer derivative of the present invention does not contain an azide group which is a high-energy functional group, and therefore has no explosion risk and excellent thermal stability. In addition, since the main chain is a polyether, unlike polyethylene-based polyolefin polymer, the polymer main chain is highly flexible and has a low glass transition temperature, so that it can be used as a soft material.
Further, according to the method for synthesizing the polymer derivative of the present invention, the synthesis conditions of the polymer in which all the azide groups of the glycidyl azide polymer are converted to 4-position-modified-1,2,3-triazole groups, the copper catalyst used in the reaction, A convenient method for polymer isolation and purification from an excess of alkyne compound is provided.

It is a figure which shows the scheme of the synthesis | combining method of the polymer derivative of this invention. FIG. 3 is a diagram showing ¹ H and ¹³ C-NMR results of the polymer derivative of Example 1. FIG. 3 is a diagram showing ¹ H-NMR results of a polymer derivative of Example 2. FIG. 3 is a diagram showing ¹ H and ¹³ C-NMR results of the polymer derivative of Example 3. FIG. 4 is a diagram showing ¹ H and ¹³ C-NMR results of the polymer derivative of Example 4. FIG. 6 is a diagram showing ¹ H-NMR results of the polymer derivative of Example 5. FIG. 6 is a diagram showing ¹ H and ¹³ C-NMR results of the polymer derivative of Example 6. FIG. 6 is a diagram showing ¹ H and ¹³ C-NMR results of the polymer derivative of Example 7. FIG. 6 is a diagram showing ¹ H and ¹³ C-NMR results of the polymer derivative of Example 8. FIG. 6 is a diagram showing ¹ H and ¹³ C-NMR results of the polymer derivative of Example 9. FIG. 4 is a graph showing ¹ H and ¹³ C-NMR results of the polymer derivative of Example 10. FIG. 4 is a diagram showing ¹ H and ¹³ C-NMR results of the polymer derivative of Example 11. FIG. 4 is a diagram showing ¹ H-NMR results of a polymer derivative of Example 12. FIG. 4 is a graph showing the ¹ H-NMR result of the polymer derivative of Example 13. FIG. 14 is a graph showing ¹ H-NMR results of the polymer derivative of Example 14. It is a figure which shows the result of the ultraviolet-visible absorption spectrum of the polymer derivative of Example 14. It is a figure which shows the result of the fluorescence spectrum of the polymer derivative of Example 14. It is a figure which shows the thermal stability of a glycidyl azide polymer and the polymer derivative of an Example. It is a figure which shows the thermal stability of the polymer in which some azide groups of the glycidyl azide polymer remained.

  The polymer derivative of the present invention is represented by the following general formula (1).

（１）

(1)

  In the formula, R is an alkyl group, a halogen group, a hydroxyl group, an aldehyde group, an amino group, a cyano group, a nitro group, a carboxyl group, a phosphoric acid group, a sulfo group, a thiol group, a vinyl group, or a cyclic group having 3 to 30 carbon atoms. A substituent selected from organic compounds, which is directly bonded to a triazole group, or an ester bond, an amide bond, an aliphatic hydrocarbon chain having 1 to 30 carbon atoms, a cyclic organic compound having 3 to 30 carbon atoms, They are bonded via one or more types of spacer units selected from oligoethylene glycol chains or alkyl ether chains having 2 to 10 repeats.

The alkyl group is a linear or branched lower alkyl group, specifically, a linear or branched alkyl group having 1 to 6 carbon atoms.
Binding through an ester bond or an amide bond means the following formula (19) or (20).

（１９）

(19)

（２０）

(20)

  The C3-C30 cyclic organic compound may be a monocyclic compound or a condensed ring compound. Monocyclic compounds include cycloalkanes such as cyclopropane, cyclobutane and cyclohexane, and aromatic rings such as benzene. The condensed ring compound is a condensate of a plurality of monocyclic compounds, and includes 2 to 5 monocyclic compounds. Specifically, compounds such as acene, phenanthrene, chrysene, and pyrene are included. Cyclic organic compounds also include heterocyclic compounds such as thiophene and tetrahydrofuran.

  The aliphatic hydrocarbon chain may be a linear or branched saturated hydrocarbon chain, or may be a linear or branched unsaturated hydrocarbon chain. Preferably it is a C1-C12 linear or branched saturated hydrocarbon chain.

The oligoethylene glycol chain means a structure in which —O— (C ₂ H ₄ ) — is repeatedly bonded. The number of repetitions is 2-10.

The alkyl ether chain is a unit having a structure of —C _m H _2m —O— or —CH ₂ —O—C _m H _2m —O—, and m is a natural number of 1 to 18.

  N in the formula is the number of repetitions, and is selected so that the molecular weight of the polymer derivative of the present invention falls within the range of 2,000 to 8 million.

  The substituent R in the formula is a substituent that chemically modifies the fourth position of the triazole ring, and may be all the same in the polymer or may be a plurality of different ones. When all the substituents R are the same, it is a glycidyl-4-position-modified-1,2,3-triazole derivative polymer having one type of monomer as a structural unit, and when different, two or more types of monomers are used as a structural unit. It is a glycidyl-4-position modified 1,2,3-triazole derivative polymer. For example, when R is two or three different substituents, the polymer derivative of the present invention is represented by the formula (2) or (3). As described above, the substituent R may be bonded to the triazole group via a spacer molecule. The substituent R may be bonded to carbon at the terminal of the spacer molecule as shown in the Examples, but the bonding position is not particularly limited.

（２）

(2)

（３）

(3)

  The sum of a and b or the sum of a, b and c in formulas (2) and (3) is n, and n is in the range of 2,000 to 8 million in the molecular weight of the polymer derivative of the present invention. Selected as

  The monomer constituting the polymer derivative of the present invention may be three or more types as shown in the formula (15).

（１５）

(15)

  In formula (15), a, b,. . . , Z is n, and n is selected such that the molecular weight of the polymer derivative of the present invention falls within the range of 2,000-8 million

Substituents R, R ¹ , R ² , R ³ , R ^a , R ^b . . . Or ^Rz is specifically a substituent represented by the following formulas (4) to (14).

（４）

(4)

（５）

(5)

（６）

(6)

（７）

(7)

（８）

(8)

（９）

(9)

（１０）

(10)

（１１）

(11)

（１２）

(12)

（１３）

(13)

（１４）

(14)

  Since the polymer derivative of the present invention does not contain any azide group, there is no risk of explosion and it has excellent thermal stability. In addition, since the main chain is a polyether, unlike polyethylene-based polyolefin polymer, the polymer main chain is highly flexible and has a low glass transition temperature, so that it can be used as a soft material.

The polymer derivative of the present invention comprises N, N-dimethylformamide (DMF) in the presence of a glycidyl azide polymer (represented by formula (16)) and at least one alkyne compound represented by formula (17). ), A reaction in an organic solvent such as dimethyl sulfoxide (DMSO) or tetrahydrofuran (THF), wherein the molar ratio of alkyne compound / azide group is 1 or more, and no unreacted azide group remains. And The reaction scheme is shown in FIG.
As the reaction temperature is higher, the reaction is completed in a shorter time. However, depending on the type of alkyne compound, the boiling point is lower. Therefore, if the reaction is performed at a higher temperature, the alkyne compound is vaporized, so an excess alkyne compound is required. Moreover, although reaction is completed in a short time, so that solution concentration is high, when a solution concentration is high, the polymer entangles and the example which the reaction liquid has changed to the gel is seen. Once gelled, the polymer and alkyne compound are not stirred and mixed, so that the conversion efficiency to the triazole group is deteriorated, and purification is hindered because re-dissolution is difficult. In order to prevent gelation, the solution concentration (g / mL) of the glycidyl azide polymer is preferably 2% or less. However, if the concentration is less than 1%, it is not preferable because more alkyne compounds are required to convert azide groups to triazole groups or the reaction time must be extended. It is desirable to use a catalyst for the reaction. For example, a copper-based catalyst such as tetrakis acetonitrile copper (I) hexafluorophosphate or copper sulfate is desirable.

（１６）

(16)

（１７）

(17)

R in the formula (17) is the same as described above.
In general, the molecular weight of the polymer varies, and the molecular weight of the polymer derivative of the present invention varies depending on the glycidyl azide polymer used as a starting material. Since the glycidyl azide polymers used in the examples include those having a molecular weight of 2,000 to 5,000,000, the molecular weight range of the polymer derivative of the present invention is in the range of 2,000 to 8,000,000. .
Further, by reacting two or more kinds of alkynes with a glycidyl azide polymer, a copolymer type polymer derivative having two or more kinds of monomers represented by the above formula (2), (3) or (15) as a structural unit is obtained. be able to.
What is necessary is just to perform the purification procedure of the obtained polymer derivative of this invention according to the following procedures. The copper catalyst can be removed by adsorbing to a cation exchange resin in solution or chelating with an aqueous solution of ethylenediaminetetraacetic acid disodium salt. Excess alkyne compound can be removed by dropping the polymer solution into a solvent that is a poor solvent for the polymer and a good solvent for the alkyne compound. The polymer derivative of the present invention is recovered as a precipitate.

  The glycidyl azide polymer can be obtained by reacting polyepichlorohydrin (represented by formula (18)) with sodium azide in DMF at about 80 ° C.

（１８）

(18)

Hereinafter, the present invention will be described in more detail based on examples.
The glycidyl azide polymer used in the examples was synthesized by reacting polyepichlorohydrin (Sigma-Aldrich, molecular weight 700,000) with sodium azide in DMF at 80 ° C. for 24 hours. The polymer has a molecular weight distribution, and the glycidyl azide polymer sample used as a starting material contains a molecular weight of 2,000 to 5 million at the same time.

Modification with 2-propynylbenzene Glycidyl azide polymer (0.30 g) was dissolved in 15 mL of DMF at 40 ° C., followed by tetrakis acetonitrile copper (I) hexafluorophosphate (56 mg) and 2-propynylbenzene (0.75 mL). Was added. The reaction was conducted with stirring at 40 ° C. for 24 hours under an argon atmosphere. To the reaction solution, 15 mL of DMF and 15 g of cation exchange resin were added to adsorb copper ions. After removing the cation exchange resin by filtration, the solvent was distilled off by an evaporator. In order to completely remove DMF, a polymer solution dissolved in 10 mL of dichloromethane was added dropwise to 300 mL of diethyl ether with stirring. The precipitated polymer was dissolved in 200 mL of dichloromethane and washed with 200 mL of ethylenediaminetetraacetic acid aqueous solution to completely remove copper ions. The dichloromethane layer was collected, dried over magnesium sulfate, filtered, concentrated with an evaporator, and then again taken into diethyl ether to precipitate the polymer. The polymer was recovered by filtration and dried under reduced pressure to obtain a modified polymer in a yield of 98%. The synthesis was confirmed by ¹ H and ¹³ C-NMR. Deuterated chloroform was used as the solvent. The results of ¹ H and ¹³ C-NMR (proton nuclear magnetic resonance and carbon satin nuclear magnetic resonance) are shown in FIG.

Modification with 1-tert-butyl-4-ethynylbenzene After dissolving glycidyl azide polymer (0.30 g) in 15 mL of DMF at 40 ° C., copper sulfate pentahydrate (20 mg), sodium ascorbate (30 mg), And 1-tert-butyl-4-ethynylbenzene (1.0 mL) was added. The reaction was conducted with stirring at 50 ° C. for 20 hours under an argon atmosphere. 6 mL of DMF was added to the reaction solution and dropped into 250 mL of an aqueous solution of disodium ethylenediaminetetraacetate to precipitate the polymer, and the copper catalyst and sodium ascorbate were removed. The polymer was washed sequentially with 200 mL of methanol and acetone and then dried under reduced pressure to obtain a modified polymer in a yield of 87%. The synthesis was confirmed by ¹ H-NMR. Deuterated dichloromethane was used as the solvent. The results are shown in FIG.

Modification with 2-propynylcyclohexane Glycidyl azide polymer (0.30 g) was dissolved in 15 mL of DMF at 40 ° C., followed by tetrakisacetonitrile copper (I) hexafluorophosphate (56 mg) and 2-propynylcyclohexane (0.86 mL). Was added. The reaction was conducted with stirring at 40 ° C. for 24 hours under an argon atmosphere. 15 mL of DMF and 15 g of cation exchange resin were added to the reaction solution to adsorb copper ions. After removing the cation exchange resin by filtration, the solvent was distilled off by an evaporator. In order to completely remove DMF, a polymer solution dissolved in 10 mL of dichloromethane was added dropwise to 300 mL of diethyl ether with stirring. The precipitated polymer was dissolved in 200 mL of dichloromethane and washed with 200 mL of ethylenediaminetetraacetic acid aqueous solution to completely remove copper ions. The dichloromethane layer was collected, dried over magnesium sulfate, filtered, concentrated with an evaporator, and then again taken into diethyl ether to precipitate the polymer. The polymer was recovered by filtration and dried under reduced pressure to obtain a modified polymer in a yield of 84%. The synthesis was confirmed by ¹ H and ¹³ C-NMR. Deuterated chloroform was used as the solvent. The results are shown in FIG.

Modification with 1-hexyne After dissolving glycidyl azide polymer (0.30 g) in 15 mL of DMF at 40 ° C., tetrakis acetonitrile copper (I) hexafluorophosphate (56 mg) and 1-hexyne (0.69 mL) were added. did. The reaction was conducted with stirring at 40 ° C. for 24 hours under an argon atmosphere. 15 mL of DMF and 15 g of cation exchange resin were added to the reaction solution to adsorb copper ions. After removing the cation exchange resin by filtration, the solvent was distilled off by an evaporator. In order to completely remove DMF, a polymer solution dissolved in 10 mL of dichloromethane was added dropwise to 300 mL of diethyl ether with stirring. The precipitated polymer was dissolved in 200 mL of dichloromethane and washed with 200 mL of ethylenediaminetetraacetic acid aqueous solution to completely remove copper ions. The dichloromethane layer was collected, dried over magnesium sulfate, filtered, concentrated with an evaporator, and then again taken into diethyl ether to precipitate the polymer. The polymer was recovered by filtration and dried under reduced pressure to obtain a modified polymer in a yield of 87%. The synthesis was confirmed by ¹ H and ¹³ C-NMR. Deuterated chloroform was used as the solvent. The results are shown in FIG.

Modification with 1-pentyne Glycidyl azide polymer (0.11 g) was dissolved in 5 mL of DMF at 40 ° C., then copper sulfate pentahydrate (7 mg), sodium ascorbate (11 mg), and 1-pentyne (0. 20 mL) was added. The reaction was conducted with stirring at 40 ° C. for 24 hours under an argon atmosphere. 10 mL of DMF and 5 g of cation exchange resin were added to the reaction solution to adsorb copper ions. After removing the cation exchange resin by filtration, the solvent was distilled off by an evaporator. In order to completely remove DMF, a polymer solution dissolved in 5 mL of dichloromethane was added dropwise to 100 mL of diethyl ether with stirring. The precipitated polymer was dissolved in 100 mL of dichloromethane and washed with 100 mL of ethylenediaminetetraacetic acid aqueous solution to completely remove copper ions. The dichloromethane layer was collected, dried over magnesium sulfate, filtered, concentrated with an evaporator, and then again taken into diethyl ether to precipitate the polymer. The polymer was recovered by filtration and dried under reduced pressure to obtain a modified polymer in a yield of 84%. The synthesis was confirmed by ¹ H-NMR. Deuterated dichloromethane was used as the solvent. The results are shown in FIG.

Modification with 3,3-dimethyl-1-butyne After glycidyl azide polymer (0.30 g) was dissolved in 15 mL of DMF at 40 ° C., tetrakis acetonitrile copper (I) hexafluorophosphate (56 mg) and 3,3- Dimethyl-1-butyne (0.93 mL) was added. The reaction was conducted with stirring at 40 ° C. for 24 hours under an argon atmosphere. 15 mL of DMF and 15 g of cation exchange resin were added to the reaction solution to adsorb copper ions. After removing the cation exchange resin by filtration, the solvent was distilled off by an evaporator. In order to completely remove DMF, a polymer solution dissolved in 10 mL of dichloromethane was added dropwise to 300 mL of diethyl ether with stirring. The precipitated polymer was dissolved in 200 mL of dichloromethane and washed with 200 mL of ethylenediaminetetraacetic acid aqueous solution to completely remove copper ions. The dichloromethane layer was collected, dried over magnesium sulfate, filtered, concentrated with an evaporator, and then again taken into diethyl ether to precipitate the polymer. The polymer was recovered by filtration and dried under reduced pressure to obtain a modified polymer in a yield of 85%. The synthesis was confirmed by ¹ H and ¹³ C-NMR. Deuterated chloroform was used as the solvent. The results are shown in FIG.

Modification with α-methyl, ω-propadyl-triethylene glycol After dissolving glycidyl azide polymer (0.27 g) in 15 mL of THF at 40 ° C., tetrakis acetonitrile copper (I) hexafluorophosphate (50 mg) and α-methyl , ω-propadyl-triethylene glycol (0.70 mL) was added. The reaction was allowed to stir at 50 ° C. for 24 hours under an argon atmosphere. After adding 20 mL of THF to the reaction solution, 15 gg of cation exchange resin was added to adsorb copper ions. After removing the cation exchange resin by filtration, the solution was concentrated by an evaporator. The polymer was precipitated by dropping the polymer solution into 300 mL of diethyl ether. The polymer was recovered by filtration and dried under reduced pressure to obtain a modified polymer in a yield of 88%. The synthesis was confirmed by ¹ H and ¹³ C-NMR. Heavy DMSO was used as the solvent. The results are shown in FIG.

A glycidyl azide polymer modified with methyl propiolate (0.30 g) was dissolved in 20 mL of DMF at 40 ° C., followed by tetrakis acetonitrile copper (I) hexafluorophosphate (56 mg) and methyl propiolate (0.36 mL). Was added. The reaction was conducted with stirring at 40 ° C. for 24 hours under an argon atmosphere. In order to remove copper ions, 15 mL of DMF and 15 g of cation exchange resin were added to the reaction solution. After removing the cation exchange resin by filtration, the solution was concentrated by an evaporator. In order to completely remove copper ions, the polymer solution was added dropwise to an aqueous solution of disodium ethylenediaminetetraacetate (300 mL). The precipitated polymer was collected by filtration and washed with hexane. The modified polymer was obtained in 98% yield by drying under reduced pressure. The synthesis was confirmed by ¹ H and ¹³ C NMR. Heavy DMSO was used as the solvent. The results are shown in FIG.

The polymer (0.30 g) synthesized in Example 8 was dissolved in a mixed solvent of DMF and water (15 mL / 1.5 mL). After adding 0.90 g of potassium hydroxide, the reaction solution was reacted with stirring at 60 ° C. for 16 hours under an argon atmosphere. After removing the solvent with an evaporator, the polymer was dissolved in 100 mL of distilled water. After removing insoluble components by filtration, 1 molar hydrochloric acid was added to bring the pH of the solution to 1. After confirming that the polymer had precipitated, the solvent was discarded by decantation. The polymer was washed with a small amount of water and hexane, and then dried under reduced pressure to obtain a deesterified polymer in a yield of 100%. The synthesis was confirmed by ¹ H and ¹³ C NMR. Heavy DMSO was used as the solvent. The results are shown in FIG.

Two types of alkynes (methyl propiolate, hexyne) were reacted with glycidyl azide polymer.
Glycidyl azide polymer (0.30 gg) was dissolved in 20 mL DMF at 40 ° C., followed by tetrakis acetonitrile copper (I) hexafluorophosphate (56 mg), methyl propiolate (0.18 mL) and 1-hexyne (0 .23 mL) was added. The reaction was conducted with stirring at 40 ° C. for 24 hours under an argon atmosphere. In order to remove copper ions, 15 mL of DMF and 15 g of cation exchange resin were added to the reaction solution. After removing the cation exchange resin by filtration, the solution was concentrated by an evaporator. In order to completely remove copper ions, the polymer solution was added dropwise to an aqueous solution of disodium ethylenediaminetetraacetate (300 mL). The precipitated polymer was collected by filtration and washed with hexane. The copolymer was obtained in 97% yield by drying under reduced pressure. The synthesis was confirmed by ¹ H and ¹³ C NMR. Heavy DMSO was used as the solvent. The results are shown in FIG.

The polymer (0.30 g) obtained in Example 10 was dissolved in a mixed solvent of DMF and water (15 mL / 1.5 mL). After adding 0.90 g of potassium hydroxide, the reaction solution was reacted with stirring at 60 ° C. for 16 hours under an argon atmosphere. After removing the solvent with an evaporator, the polymer was dissolved in 100 mL of distilled water. After removing insoluble components by filtration, 1 molar hydrochloric acid was added to bring the pH of the solution to 1. After confirming that the polymer had precipitated, the solvent was discarded by decantation. The polymer was washed with a small amount of water and then dissolved in 20 mL DMF. The polymer solution was dried with magnesium sulfate, filtered, and concentrated by an evaporator. The polymer solution was added dropwise to 300 mL of dichloromethane with stirring. The precipitated polymer was collected by filtration, washed with water and hexane, and then dried under reduced pressure to obtain a copolymer with a yield of 90%. The synthesis was confirmed by ¹ H and ¹³ C NMR. Heavy DMSO was used as the solvent. The results are shown in FIG.

Two types of alkynes (hexyne and α-methyl, ω-propazyl-tetraethylene glycol) were reacted with glycidyl azide polymer.
Glycidyl azide polymer (0.30 gg) was dissolved in 15 mL of DMF at 40 ° C., followed by tetrakis acetonitrile copper (I) hexafluorophosphate (50 mg), 1-hexyne (0.34 mL) and α-methyl, ω- Propazil-tetraethylene glycol (0.67 mL) was added. The reaction was allowed to stir at 50 ° C. for 24 hours under an argon atmosphere. In order to remove copper ions, 15 mL of DMF and 15 g of cation exchange resin were added to the reaction solution. After removing the cation exchange resin by filtration, the solution was concentrated by an evaporator. The polymer solution was added dropwise to 300 mL of diethyl ether with stirring. The precipitated polymer was dissolved in 200 mL of dichloromethane and washed with 200 mL of ethylenediaminetetraacetic acid aqueous solution to completely remove copper ions. The dichloromethane layer was collected, dried over magnesium sulfate, filtered, concentrated with an evaporator, and then again taken into diethyl ether to precipitate the polymer. The polymer was recovered by filtration and dried under reduced pressure to obtain a modified polymer in 89% yield. The synthesis was confirmed by ¹ H-NMR. Deuterated chloroform was used as the solvent. The results are shown in FIG.
Further, it was confirmed from the peak area of the NMR spectrum that the abundance ratio of the alkyl chain to the ethylene glycol chain in the copolymer was 2: 1.

Three alkynes (methyl propiolate, hexyne and 1-ethynylpyrene) were reacted with glycidyl azide polymer.
Glycidyl azide polymer (0.30 g) was dissolved in 15 mL of DMF at 40 ° C., and 8 μL was taken from tetrakis acetonitrile copper (I) hexafluorophosphate (56 mg) and 1-ethynylpyrene (0.36 M DMF solution). Added). The reaction was conducted with stirring at 40 ° C. for 2 hours under an argon atmosphere. Further, methylpropiolate (0.13 mL) and 1-hexyne (0.46 mL) were added, and the mixture was allowed to react with stirring at 40 ° C. for 24 hours under an argon atmosphere. In order to remove copper ions, 15 mL of DMF and 15 g of cation exchange resin were added to the reaction solution. After removing the cation exchange resin by filtration, the solution was concentrated by an evaporator. In order to completely remove copper ions, the polymer solution was added dropwise to an aqueous solution of disodium ethylenediaminetetraacetate (200 mL). The precipitated polymer was collected by filtration and washed with hexane. By drying under reduced pressure, 0.56 g of the modified polymer was obtained. The synthesis was confirmed by ¹ H-NMR. Heavy DMSO was used as the solvent. The results are shown in FIG.

The polymer (0.30 g) obtained in Example 13 was dissolved in a mixed solvent of DMF and water (15 mL / 1.0 mL). After adding 0.90 g of potassium hydroxide, the reaction solution was reacted with stirring at 40 ° C. for 16 hours under an argon atmosphere. After removing the solvent with an evaporator, the polymer was dissolved in 100 mL of distilled water. After removing insoluble components by filtration, the pH of the solution was adjusted to 1 by adding 2 molar hydrochloric acid. After confirming that the polymer had precipitated, the solvent was discarded by decantation. The polymer was washed with water and hexane and then dried under reduced pressure to obtain 0.24 g of a copolymer. The synthesis was confirmed by ¹ H-NMR. Heavy DMSO was used as the solvent. The results are shown in FIG. The ultraviolet-visible absorption spectrum and fluorescence spectrum of the obtained copolymer are shown in FIGS. The polymer was dissolved in DMSO. The peaks seen in these spectra are based on the absorption and emission of pyrene introduced into the copolymer.

  From Examples 1-14, it can be understood that the substituent R of the polymer derivative of the present invention is not limited to a specific substituent. It can also be understood that the copolymer derivative of the present invention comprising a plurality of different constituent monomers can be obtained by subjecting different types of alkyne compounds to the reaction (Examples 10-14).

The pyrolysis properties of the glycidyl azide polymer and the polymer derivative of the present invention were compared.
The thermal decomposition characteristics of the glycidyl azide polymer and the polymers obtained in Examples 1, 3, 4 and 6 are shown in FIG. The curve indicated by reference numeral 1 in the figure indicates the decomposition state of the glycidyl azide polymer, and the plurality of curves indicated by reference numeral 2 indicate the decomposition curves of the polymers obtained in Experimental Examples 1, 3, 4, and 6. In the glycidyl azide polymer, decomposition of the azide group occurs at around 250 ° C., and the mass is lost as much as 40%. It can be seen that when all azide groups are converted to 4-position-modified 1,2,3-triazole groups, they are not decomposed to around 400 ° C.

  By changing the substituent R, the solubility of the polymer can be changed. Solubility was confirmed with respect to the polymer obtained by Example 1,3,4,6,8,9. The results are shown in Table 1. It turns out that solubility can be controlled by the kind of alkyne compound used for modification. The starting glycidyl azide polymer is insoluble in water, while the polymer of Example 9 is soluble in water. By selecting the type of alkyne compound, a polymer having completely different solubility from that of glycidyl azide polymer can be produced.

According to the present invention, a functional polymer having amphiphilic properties having a hydrophilic group and a hydrophobic group simultaneously as in Example 11 can be produced. Carboxylic acid and hydrocarbon chain correspond to the hydrophilic part and the hydrophobic part, respectively.

  Furthermore, as in Example 14, a fluorescent probe such as pyrene can be introduced into the amphiphilic polymer. As described above, the present invention makes it possible to freely add functions as required.

  Differential scanning calorimetry was performed on the polymers and glycosidyl azide polymers obtained in Examples 1, 3, 4, 6, 8, and 9 to determine glass transition temperatures. The results are shown in Table 2. It can be seen that the glass transition temperature can be controlled by the type of alkyne compound used for modification. Since the main chain of the polymer obtained in the present invention is a flexible polyether, the glass transition temperature is lower than that of a polyolefin-based polymer such as polystyrene or polymethyl methacrylate. Such a feature can be expected to be applied as a soft material.

Table 3 shows the synthesis conditions and recovery rates of the glycidyl-4 position-modified 1,2,3-triazole derivative polymers of Examples 1 to 8. Table 4 shows examples that did not react well as Comparative Examples 1 to 6. In some examples, the conversion of the glycidyl azide polymer to 1,2,3-triazole did not reach 100%. In other examples, the reaction solution changed to a gel. In the table, glycidyl azide polymer is expressed as GAP.
The higher the reaction temperature, the shorter the reaction. Depending on the type of alkyne compound, the boiling point is low, and if it reacts at a high temperature, it vaporizes. Therefore, an excess alkyne compound is required for 100% conversion (Comparative Examples 2, 3, 4). Moreover, although reaction is complete | finished in a short time, so that solution concentration is high, when a solution concentration is high, the polymer is entangled and the example which the reaction liquid has gelatinized is seen (Comparative Examples 1, 5, and 6). Once gelled, it is difficult to re-dissolve and hinders purification. Gelation could be prevented by increasing the amount of solvent and decreasing the solution concentration.

As shown in Table 4, the reaction between the glycidyl azide polymer and the alkyne compound may not completely proceed.
FIG. 19 shows the thermal decomposition characteristics of the glycidyl-4-position partially modified-1,2,3-triazole derivative polymer in which 20% of the azide group remains. The weight loss due to the decomposition of the azide group occurs around 250 ° C., and it can be seen that the remaining azide group is a problem for practical application as a non-explosive material.

Claims (6)

A glycidyl-4-position modified 1,2,3-triazole derivative polymer represented by the following general formula (1).

(1)
(In the formula, R is an alkyl group, a halogen group, a hydroxyl group, an aldehyde group, an amino group, a cyano group, a nitro group, a carboxyl group, a phosphoric acid group, a sulfo group, a thiol group, a vinyl group, or a cyclic group having 3 to 30 carbon atoms. A substituent selected from organic compounds, which is directly bonded to a triazole group, or an ester bond, an amide bond, an aliphatic hydrocarbon chain having 1 to 30 carbon atoms, a cyclic organic compound having 3 to 30 carbon atoms, It is bonded via one or more spacer units selected from oligoethylene glycol chains or alkyl ether chains having 2 to 10 repeats,
n is the number of repetitions, and is selected so that the molecular weight of the glycidyl-4-position-modified-1,2,3-triazole derivative polymer falls within the range of 2,000-8 million. ) The glycidyl-4 position-modified 1,2,3-triazole derivative polymer according to claim 1, wherein the glycidyl-4 position-modified-1,2,3-triazole derivative polymer is represented by the following general formula (2).

(2)
(Wherein R ¹ and R ² are an alkyl group, a halogen group, a hydroxyl group, an aldehyde group, an amino group, a cyano group, a nitro group, a carboxyl group, a phosphoric acid group, a sulfo group, a thiol group, a vinyl group, or a carbon number of 3 to 3. A substituent selected from 30 cyclic organic compounds, which is directly bonded to a triazole group, or an ester bond, an amide bond, an aliphatic hydrocarbon chain having 1 to 30 carbon atoms, and a ring having 3 to 30 carbon atoms Are bonded via one or more kinds of spacer units selected from the formula organic compounds, oligoethylene glycol chains having 2 to 10 repeats or alkyl ether chains,
The sum of a and b is n. ) The glycidyl-4 position-modified 1,2,3-triazole derivative polymer according to claim 1, wherein the glycidyl-4 position-modified-1,2,3-triazole derivative polymer is represented by the following general formula (3).

(3)
(Wherein R ¹ , R ² and R ³ are alkyl groups, halogen groups, hydroxyl groups, aldehyde groups, amino groups, cyano groups, nitro groups, carboxyl groups, phosphate groups, sulfo groups, thiol groups, vinyl groups or carbons. A substituent selected from a cyclic organic compound of 3 to 30 and directly bonded to a triazole group, or an ester bond, an amide bond, an aliphatic hydrocarbon chain of 1 to 30 carbon atoms, 3 to 3 carbon atoms 30 cyclic organic compounds, bonded through one or more types of spacer units selected from oligoethylene glycol chains or alkyl ether chains having 2 to 10 repeats,
The sum of a, b and c is n. ) The glycidyl-4 position according to any one of claims 1 to 3, wherein R, R ¹ , R ² or R ³ is a substituent selected from substituents represented by the following general formulas (4) to (14). Modified 1,2,3-triazole derivative polymer.

(4)

(5)

(6)

(7)

(8)

(9)

(10)

(11)

(12)

(13)

(14) The glycidyl-4 position-modified 1,2,3-triazole derivative polymer according to claim 1, wherein the glycidyl-4 position-modified-1,2,3-triazole derivative polymer is represented by the following general formula (15).

(15)
(Wherein R ^a , R ^b ,... R ^z are alkyl groups, halogen groups, hydroxyl groups, aldehyde groups, amino groups, cyano groups, nitro groups, carboxyl groups, phosphate groups, sulfo groups, thiol groups, A substituent selected from a vinyl group or a cyclic organic compound having 3 to 30 carbon atoms, which is directly bonded to a triazole group, or an ester bond, an amide bond, an aliphatic hydrocarbon chain having 1 to 30 carbon atoms, It is bonded via one or more types of spacer units selected from cyclic organic compounds having 3 to 30 carbon atoms, oligoethylene glycol chains or alkyl ether chains having 2 to 10 repetitions,
a, b,. . . , Z is n, and n is selected such that the molecular weight of the glycidyl-4-position modified-1,2,3-triazole derivative polymer is in the range of 2,000-8 million. )   A method of reacting a glycidyl azide polymer with at least one alkyne, wherein the molar ratio of alkyne compound / azide group is 1.0 or more, no unreacted azide group remains, and the reaction solution does not form a gel. A method for synthesizing a glycidyl-4-position-modified 1,2,3-triazole derivative polymer, characterized by reacting under conditions.

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