Title of Invention

GLYCIDYL 4-FUNCTIONALIZED- l,2,3-TRIAZOLE POLYMER DERIVATIVES AND METHOD FOR SYNTHESIS OF THE SAME

Technical Field

[0001]

This invention relates to glycidyl 4-functionalized- l,2,3"triazole polymer derivatives obtained by converting all the azide groups of a glycidyl azide polymer into 4-functionalized- 1,2,3-triazole groups.

Background Art

[0002]

Click chemistry is a concept to generate substances quickly and reliably by joining small module units together, and is used to find useful chemical compounds.

[0003]

Azide-alkyne Huisgen cycloaddition reaction is one of the most popular reactions in click chemistry. This reaction is a 1,3-dipolar cycloaddition between an azide and a carbon-carbon triple bond of the alkyne to give a 1,2,3-triazole group. Many useful substances have been synthesized from various combinations of azide and alkyne compounds (Non-patent literatures 1, 2).

Some research groups have already reported the click functionalization of azide-functionalized polymer (Non-patent literature 3), but azide-functionalized polymers or their precursors were prepared through polymerization of the monomers, which requires the experience and skills of polymer synthesis .

Glycidyl azide polymer is an azide -functionalized polymer which can be synthesized easily from commercially-available polymer polyepichlorohydrin. Glycidyl azide polymer has been studied as explosive or propellant materials (Patent literature 1, Non-patent literatures 4, 5). A research group has reported the application of glycidyl azide polymer as a curing agent to solidify the propellant, in which glycidyl azide polymers were chemically cross-linked using azide-alkyne Huisgen cycloaddition reaction. In this study, most of the azide groups were kept unreacted, because the cross-linked glycidyl azide polymer also acts as a propellant. The explosion energy of glycidyl azide polymer is originated from high-energy chemical bond of azide group. In the history of glycidyl azide polymer, nobody has tried to quench all azide groups of glycidyl azide polymer (Non-patent literatures 6, 7), maybe because everybody has recognized that glycidyl azide polymer is a high energy material, and nobody has imagined to expand its application field towards non-explosive materials.

Citation List

Patent Literature

[0004]

Patent literature l: JP 1995 -215790 A

Non-patent Literature

[0005]

Non-patent literature 1 : Angewandte Chemie International Edition 2002, 41, 2596.

Non-patent literature 2- ^' Macromolecular Rapid Communications 2007, 28, 15.

Non-patent Literature 3- Macromolecules 2007, 40, 796.

Non-patent literature 4 ^' Defence Science Journal, 2008, 58, 86 Non-patent literature 5: Propellants Explosives, Pyrotechnics, 1991, 16, 177.

Non-patent literature 6 ^' · Journal of Applie d Polymer Science, 2009, 1 14, 398.

Non-patent literature T- Propellants Explosives, Pyrotechnics, 2012, 37, 59.

Summary of Invention

Technical Problem

[0006]

An objective of this invention is to provide a polymer material having a new function by using glycidyl azide polymer as a starting material.

Solution to Problem

[0007]

Glycidyl 4-functionalized- l,2,3-triazole polymer derivatives of this invention (hereinafter simply referred to as the current ^_ invented polymer derivatives) are represented by general formula (l) shown below.

[0009]

R is a substituent group selected from alkyl, halogen, hydroxyl, aldehyde, amino, cyano, nitro, carboxyl, phosphate, sulfo, thiol, and vinyl groups or cyclic organic compounds having carbon number of 3 to 30, and R is directly bound to triazole group or bound through one or more types of spacer unit selected from ester bond, amide bond, aliphatic hydrocarbon chains having carbon number of 1 to 30, cyclic organic compounds having carbon number of 3 to 30, and oligo (ethylene glycol) chains having number of repeating unit of 2 to 10 or alkyl ether chains, and n is the number of repeating unit which covers the polymer molecular weight from 2000 to 8.0 million.

[0010]

The polymer derivative's synthesis method of this invention allows glycidyl azide polymer to react with at least one type of alkyne, and is characterized in that the molar ratio of (alkyne compound)/(azide group) is equal to or more than unity 1.0, that unreacted azide group does not exist, and that the reaction completes under the condition that the reaction mixture does not change to the physical gel.

Advantageous Effect of Invention

[0011]

The current-invented polymer derivatives are obtained by using glycidyl azide polymer as a synthetic starting material and allowing it to react with alkyne, thereby converting all the azide groups of the glycidyl azide polymer into 4-functionalized- 1,2,3-triazol groups. Unlike conventional chemical modification of glycidyl azide polymers, the current invented polymer derivatives have no high-energy functional group of azide group. As a consequence, these polymers have excellent thermal stability and there is no risk of explosion. Furthermore, since its polymer main chain is polyether, unlike polyolefin polymers with polyethylene main chain, the polymer backbone is highly flexible and its glass-transition temperature is low. This property is suitable for the application of this material to the soft materials.

In addition, the synthesis method of the polymer derivatives in this invention provides a synthetic condition of the polymers to convert all the azide groups of glycidyl azide polymer to 4-functionalized- l,2,3-triazole groups; and an easy work-up process to isolate the polymers from copper catalysis used in the reaction and from excess amounts of alkyne compound.

Brief Description of Drawings

[0012]

FIG. 1 is a chart showing the scheme of synthesis method of the polymer derivatives in this invention.

FIG. 2 is a chart showing the result of Ή and ¹³ C-NMR of the current-invented polymer derivatives obtained in Example 1.

FIG. 3 is a chart showing the result of ^! H-NMR of the current-invented polymer derivatives obtained in Example 2.

FIG. 4 is a chart showing the result of Ή and ¹³ C"NMR of the current-invented polymer derivatives obtained in Example 3.

FIG. 5 is a chart showing the result of Ή and ¹³ C-NMR of the current-invented polymer derivatives obtained in Example 4.

FIG. 6 is a chart showing the result of ^! H-NMR of the current-invented polymer derivatives obtained in Example 5.

FIG. 7 is a chart showing the result of Ή and ¹³ C"NMR of the current-invented polymer derivatives obtained in Example 6.

FIG. 8 is a chart showing the result of ^X H and ¹³ C-NMR of the current-invented polymer derivatives obtained in Example 7.

FIG. 9 is a chart showing the result of *Η and ¹ C-NMR of the current-invented polymer derivative obtained in Example 8.

FIG. 10 is a chart showing the result of Ή and ¹³ C-NMR of the current-invented polymer derivatives obtained in Example 9.

FIG. 11 is a chart showing the result of Ή and ¹³ C"NMR of the current-invented polymer derivatives obtained in Example 10.

FIG. 12 is a chart showing the result of *H and ¹³ C"NMR of the current-invented polymer derivatives obtained in Example 11.

FIG. 13 is a chart showing the result of ^! H-NMR of the current-invented polymer derivatives obtained in Example 12.

FIG. 14 is a chart showing the result of ^! H-NMR of the current-invented polymer derivative obtained in Example 13.

FIG. 15 is a chart showing the result of ^! H-NMR of the current-invented polymer derivatives obtained in Example 14.

FIG. 16 is a chart showing the result of the ultraviolet-visible absorption spectrum of the current-invented polymer derivatives obtained in Example 14.

FIG. 17 is a chart showing the result of the fluorescence spectrum of the current-invented polymer derivatives obtained in Example 14.

FIG. 18 is a chart showing the thermal stability of the glycidyl azide polymer and the current-invented polymer derivatives obtained in Examples.

FIG. 19 is a chart showing the thermal stability of the polymer that a part of the azide groups does not converted to the 4-functionalized" l,2,3-triazole group.

Description of Embodiments

[0013]

The polymer derivatives in this invention are represented general formula (l) shown below.

[0015]

In the above formula, R is a substituent group selected from alkyl, halogen, hydroxyl, aldehyde, amino, cyano, nitro, carboxyl, phosphate, sulfo, thiol, and vinyl groups or cyclic organic compounds having carbon number of 3 to 30, and R is directly bound to triazole group or bound through one or more types of spacer unit selected from ester bond, amide bond, aliphatic hydrocarbon chains having carbon number of 1 to 30, cyclic organic compounds having carbon number of 3 to 30, and oligo (ethylene glycol) chains having number of repeating unit of 2 to 10 or alkyl ether chains

[0016]

The alkyl group is a linear or branched lower alkyl group, specifically, a linear or branched lower alkyl group having carbon number of 1 to 6.

Ester bond or amide bond is bound to triazole group as follows represented by a general formula (19) or a gener al formula (20) .

(19)

[

(20)

[0019]

The cyclic organic compounds having carbon number of 3 to 30 may be monocyclic compounds or condensed-ring compounds. The monocyclic compounds include cycloalkane such as cyclopropane, cyclobutane, and cyclohexane, and aromatic rings such as benzene. The condensed-ring compounds, where some of monocyclic compounds are fused to form a single plane, contain 2 to 5 monocyclic compounds such as acene, phenanthrene, chrysene, and pyrene. Cyclic organic compounds include heterocyclic compounds such as thiophene and tetrahydrofuran.

[0020]

The aliphatic hydrocarbon chains may be straight or branched saturated hydrocarbon chains, or straight or branched unsaturated hydrocarbon chains, and preferably straight or branched saturated hydrocarbon chains having carbon number of 1 to 12.

[0021]

The oligo (ethylene glycol) chain is the unit having -0(C2H4) " repeating unit. The number of repeating unit ranges from 2 to 10.

[0022]

The alkyl ether chains are the units having -C _m H2m"0- or - CH2"0-C _m H2m"0- structure, where m is a natural number in the range from 1 to 18.

[0023]

n in the formula is the number of repeating unit which covers the polymer molecular weight from 2000 to 8.0 million.

[0024]

The substituent group in the formula, R is a substituent group introduced at the 4th position of the triazole ring. All the substituent groups in the polymer may be the same , but simultaneous introduction of some different substituents may be also possible. When all the substituent groups R are the same, the glycidyl 4 functionalized- 1,2,3-triazole polymer derivatives have one type of monomer as a constituent unit. When different substituent groups are introduced, the glycidyl 4-functionalized- 1,2,3-triazole polymer derivatives have a constituent unit containing two or more types of monomers. For example, when R is two or three substituent groups, the current-invented polymer derivatives are represented by formula (2) or (3). Furthermore, as described above, the substituent group R may be bound to triazole group with spacer molecules. As shown in Examples, the substituent group R may be bound to the terminal carbon of spacer molecules and the binding position is not limited.

[0025]

(2)

(3)

[0027]

The sum of a and b, or that of a, b, and c in formulae (2) and (3) is equal to n, which covers the polymer molecular weight from 2000 to 8.0 million.

[0028]

Three or more types of monomers as shown in formula (15) may be adopted to constitute the current-invented polymer derivatives.

[0029]

(15)

[0030]

The sum of a, b, and z in formula (15) is equal to n covers the polymer molecular weight from 2000 to 8.0 million

[0031] The substituent groups R, R ¹ , R ² , R ³ , R ^a , R ^b ... ,or R ^z bonded at the 4th position of the triazole ring in the formula are specific substituent groups represented by formulae (4) to (14) shown below.

(4)

[0033]

[0034]

(6)

[0035]

(7)

[0036]

(8)

[0037]

(9)

[0038]

do)

[0039]

(11)

[0040]

(12)

[0041]

(13)

[0042]

(14)

[0043]

The current-invented polymer derivatives do not contain azide groups at all, and consequently they are thermally stable and free from the risk of explosion. In addition, since the polymer main chain is polyether, unlike polyolefin polymer with polyethylene main chain, the polymer backbone is highly flexible and glass-transition temperature is low. This is the reason why the current-invented polymer derivatives can be used as soft materials.

[0044]

The synthesis method of the current-invented polymer derivative allows glycidyl azide polymer (represented by formulae (16)) and at least one type of alkyne compound represented by formula (17) to react each other in an organic Solvent such as ^iV-dimethylformamide (DMF), dimethylsulfoxide (DMSO) or tetrahydrofuran (THF) in the presence of a catalyst, and is characterized in that the molar ratio of (alkyne compound)/(azide group) is equal to or more than unity 1.0 and that unreacted azido group does not exist. FIG. 1 shows the reaction scheme.

Higher reaction temperature completes the reaction in shorter rime. However, since the boiling point of some alkyne compounds is low, the evaporation of the alkyne compounds may occur if the reaction temperature set to high, and thereby the excess amount of alkyne derivatives are required. Meanwhile, higher concentration of the solution completes the reaction in shorter time, but if the concentration of the solution set to high, the reaction solution have changed to physical gel in some cases due to the entanglement of the polymers. Once the solution changes to physical gel, the reaction does not proceed efficiently due to the suppression of mixing and diffusion of the polymer and alkyne compounds. In addition, it is difficult to re-dissolve the physical gel, which makes impossible to purify the polymer. In order to prevent gelation, the solution concentration of glycidyl azide polymer (g/mL) is preferably equal to or less than 2%. However, much lower concentration than 1% is not preferable, because it requires more alkyne compounds and longer reaction time. It is desirable to use a catalyst in the reaction. Copper catalysts such as tetrakis acetonitrile copper (I) hexafluorophosphate and copper sulfate are preferable.

[0045]

(16)

[0046]

(17)

[0047]

R in formula (17) is the same described above.

The molecular weight of the current-invented polymer derivatives depends on that of glycidyl azide polymer used as a starting material. Generally, the polymer has molecular weight distribution. Since glycidyl azide polymer used in Examples contains the polymer with the molecular weight from 2000 to 5.0 million, the molecular weight of the current-invented polymer derivatives covers from 2000 to 8.0 million.

Furthermore, by allowing two or more types of alkynes to react with glycidyl azide polymer, the copolymer-type polymer derivatives having two or more types of monomers as constituent units can be obtained. These copolymers are represented by formula (2), (3), or

(15).

The work-up process of the current-invented polymer derivatives refers to the methods described below. Copper catalysis can be removed by the adsorption using a cation exchange resin in the solution or by the chelation using disodium ethylenediaminetetraacetate aqueous solution. Excess amounts of alkyne compounds can be removed by adding polymer solution dropwise to a solvent which can dissolve the alkyne compound but cannot dissolve the polymer. The polymer can be recovered as a precipitate.

[0048]

The glycidyl azide polymer can be obtained by allowing polyepichlorohydrin (represented by formula (18)) to react with sodium azide in DMF at approximately 80°C.

(18)

[0050]

This invention will hereinafter be described further in detail by referring to examples.

The glycidyl azide polymer used in the examples was obtained by allowing the polyepichlorohydrin (Sigma-Aldrich Co., average molecular weight: 700,000) to react with sodium azide in DMF at 80°C for 24 hours. The polymer has molecular weight distribution. Glycidyl azide polymer used as the starting material contains the polymers with the molecular weight range from 2000 to 5.0 million. Example 1

[0051]

Modification by 2-propynylbenzene

Glycidyl azide polymer (0.30 g) was dissolved in DMF (15 mL) at 40°C. Tetrakis acetonitrile copper (I) hexafluorophosphate (56 mg) and 2-propynylbenzene (0.75 mL) were added to the reaction mixture. The reaction mixture was stirred at 40°C under Ar atmosphere for 24 hours. After adding DMF (15 mL), the cation exchange resin (15 g) was added to remove the copper ions. After the filtration to remove cation exchange resin, the solvent was removed by evaporation. In order to remove DMF completely, the polymer was dissolved in dichloromethane (10 mL), then the polymer solution was added dropwise to diethyl ether (300 mL) with stirring. The precipitated polymer was dissolved in dichloromethane (200 mL), and washed with ethylenediaminetetraacetic acid two sodium salt aqueous solution (200 mL) to remove copper ion completely. The organic layer was recovered, dried with MgSC« 4 and concentrated by evaporation. The polymer solution was added dropwise to diethyl ether with stirring. The polymer was recovered by filtration and dried under vacuum. The functionalized polymer was obtainable in 98% yield. The synthesis was confirmed by ^X H and ¹³ C NMR. Deuterated chloroform was used as solvent. FIG. 2 shows the results of ^X H and ¹³ C ^_ NMR (proton nuclear magnetic resonance and ¹³ C nuclear magnetic resonance).

Example 2

[0052]

Modification by l-tert-butyl-4-ethynylbenzene

Glycidyl azide polymer (0.30 g) was dissolved in DMF (15 mL) at 40°C. Copper sulfate pentahydrate (20 gm), sodium ascorbate (30 mg), and l-tert-butyl-4-ethynylbenzene (1.0 mL) were added to the reaction mixture. The reaction mixture was stirred at 50°C under Ar atmosphere for 20 hours for reaction to occur. DMF (6 mL) was added to the reaction mixture, and the reaction mixture was then added dropwise to ethylenediaminetetraacetic acid two sodium salt aqueous solution (250 mL) to form a precipitate of polymer and remove copper catalyst and the sodium ascorbate. After the polymer was washed sequentially with methanol (200 mL) and acetone (200 mL), and then dried under vacuum. The functionalized polymer was thus obtained in 87% yield. The synthesis was confirmed by ^! H-NMR. Deuterated dichloromethane was used as solvent. FIG. 3 shows the results obtained.

Example 3

[0053]

Modification by 2-propynylcyclohexane

Glycidyl azide polymer (0.30 g) was dissolved in DMF (15 mL) at 40°C. Tetrakis acetonitrile copper (I) hexafluorophosphate (56 mg) and 2-propynylcyclohexane (0.86 mL) were added to the reaction mixture. The reaction mixture was stirred at 40°C under Ar atmosphere for 24 hours. After adding DMF (15 mL), the cation exchange resin (15 g) was added to remove the copper ions. After the filtration to remove cation exchange resin, the solvent was removed by evaporation. In order to remove DMF completely, the polymer was dissolved in dichloromethane (10 mL), then the polymer solution was added dropwise to diethyl ether (300 mL) with stirring. The precipitated polymer was dissolved in dichloromethane (200 mL), and washed with ethylenediaminetetraacetic acid two sodium salt aqueous solution (200 mL) to remove copper ion completely. The organic layer was recovered, dried with MgS04 and concentrated by evaporation. The polymer solution was added dropwise to diethyl ether with stirring. The polymer was recovered by filtration and dried under vacuum. The functionalized polymer was obtainable in 84% yield. The synthesis was confirmed by ^: H and ¹³ C-NMR. Deuterated chloroform was used as solvent. FIG. 4 shows the results obtained.

Example 4

[0054]

Modification by 1-hexyne

Glycidyl azide polymer (0.30 g) was dissolved in DMF (15 mL) at 40°C. Tetrakis acetonitrile copper (I) hexafluorophosphate (56 mg) and 1-hexyne (0.69 mL) were added to the reaction mixture. The reaction mixture was stirred at 40°C under Ar atmosphere for 24 hours. After adding DMF (15 mL), the cation exchange resin (15 g) was added to remove the copper ions. After the filtration to remove cation exchange resin, the solvent was removed by evaporation. In order to remove DMF completely, the polymer was dissolved in dichloromethane (10 mL), then the polymer solution was added dropwise to diethyl ether (300 mL) with stirring. The precipitated polymer was dissolved in dichloromethane (200 mL), and washed with ethylenediaminetetraacetic acid two sodium salt aqueous solution (200 mL) to remove copper ion completely. The organic layer was recovered, dried with MgS0 ₄ and concentrated by evaporation. The polymer solution was added dropwise to diethyl ether with stirring. The polymer was recovered by filtration and dried under vacuum. The functionalized polymer was obtainable in 87% yield. The synthesis was confirmed by Ή and ¹³ C"NMR. Deuterated chloroform was used as solvent. FIG. 5 shows the results obtained. Example 5

[0055]

Modification by 1-pentine

Glycidyl azide polymer (0.11 g) was dissolved in DMF (5 mL) at 40°C. Copper sulfate pentahydrate (7 mg), sodium ascorbate (11 mg), and 1-pentine (0.20 n L) were added to the reaction mixture. The reaction mixture was stirred at 40°C under Ar atmosphere for 24 hours for reaction to occur. DMF (10 mL) and cation ion exchange resin (5 g) were added to the reaction mixture to allow them to adsorb copper ions. After the cation ion exchange resin was removed by filtration, the solvent was removed by evaporation. In order to remove DMF completely, the polymer was dissolved in dichloromethane (5 mL), and the polymer solution was added dropwise to diethyl ether (100 mL) while stirring. The precipitated polymer was dissolved in dichloromethane (100 mL), and washed with ethylenediaminetetraacetic acid two sodium salt aqueous solution (100 mL) to remove copper ions completely. The dichloromethane layer was recovered, dried with MgS0 ₄ , filtered, concentrated by evaporation, and then added dropwise again to diethyl ether to form a precipitate of polymer. The polymer was recovered by filtration and dried under vacuum. The functionalized polymer was thus obtained in 84% yield. The synthesis was confirmed by Ή-ΝΜίί,. Deuterated dichloromethane was used as solvent. FIG. 6 shows the results obtained.

Example 6

[0056]

Modification by 3,3-dimethyl-l-butyne

Glycidyl azide polymer (0.30 g) was dissolved in DMF (15 mL) at 40°C. Tetrakis acetonitrile copper (I) hexafluorophosphate (56 mg) and 3,3'dimethyl- 1-butyne (0.93 mL) were added to the reaction mixture. The reaction mixture was stirred at 40°C under Ar atmosphere for 24 hours. After adding DMF (15 mL), the cation exchange resin (15 g) was added to remove the copper ions. After the filtration to remove cation exchange resin, the solvent was removed by evaporation. In order to remove DMF completely, the polymer was dissolved in dichloromethane (10 mL), then the polymer solution was added dropwise to diethyl ether (300 mL) with stirring. The precipitated polymer was dissolved in dichloromethane (200 mL), and washed with ethylenediaminetetraacetic acid two sodium salt aqueous solution (200 mL) to remove copper ion completely. The organic layer was recovered, dried with MgS0 ₄ and concentrated by evaporation. The polymer solution was added dropwise to diethyl ether with stirring. The polymer was recovered by filtration and dried under vacuum. The functionalized polymer was obtainable in 85% yield. The synthesis was confirmed by ^X H and ¹³ C"NMR. Deuterated chloroform was used as solvent. FIG. 7 shows the results obtained.

Example 7

[0057]

Modification by a-methyl, ω-propargyl-triethylene glycol

Glycidyl azide polymer (0.27 g) was dissolved in tetrahydrofuran (15 mL) at 40°C. Tetrakis acetonitrile copper (I) hexafluorophosphate (50 mg) and a-methyl, arpropargyl-triethylene glycol (0.70 mL) were added to the reaction mixture. The reaction mixture was stirred at 50°C under Ar atmosphere for 24 hours. After adding tetrahydrofuran (20 mL), the cation exchange resin (15 g) was added to remove the copper ions. After the filtration to remove cation exchange resin, the solution was concentrated by evaporation. The polymer solution was added dropwise to diethyl ether (300 mL) with stirring. The polymer was recovered by centrifugation and dried under vacuum. The functionalized polymer was obtainable in 88% yield. The synthesis was confirmed by ^Χ Η and ¹³ C-NMR. Deuterated DMSO was used as solvent. FIG. 8 shows the results obtained.

Example 8

[0058]

Modification by methyl propiolate

Glycidyl azide polymer (0.30 g) was dissolved in DMF (20 mL) at 40°C. Tetrakis acetonitrile copper (I) hexafluorophosphate (56 mg) and methyl propiolate (0.36 mL) were added to the reaction mixture. The reaction mixture was stirred at 40 °C under Ar atmosphere for 24 hours. After adding DMF (15 mL), the cation exchange resin (15 g) was added to remove the copper ions. After the filtration to remove cation exchange resin, the solution was concentrated by evaporation. In order to remove copper ion completely, the polymer solution was added dropwise to ethylenediaminetetraacetic acid two sodium salt aqueous solution (300 mL) with stirring. The precipitated polymer was recovered by filtration, washed with hexane and dried under vacuum. The functionalized polymer was obtainable in 98% yield. The synthesis was confirmed by Ή and ¹³ C-NMR. Deuterated DMSO was used as solvent. FIG. 9 shows the results obtained.

Example 9

[0059]

The polymer obtained in Example 8 (0.30 g) was dissolved in mixture of DMF and water (15 mL / 1.5 mL). Potassium hydroxide (0.90 g) was added to the reaction mixture. The reaction mixture was stirred at 60°C under Ar atmosphere for 16 hours. After removing the solvent by evaporation, the polymer was dissolved in distilled water (100 mL). The insoluble staff was removed by filtration, then the pH of the solution changed to 1 by adding 1 molar hydrochloric acid. Since the polymer was precipitated, the aqueous phase was removed by decantation. The polymer was washed with small amount of water and hexane, and then dried under vacuum. The functionalized polymer was obtainable in 100%. The synthesis was confirmed by ^: H and ¹³ C"NMR. Deuterated DMSO was used as solvent. FIG. 10 shows the results obtained. Example 10

[0060]

Two alkynes, 1-hexyne and methyl propiolate, were reacted with glycidyl azide polymer. Glycidyl azide polymer (0.30 g) was dissolved in DMF (20 mL) at 40°C. Tetrakis acetonitrile copper (I) hexafluorophosphate (56 mg), methyl propiolate (0.18 mL) and 1-hexyne (0.23 mL) were added to the reaction mixture. The reaction mixture was stirred at 40°C under Ar atmosphere for 24 hours. After adding DMF (15 mL), the cation exchange resin (15 g) was added to remove the copper ions. After the filtration to remove cation exchange resin, the solution was concentrated by evaporation. In order to remove copper ion completely, the polymer solution was added dropwise to ethylenediaminetetraacetic acid two sodium salt aqueous solution (300 mL) with stirring. The precipitated polymer was recovered by filtration, washed with hexane and dried under vacuum. The functionalized polymer was obtainable in 97% yield. The synthesis was confirmed by Ή and ¹³ C-NMR. Deuterated DMSO was used as solvent. FIG. 11 shows the results obtained.

Example 11 [0061]

The polymer obtained in Example 10 (0.30 g) was dissolved in mixture of DMF and water (15 mL / 1.5 mL). Potassium hydroxide (0.90 g) was added to the reaction mixture. The reaction mixture was stirred at 60°C under Ar atmosphere for 16 hours. After removing the solvent by evaporation, the polymer was dissolved in distilled water (100 mL). The insoluble staff was removed by filtration, then the pH of the solution changed to 1 by adding 1 molar hydrochloric acid. Since the polymer was precipitated, the aqueous phase was removed by decantation. After washing the polymer with small amount of water, the polymer was dissolved in DMF (20 mL). The polymer solutio n was dried with MgSC* 4, filtrated and concentrated by evaporation. The polymer solution was added dropwise to dichloromethane (300 mL) with stirring. The polymer was recovered by filtration, washed with water and hexane and dried under vacuum. The functionalized polymer was obtainable in 90% yield. The synthesis was confirmed by ^: H and ¹³ C-NMR. Deuterated DMSO was used as solvent. FIG. 12 shows the results obtained.

Example 12

[0062]

Two alkynes, 1-hexyne and a-methyl, ω-propargyl-tetraethylene glycol, were reacted with glycidyl azide polymer. Glycidyl azide polymer (0.30 g) was dissolved in DMF (15 mL) at 40°C. Tetrakis acetonitrile copper (I) hexafluorophosphate (50 mg), 1 -hexyne (0.34 mL) and a-methyl, ω -propargyl-tetraethylene glycol (0.67 mL) were added to the reaction mixture. The reaction mixture was stirred at 50°C under Ar atmosphere for 24 hours. After adding DMF (15 mL), the cation exchange resin (15 g) was added to remove the copper ions. After the filtration to remove cation exchange resin, the solution was concentrated by evaporation. The polymer solution was added dropwise to diethyl ether (300 mL) with stirring. The precipitated polymer was dissolved in dichloromethane (200 mL), and washed with ethylenediaminetetraacetic acid two sodium salt aqueous solution (200 mL) to remove copper ion completely. The organic layer was recovered, dried with MgS0 ₄ and concentrated by evaporation. The polymer solution was added dropwise to diethyl ether with stirring. The polymer was recovered by filtration and dried under vacuum. The functionalized copolymer was obtainable in 89% yield. The synthesis was confirmed by ^! H-NMR. Deuterated chloroform was used as solvent. FIG. 13 shows the results obtaine d.

The ratio of alkyl chain to ethylene glycol chain in the copolymer is 2 : 1, which is calculated from the integrals of NMR peak areas.

Example 13

[0063]

Three alkynes, methyl propiolate, 1-hexine, and 1-ethynylpyrene, were reacted with glycidyl azide polymer. Glycidyl azide polymer (0.30 g) was dissolved in DMF (15 mL) at 40°C. Tetrakis acetonitrile copper (I) hexafluorophosphate (56 mg) and 1 -ethynylpyrene (8 μϋι from 0.36 M DMF solution) were added to the reaction mixture. The reaction mixture was stirred at 40°C under Ar atmosphere for two hours while stirring for reaction to occur. Methyl propiolate (0.13 mL) and 1-hexine (0.46 mL) were then added to the reaction mixture, which was stirred at 40°C under Ar atmosphere for 24 hours while stirring. In order to remove copper ions, DMF (15 mL) and cation ion exchange resin (15 g) were added to the reaction mixture. After the cation ion exchange resin was removed by filtration, the solution was concentrated by evaporation. To remove copper ions completely, the polymer solution was added dropwise to ethylenediaminetetraacetic acid two sodium salt aqueous solution (200 mL). The precipitated polymer was recovered by filtration, washed with hexane, and dried under vacuum. The functionalized polymer (0.56 g) was thus obtained. The synthesis was confirmed by ^! H-NMR. Deuterated DMSO was used as solvent. FIG. 14 shows the results obtained.

Example 14

[0064]

The polymer obtained in Example 13 (0.30 g) was dissolved in mixture of DMF and water (15 mL/1.0 mL). Potassium hydroxide (0.90 g) was added to the reaction mixture. The reaction mixture was stirred at 40°C for 16 hours while stirring for reaction to occur. After the solvent was removed by evaporation, the polymer was dissolved in distilled water (100 mL). The insoluble staff was removed by filtration, and then 2-molar hydrochloric acid was added to change the pH of the solution to 1. After checking that the polymer had precipitated, the aqueous phase was removed by decantation. The polymer was washed with water and hexane, and then dried under vacuum. The copolymer (0.24 g) was thus obtained. The synthesis was confirmed by Ή-ΝΜΕ,. Deuterated DMSO was used as solvent. FIG. 15 shows the results obtained. FIG. 16 and 17 respectively show the ultraviolet-visible absorption spectrum and fluorescence spectrum of the obtained copolymer. The polymer was dissolved in DMSO. The peak in these spectra is respectively based on absorption and emission of pyrene introduced in the copolymer.

[0065]

It was found from Examples 1 to 14 that the substituent R in the current-invented polymer derivatives is not restricted in the specific substituent groups. It was also found that by simultaneous functionalization using different types of alkyne compounds, the copolymer-type polymer derivatives can be obtained (Examples 10-14). Example 15

[0066]

Thermal decomposition behavior of the current-invented polymer derivatives was compared with that of glycidyl azide polymer.

FIG. 18 shows the thermal decomposition characteristics of the glycidyl azide polymer and those of the polymers obtained in Examples 1, 3, 4, and 6. The curve marked as 1 in the chart represents the decomposition profile of glycidyl azide polymer, and the rest of the curves marked as 2 are the decomposition profiles of the polymers obtained in Examples 1, 3, 4, and 6. In the case of glycidyl azide polymer, decomposition of the azide group occurred at around 250°C. At this temperature, glycidyl azide polymer lost its weight as large as 40%. After converting all the azide groups to 4-functionalized 1,2, 3-triazole groups, decomposition did not occur until the temperature reached approximately 400°C.

Example 16

[0067]

The solubility of the polymers was controllable by changing the substituent R. The solubility of polymers obtained in Examples 1, 3, 4, 6, 8, and 9 was checked. Table 1 shows the results obtained. It is apparent that the solubility can be controlled depending on the types of alkyne compounds to be used for modification. The starting material glycidyl azide polymer is insoluble in water, but the polymers obtained in Example 9 dissolve in water. By selecting types of alkyne compounds, a polymer having completely different solubility from glycidyl azide polymer can be produced.

[0068]

According to this invention, as in the case of Example 11, an amphiphilic functional copolymer having both hydrophilic and hydrophilic groups can be produced. The carboxylic acid and hydrocarbon chain corresponds to hydrophilic and hydrophobic units, respectively.

[0069]

Furthermore, as in the case of Example 14, fluorescent probe such as pyrene can be introduced to the amphiphilic copolymer. This invention thus allows tailor-made functionalization.

[0070]

Table 1

Solvent in which

Polymer

the polymer is soluble

Polymer

obtained in Dichloromethane, DMF, DMSO

Example 1

Polymer

obtained in Dichloromethane, THF

Example 3

Polymer

Dichloromethane, THF, DMF,

obtained in

DMSO

Example 4

Polymer

obtained in Dichloromethane, DMF, DMSO

Example6

Polymer

obtained in DMF, DMSO

Example 8

Polymer

0.1N sodium hydroxide

obtained in

aqueous solution, DMSO

Example 9

Example 17

[0071]

The polymers obtained in Examples 1, 3, 4, 6, 8 , and 9 and glycidyl azide polymer were subjected to differential scanning calorimetry to determine their glass-transition temperatures. Table 2 shows the results obtained. It is apparent that the glass-transition temperatures can be controlled depending on the types of alkyne compounds to be used for modification. Since the main chain of the current-invented polymer is flexible polyether, their glass-transition temperatures are lower than those of polyolefin polymers such as polystyrene and polymethyl methacrylate. Thanks to this characteristic, the current-invented polymer derivatives are applicable to soft materials.

[0072]

Table 2

Glass -transition

Polymer

temperature

15

Glycidyl azide polymer -46°C

Polymer obtained in

60°C

Example 1

Polymer obtained in

57°C

Example 3

Polymer obtained in

20°C

Example 4 20

Polymer obtained in

55°C

Example 6

Polymer obtained in

64°C

Example 8

Polymer obtained in

Example 9 lire

[0073]

Table 3 summarizes the reaction conditions and recovery yield of the glycidyl 4-functionalized- 1,2,3-triazole polymer derivatives in Example 1 to 8. Table 4 lists unsuccessful examples as Comparative Examples 1 to 6. In some cases, 100% conversion of the azide group in the glycidyl azide polymer was not achieved. In other cases, the reaction mixture changed to the physical gel. The glycidyl azide polymer is abbreviated as GAP in the table.

Higher reaction temperature completes the reaction in shorter time. However, since the boiling point of an alkyne compound is low, the evaporation of the alkyne compound may occur, and thereby the excess amount of alkyne compound was required to achieve 100% conversion (Comparative Examples 2, 3, and 4). Higher concentration of the solution completes the reaction in shorter time, but if the concentration of the solution is too high, the reaction mixture changed to the physical gel due to the entanglement of the polymers (Comparative Examples 1, 5, and 6). Once gelation occurs, it is difficult to re-dissolve the polymer, which makes impossible to purify the polymer. Gelation was prevented by increasing the amount of solvent, thus decreasing the concentration of the solution.

[0074]

Table 3

^—

-

-

-

- a) 2-Propynylbenzene, b) 1- iei'i-Butyl-4-ethynylbenzene, c) 2-Propynylcyclohexane, d) 1 -Hexyne, e) i-Pentyne, f) 3,3-Dimethyl- 1-butyne, g) D -Metnyl, C -propargyl triethylene glycol, h) Methyl propiolate, i) CuS04- 5H ₂ 0, j) CuCMeCNVPFe, k) Sodium ascorbate.

[0075]

Table 4

-

-

-

-

- - a) 2-Propynylcyclohexane, b) 3, 3-Dimethyl- l-butyne, c) 1-Decyne, d) CuS0 ₄ - 5H ₂ 0, e) Cu(MeCN) ₄ ^■ PFe, f) Sodium ascorbate, g) Gelation, (h) Less than 100% conversion of azido group

[0076]

As shown in Table 4, the reaction of the glycidyl azide polymer with alkyne compounds does not proceed completely in some cases. FIG. 19 displays the thermal decomposition characteristics of glycidyl 4-functionalized-l, 2, 3"tiazole polymer derivatives containing 20% unreacted azido groups. The weight decreased at around 250°C due to the decomposition of unreacted azido group. It is clear that the unreacted azido group is problematic for the practical application toward non-explosive materials.