Next Article in Journal
Sources, Chemical Functionalization, and Commercial Applications of Nanocellulose and Nanocellulose-Based Composites: A Review
Next Article in Special Issue
Cyclodextrins and Their Polymers Affect the Lipid Membrane Permeability and Increase Levofloxacin’s Antibacterial Activity In Vitro
Previous Article in Journal
Improving the Performance of Polymer Solar Cells with Benzo[ghi]perylenetriimide-Based Small-Molecules as Interfacial Layers
Previous Article in Special Issue
Amphiphilic Diblock Copolymers Bearing Poly(Ethylene Glycol) Block: Hydrodynamic Properties in Organic Solvents and Water Micellar Dispersions, Effect of Hydrophobic Block Chemistry on Dispersion Stability and Cytotoxicity
 
 
Search for Articles:
Title / Keyword
Author / Affiliation / Email
Journal
Article Type
 
 
Advanced Search
 
Section
Special Issue
Volume
Issue
Number
Page
 
Journals
Polymers
Volume 14
Issue 20
10.3390/polym14204467
polymers-logo
Submit to this Journal Review for this Journal Propose a Special Issue
► Article Menu

Article Menu

share Share announcement Help format_quote Cite question_answer Discuss in SciProfiles thumb_up
...
Endorse textsms
...
Comment
first_page
settings
Order Article Reprints
Font Type:
Arial Georgia Verdana
Font Size:
Aa Aa Aa
Line Spacing:
Column Width:
Background:
Article

Synthesis of Functional Polyesters N-(2,3-epoxypropyl)-4,5,6,7-tetrahydroindole by Anionic Ring-Opening Polymerization

by
Marina Markova
,
Artem Emel’yanov
,
Inna Tatarinova
and
Alexander Pozdnyakov
*
A.E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, 1 Favorsky Str., 664033 Irkutsk, Russia
*
Author to whom correspondence should be addressed.
Polymers 2022, 14(20), 4467; https://doi.org/10.3390/polym14204467
Submission received: 31 August 2022 / Revised: 13 October 2022 / Accepted: 18 October 2022 / Published: 21 October 2022
(This article belongs to the Special Issue Properties and Characterization of Polymers in Nanomaterials)
Browse Figures
Versions Notes

Abstract

:
The functional polyethers of N-(2,3-epoxypropyl)-4,5,6,7-tetrahydroindole (in up to 61% yield, Mw = 8.7–11.7 kDa) and copolymers with ethylene glycol methylglycidyl ether (Mw = 5.6–14.2 kDa) and ethylene glycol vinylglycidyl ether (Mw = 6.4–12.3 kDa) have been synthesized via anionic ring-opening polymerization in the presence of KOH without solvent. The polymerization involves the opening of the epoxy ring to deliver the linear polyethers bearing free tetrahydroindole rings and oxyethylene or vinyloxy groups in the side chain. The polyethers are soluble in ethanol, benzene, chloroform, dioxane, DMF, and DMSO. The polyethers obtained exhibit the properties of high-resistance organic semiconductors: their electrical conductivity reaches 10−14 S/cm.

1. Introduction

Epoxy derivatives of heterocyclic compounds are valuable monomers for the design of high-tech polymeric materials. For instance, polymers of N-oxiranylmethylcarbazole are employed for recording and transmitting information. They are also used in devices that convert solar radiation energy into electrical one (solar photocells) and as photocapacitors [1,2,3,4,5,6,7]. Optical properties and film-forming ability of isolated carbazole molecules (photoluminescence maxima at 352 and 368 nm), compositions of low molecular weight epoxy resin Ruetapox 0162 with various amounts of 9-(2,3-epoxypropyl)carbazole and cured with isophoronediamine, can be exploited in LED fabrication [8]. Epoxy monomers can also be used to produce photopolymerizable compositions (PPC) in laser stereolithography with ultraviolet photoinitiating radiation [9].
Graft copolymers of N-epoxypropylpyrrole with polysiloxanes possess electrical conductivity in the range of 0.3–3.0 S/cm [10]. Copolymers of N-epoxypropylpyrrole with pyrrole, obtained by oxidative polycondensation, were claimed to be thin-film amperometric biosensors for urea [11] and galactose [12].
Polymers containing 4,5,6,7-tetrahydroindole and 1,2,4-triazole moieties in the side chain possess solubility, film-forming properties, and the ability to form complexes. The electrical conductivity of the obtained copolymers varies in a wide range from 10−15 S cm−1 to 10−7 S cm−1 (from dielectric to conductive material) depending on the composition and degree of doping with iodine [13].
Currently, only unsubstituted N-epoxypropylpyrrole is employed synthetic and applied research. The development of a general expedient method for the synthesis of pyrroles from ketoximes and acetylene in the presence of superbasic systems such as KOH/DMSO (Trofimov’s reaction) [14,15,16,17,18,19,20] opened the door to a plethora of pyrrole derivatives including 4,5,6,7-tetrahydroindole.
The improvement of the synthesis method of 4,5,6,7-tetrahydroindole [21,22,23], which makes it possible to obtain inexpensive THI on an industrial scale, accelerated the process of practical use of 4,5,6,7-tetrahydroindole derivatives. Thus, the prospects of using THI derivatives in the synthesis of drugs for the treatment of diseases such as Alzheimer’s disease and diabetes mellitus are shown [24]. THI derivatives are also promising in the treatment of oncological [25,26], viral [26], neurodegenerative diseases [27].
4,5,6,7-Tetrahydroindole is a “starting material” for the preparation of a new reactive class of epoxides, which are prospective building blocks for design of special polymeric semiconductors and photosensitive materials, intermediates of pharmacologically active compounds.
In the present work, we report for the first time the anionic homopolymerization of N-(2,3-epoxypropyl)-4,5,6,7-tetrahydroindole (EPTHI) and its copolymerization with ethylene glycol methylglycidyl ether and ethylene glycol vinylglycidyl ether.
The O–C–C–O bond sequence acts as a significant electron donor, providing polymers with polyoxide groups with hydrophilic properties such as solubility in many nonpolar organic solvents. In recent years, polyethylene oxides have become an object of scientific interest, such as drug delivery, tissue implantation and wound healing [28,29].
Over the last decade, polyethers, i.e., polymers containing the ether groups in the main chain (polyethylene oxides and polyalkylene oxides), have attracted much attention due to their possible applications as new safe electrolyte materials in energy storage devices such as lithium-ion batteries (solid polymer electrolytes). They are flexible, light, and non-flammable, they don’t leak [30,31,32,33].
The use of ethylene glycol methylglycidyl ether (EGMGE) and ethylene glycol vinylglycidyl ether (EGVGE) as comonomers enables to combine two important structural motifs, alkylpyrrole and oxyethylene (methyl ether or vinyl ether) in the desired polyether.

2. Materials and Methods

2.1. Materials

The IR absorption spectra of the synthesized polymers were recorded on a “Bruker Vertex 70” spectrometer (400–4000 cm−1) using films. 1H NMR spectra were recorded on a “Bruker DPX 400” (1H, 400.13 MHz) in CDCl3 using hexamethyldisiloxane as an internal standard. Number average molecular weight (Mn) and molecular weight distribution (Mw/Mn) were determined by size exclusion chromatography using a Shimadzu LC-20 Prominence liquid chromatograph equipped with a differential refractive index detector. Separation was carried out on an Agilent PolyPore column (7.5 × 300 mm, granule size 5 µm, separation range 200–2 × 106 g/mol) with a guard column in isocratic mode at 50 °C in N,N-dimethylformamide (eluent). The flow rate of the mobile phase was 1 mL/min, the sample volume was 20 µL. Polystyrene High EasiVials (Agilent, Santa Clara, CA, USA) standards with a narrow molecular weight distribution in the range from 162 to 6.6 × 106 g/mol was used to construct the calibration curve. The data was processed using Lab Solutions software. Elemental analysis was performed on a FLASH 1112 series EA instrument from Thermo Finnigan (Parma, Italy). The electrical conductivity of the polymers was measured using a standard E6-13A teraohmmeter. The studied samples were prepared in the form of tablets by pressing under a pressure of 700 kg/cm2. Thermal analysis of polymers was carried out using a thermogravimetric analyzer TGA i1000 (Instrument Specialists Incorporated, Twin Lake, WI, USA) at a heating rate of 10 °C/min from 25 to 900 °C in air.

2.2. Methods

2.2.1. Synthesis of N-(2,3-epoxypropyl)-4,5,6,7-tetrahydroindole

The reaction occurs through reaction of K-salt obtained in situ from KOH and 4,5,6,7-tetrahydroindole in a solution of toluene with epichlorohydrin, with azeotropic removal of water. The yields of N-(2,3-epoxypropyl)-4,5,6,7-tetrahydroindole were 68% [34] (Scheme 1):

2.2.2. Synthesis of Ethylene Glycol Methylglycidyl Ether (EGMGE)

EGMGE was synthesized from ethylene glycol methyl ether and epichlorohydrin in 19% yield according to [35] (Scheme 2):
Ethylene glycol methyl ether (76.00 g, 1.00 mol) and NaOH (40.00 g, 1.00 mol) were placed into a flask equipped with a stirrer, dropping funnel and thermometer. After NaOH was partially dissolved, epichlorohydrin (138.00 g, 1.50 mol) was added slowly (dropwise) to the reaction mixture upon stirring, maintaining the temperature at 20–25 °C. At this temperature, the mixture was stirred for 8 h. Then the reaction mixture was diluted with ice water (80 mL) and was extracted with diethyl ether (100 mL). The ether was removed on a water bath and the product was fractionated in vacuo to give EGMGE (25.4 g, 19%), b.p. = 71 °C/10 mm Hg; nD20 = 1.4260. Found, %: C 53.88, H 8.82. C6H12O3. Calculated, %: C 54.54, H 9.09.
EGVGE was used in 99.9% purity (GLC control), the constants corresponded to the literature data: b.p. = 76 °C/6 mm Hg, nD20 = 1.4480, d420 = 1.0333 [35]. The diethyl ether was purified by distillation.

2.2.3. Anionic polymerization of N-(2,3-epoxypropyl)-4,5,6,7-tetrahydroindole (typical procedure)

EPTHI (0.56 g, 3.16 mmol) and powdered KOH (0.011 g, 2 wt.%) were heated (90 °C) for 14 h under argon atmosphere upon stirring. After cooling, benzene (0.3 mL) was added to the reaction mixture (viscous, tarry mass). The target polymer EPTHI P7 was isolated by precipitation into hexane. The formed resin was washed with hexane and dried to constant weight to give hardened fragile dark-red resin with m.p. 127–130 °C (0.34 g, 61%), soluble in benzene, chloroform, ethanol, dioxane, DMF, and DMSO. Homopolymers P1–P6, P8 were obtained similarly.

2.2.4. Anionic copolymerization of EPTHI with EGMGE (typical procedure)

A mixture of EPTHI (0.0036 g, 0.0203 mmol), EGMGE (0.4964 g, 3.756 mmol), and powdered KOH (0.01 g, 2 wt.%) was heated (90 °C) under an argon atmosphere for 14 h upon stirring. The reaction mixture (colorless, transparent resin) was dissolved in benzene (0.3 mL) and precipitated into hexane to give copolymer PM1 (0.42 g, 84%) as a viscous slightly yellow resin, soluble in benzene, chloroform, and DMF. Copolymers PM2–PM5 and PV1–PV5 (copolymers with EGVGE) were obtained similarly.

3. Results and Discussion

The presence of an epoxy group in the molecule N-(2,3-epoxypropyl)-4,5,6,7-tetrahydroindole opens up prospects for the use of EPTHI in polymerization and copolymerization with the epoxy ring-opening under anionic polymerization conditions.

3.1. Anionic Ring-Opening Polymerization of EPTHI

Anionic polymerization of EPTHI was carried out under argon (50–90 °C, 14 h) without a solvent in the presence of KOH (0.5–2 wt.%) or Et3N (2 wt.%) as catalyst. The reaction proceeds with the opening of the epoxy ring and the production of linear polyesters P1–P8 with free tetrahydroindole rings in the side chain (Scheme 3):
The results of polymerization are presented in Table 1.
The polyethers P1–P8 obtained are brown resinous or powdered substances with a melting point of 127–130 °C, and molecular weight of 8.7–11.7 kDa (Figure 1). The polymers are soluble in ethanol, benzene, chloroform, dioxane, DMF, and DMSO.
The 1H NMR spectrum of the EPTHI is shown in Figure 2a. The 1H NMR spectra of the obtained polyethers (Figure 2b,c) show broadened signals characteristic of polymers. The signals of the pyrrole ring protons are observed at 6.55–6.45 ppm (H-2) and 6.00–5.50 ppm (H-3), while broad signals attributable to the CH2 groups of the cyclohexane ring are detected in the region of 2.50 ppm and 1.70 ppm. The signals at 3.82–3.40 ppm are assigned to CH-O, CH2-O groups of the main polymer chain and NCH2-pyrrole and the signals of CH=CH and CH2= groups appear at 5.11 ppm and 4.48 ppm.
The formation of the CH= and CH2= groups is caused by the chain transfer reaction to the monomer, which involves the abstraction of hydrogen from the CH group of the epoxy ring (Scheme 4) or from the alkyl substituent in the epoxy ring (Scheme 5) followed by very rapid ring cleavage to produce anions [36,37,38,39]:
The chain transfer leads to generation of new anionic active sites with a double bond. Interestingly, both cis-propenyl (Scheme 4) and allyl (Scheme 5) end groups can be formed.
In the IR spectra of polyethers P1–P8, the pyrrole ring bands remain at 708 cm−1 and 690 cm−1 (bending vibrations of the C–H group), 1298 cm−1 (stretching vibrations of the C–N group, characteristic vibrations for N-substituted pyrroles), 1370 cm−1 and 1490 cm−1 (stretching vibrations of the pyrrole core) [14]. The bands of the OH and ether groups appear at 3412–3365 cm−1, 1197–1254 cm−1 and 1136–1029 cm−1, respectively.
For polyether P7, synthesized at 90 °C using 2 wt.% KOH as a catalyst, weight average (Mw) and number average (Mn) molecular weights were determined (size exclusion chromatography) to be 8.9 and 7.1 kDa, correspondingly. The sample showed a unimodal molecular weight distribution (Figure 1). The polydispersity coefficient was 1.25.
As exemplified by polyether P7, EPTHI homopolymers exhibit the properties of high-resistance organic semiconductors: the value of their electrical conductivity is at the level of 10−14 S/cm (1.4·10−14 S/cm for P7). Doping with iodine vapor leads to resinification of the polymer that makes it impossible to measure the electrical conductivity.

3.2. Anionic Ring-Opening Copolymerization of EPTHI with EGMGE and EGVGE

Anionic copolymerization of EPTHI with EGMGE and EGVGE was carried out under argon (90 °C, 14 h) without a solvent in the presence of KOH (2 wt.%) as a catalyst. The copolymerization occurs with the opening of the epoxy rings of both comonomers and the formation of soluble linear polyesters (Scheme 6).
The copolymers are resinous substances (soluble in benzene, chloroform, and DMF) with a molecular weight (Mn) of 5.6–14.2 kDa and 6.4–12.3 kDa, respectively. The results of the copolymerization are given in Table 2.
In the 1H NMR spectra (CDCl3, δ, ppm) of copolymers PM1–PM5, together with the signals of the pyrrole ring protons (5.90 ppm and 6.50 ppm) and those of the CH2 groups of the cyclohexane ring (1.65–1.85 and 2.50 ppm) [13], the signals of EGMGE are detected at 3.35 ppm (CH3-O group), 3.80–3.50 ppm (CH-O and CH2-O groups of the main polymer chain and comonomer EGMGE). The signal of the cis-propenyl end group is observed at 5.11 ppm.
The composition of copolymer was calculated from the ratio of the integral intensities of protons of the pyrrole ring (5.87 ppm) and EGMGE CH3 group (3.35 ppm).
1H NMR spectra (CDCl3, δ, ppm) of copolymers PV1–PV5 contain the following signals: 6.55 d (1H, H-2, J = 2.4 Hz), 6.4 q (1H, CH=, J = 6.84 Hz), 5.94 d (1H, H-3, J = 2.7 Hz), 4.22 dd (2H, CH2=, J = 2.20 and 14.32 Hz), 4.04 dd (2H, CH2=, J = 2.08 and 6.76 Hz), 3.9–3.5 m (4H, CH2-O, N-CH2 group), 2.57–2.40 m (4H, CH2-4, CH2-7), and 1.85–1.70 m (4H, CH2-5, CH2-6).
The IR spectra of the copolymers show low intense bands of the terminal hydroxyl groups (3567–3364 cm−1 and 1200–1197 cm−1), probably due to the chain transfer to the monomer (Scheme 4 and Scheme 5), and the ether group (two bands in the region of 1125–1031 cm−1), bending vibrations of the C–H group of the pyrrole ring (700–755 cm−1). Intense absorption bands at 2931–2815 cm−1 correspond to stretching vibrations of hydrogen in the alkyl groups. In the spectra of copolymers, the absorption bands of the EGVGE vinyl group are observed at 3073 cm−1, 3046 cm−1, and 1620 cm−1 (Figure 3).
The yield, structure, and molecular weight of the polymers depend on composition of the initial monomer mixture and reactivity of the comonomers. In copolymer PM1 (Table 2), weight average molecular weight (Mw) is 18.4 kDa, and number average (Mn) is 14.2 kDa. When mass content of EPTHI increases to 0.9, the yield of polyether PM5 decreases from 84% to 25%, Mw decreases to 8.9 kDa, and Mn reduces to 5.6 kDa, while the degree of polydispersity augments from 1.29 to 1.59 (Table 2, Figure 4).
For the system EPTHI and EGVGE, at higher content of the tetrahydroindole comonomer in the reaction mixture, the yield of copolymers PV increases from 58% (PV1) to 77% (PV5). The Mn of copolymers decreases from 12.3 to 6.3 kDa, and Mw reduces from 16.5 to 8.6 kDa, the degree of polydispersity remains almost unchanged (Table 2, Figure 4).
Chromatograms of the molecular weight distribution of copolymers PM5 and PV5 (Figure 4) containing more than 50% of EPTHI indicate the presence of up to 8% (for PM5) and 12–13% (for PV5) fractions with a molecular weight of 2.3 kDa. Sample PV5 also has a fraction (up to 25%) with a molecular weight of 4.5 kDa. Polyethers PM1, PV1 with mass content of glycidyl ethers of 0.9 have higher molecular weights (Table 2, Figure 4). These samples show a unimodal molecular weight distribution.
According to thermal analysis, polymer P7 (Figure 5, Table 1) is stable up to 275 °C. Weight loss of sample P7, which occurs smoothly up to 489 °C, is 60%. This may be due to the abstraction of tetrahydroindole from homopolymer delivering polyfused heteroaromatic systems with loss of hydrogen and aromatization. This increases thermal stability of the polymer, which is reflected on the thermal destruction curve: the second phase of the macromolecule decomposition begins at 489 °C. Further up to 550 °C (in the range of 489–550 °C), the decomposition rate of sample P7 becomes faster. In this temperature range, the weight loss is 35% (total weight loss reaches 95%). A further increase in temperature does not significantly affect the weight loss of polymer P7 and at 947 °C the total weight loss is 99.71%.
Copolymers containing EGMGE units (samples PM1 and PM5) have a lower stability (270 and 260 °C) than polymer P7. Intense weight loss of copolymer PM1, containing only 5 mol.% of EPTHI, occurs up to 408 °C and is 90%. Probably, a significant part of the ethylene glycol methyl ether molecules is abstracted from the copolymer, which apparently contributes to the formation of a more thermodynamically stable polyconjugated polyvinylene chain (polyacetylene). A further increase in temperature to 600 °C leads to a smooth loss of sample weight (0.56% loss), apparently due to the elimination of residual fragments of ethylene glycol methyl ether and tetrahydroindole. The total weight loss at 600 °C is 99.56% (the weight of the sample is 0.44% of that taken for analysis). Weight loss of polymer PM5 occurs in step-wise manner: at 378 °C it is 18%, then at 378–427 °C, weight loss is 27% (total weight loss reaches 45%). From 427 °C to 482 °C the sample decomposition rate decreases, the weight loss is 10% (the total loss reaches 55%). A further increase in temperature to 563 °C is accompanied by a 30% weight loss (the total weight loss reaches 85%). When the sample is heated to 717 °C, it does not significantly affect the weight reduction (weight loss is 2.44%, total weight loss is 87.44%). At the end of the study (at 717 °C), the weight of the sample is 12.56% of that taken for analysis (Figure 6a).
The presence of EGVGE units in the macromolecule (by eight times higher than those of EPTHI, sample PV1, EPTHI:EGVGE = 0.11:0.89) enhances the stability of the copolymer up to 310 °C. An increase in the number of EPTHI units (copolymers PV3 and PV5) reduces the stability of the copolymer to 200–230 °C. At higher temperature (417 °C), the weight loss of sample PV1 reaches 67% (total weight loss is 77%) (Figure 6b). For copolymers PV3 and PV5, weight loss occurs smoothly and at 417 °C is only 42% and 29% (total weight loss is 52% and 39%, respectively). The complete decomposition of the copolymers occurs at about 500 °C (for sample PV1) and 600 °C (for samples PV3 and PV5).

4. Conclusions

In conclusion, polyethers of N-(2,3-epoxypropyl)-4,5,6,7-tetrahydroindole have been synthesized for the first time in up to 61% yield and a molecular weight of 8.7–11.7 kDa by of anionic ring-opening polymerization with KOH or Et3N as the catalyst and without solvent. The polyethers are brown resinous or powdered substances, thermally stable up to 275 °C. EPTHI homopolymers exhibit the properties of high-resistance organic semiconductors: their electrical conductivity is at the level of 10−14 S/cm. The copolymers of EPTHI with EGMGE (yield up to 84%, Mn = 5.6–14.2 kDa, PDI = 1.29–1.59) and EGVGE (yield up to 77%, Mn = 6.4–12.3 kDa, PDI = 1.19–1.34) have been obtained. The polymerization involves the opening of the epoxy ring to produce linear polyethers with free tetrahydroindole fragments and oxyethylene or vinyloxy groups in the side chain. The polyfunctional reactive polymers and copolymers with tetrahydroindole and vinyloxy groups can be employed as macromonomers for further polymerization and copolymerization both at the pyrrole ring (cationic polymerization) and at the vinyloxy group (for copolymers with EGVGE). They provide additional opportunities for directed tuning of their properties through modification at the reactive pyrrole ring.

Author Contributions

Conceptualization, M.M., I.T. and A.P.; methodology, M.M. and A.E.; validation, I.T.; formal analysis, A.E.; investigation, M.M. and I.T.; data curation, A.P.; project administration, A.P. All authors have read and agreed to the published version of the manuscript.

Funding

This research received no external funding.

Institutional Review Board Statement

Not applicable.

Informed Consent Statement

Not applicable.

Data Availability Statement

Not applicable.

Acknowledgments

The work was performed using the equipment of the Baikal Analytical Center for Collective Use of the Siberian Branch of the Russian Academy of Sciences.

Conflicts of Interest

The authors declare no conflict of interest.

References

  1. Akhmedov, K.M.; Karimov, K.S.; Cherkashin, M.I. Method for the Manufacture of a Photocapacitor/Photocell; USSR Authors’ Certificate 1581101; State Committee for Inventions and Discoveries: Moscow, Russia, 1988. [Google Scholar]
  2. Akhmedov, K.M.; Karimov, K.S.; Shcherbakova, I.M.; Porshnev, Y.N.; Cherkashin, M.I. The synthesis and properties of N-(2,3-epoxypropyl)carbazoles and the oligomers based on them. Russ. Chem. Rev. 1990, 59, 425–439. [Google Scholar] [CrossRef]
  3. Lopatinsky, V.P.; Rovkina, N.M.; Sutyagin, V.M.; Popov, V.A. Advances in the synthesis of new organic materials. Izv. Tomsk. Politekh. Univ. 2000, 303, 244–249. [Google Scholar]
  4. Malinauskas, T.; Vilionskiene, I.; Grazulevicius, J.V.; Getautis, V.; Reina, J.A.; Sidaravicius, J. Synthesis and properties of new derivatives of poly[9-(2,3-epoxypropyl)carbazole]. Polym. Int. 2008, 57, 1159–1164. [Google Scholar] [CrossRef]
  5. Kas’yan, L.I.; Pal’chikov, V.A.; Bondarenko, Y.S. Five-membered oxaza heterocyclic compounds on the basis of epoxides and aziridines. Russ. J. Org. Chem. 2011, 47, 797–841. [Google Scholar] [CrossRef]
  6. Brocas, A.-L.; Mantzaridis, C.; Tunc, D.; Carlotti, S. Polyether synthesis: From activated or metal-free anionic ring-opening polymerization of epoxides to functionalization. Prog. Polym. Sci. 2013, 38, 845–873. [Google Scholar] [CrossRef]
  7. Figueroa-Valverde, L.; Francisco, D.C.; Maria, L.; Marcela, R.; Virginia, M.; Tomas, L.; Magdalena, A. Design and synthesis of two epoxide derivatives from 3-ethynylaniline. J. Heterocycl. Chem. 2021, 58, 1154–1163. [Google Scholar] [CrossRef]
  8. Czub, P.; Mazela, W.; Pielichowski, J. Epoxy-carbazole compositions. Part I. Compositions with 9-(2,3-epoxypropyl)carbazole. Polimery 2003, 48, 641–644. [Google Scholar] [CrossRef]
  9. Malov, I.E.; Shiganov, I.N. Features of Photopolymerizing Compositions for Stereolithography with Visible Lasers; Vestnik MGTU im. N.E. Baumana. Ser. “Mashinostroenie”; Bauman Moscow State Technical University: Moscow, Russia, 2012; pp. 91–98. Available online: http://engjournal.ru/search/keyword/920/page1.html (accessed on 1 October 2022).
  10. Gunaydin, O.; Toppare, L.; Yagci, Y.; Harabagiu, V.; Pintela, M.; Simionescu, B.C. Synthesis of conducting polysiloxane—Polypyrrole graft copolymers. Polym. Bull. 2002, 47, 501–508. [Google Scholar] [CrossRef]
  11. Bozgeyik, İ.; Şenel, M.; Çevik, E.; Abasıyanık, M.F. A novel thin film amperometric urea biosensor based on urease-immobilized on poly(N-glycidylpyrrole-co-pyrrole). Curr. Appl. Phys. 2011, 11, 1083–1088. [Google Scholar] [CrossRef]
  12. Şenel, M.; Bozgeyik, İ.; Çevik, E.; Fatih Abasıyanık, M. A novel amperometric galactose biosensor based on galactose oxidase-poly(N-glycidylpyrrole-co-pyrrole). Synth. Met. 2011, 161, 440–444. [Google Scholar] [CrossRef]
  13. Prozorova, G.F.; Ermakova, T.G.; Kuznetsova, N.P.; Pozdnyakov, A.S.; Ivanov, A.V.; Trofimov, B.A. Electrical conductivity of copolymers of 1-vinyl-1,2,4-triazole with N-vinyl-4,5,6,7-tetrahydroindole. Russ. Chem. Bull. 2015, 64, 2141–2144. [Google Scholar] [CrossRef]
  14. Trofimov, B.A.; Mikhaleva, A.I. N-Vinylpyrroles; Nauka: Moscow, Russia, 1984. [Google Scholar]
  15. Lukevics, E.; Abele, E. Recent Advances in the Synthesis of Heterocycles from Oximes. Heterocycles 2000, 53, 2285. [Google Scholar] [CrossRef]
  16. Mikhaleva, A.I.; Schmidt, E.Y. Selected Methods for Synthesis and Modification of Heterocycles; Kartsev, V.G., Ed.; IBS Press: Moscow, Russia, 2002. [Google Scholar]
  17. Meyers, R.A. (Ed.) Encyclopedia of Physical Science and Technology; IBS Press: Moscow, Russia, 2001; ISBN 978-0-12-227410-7. [Google Scholar]
  18. Trofimov, B.A.; Mikhaleva, A.I.; Shmidt, E.Y.; Ryapolov, O.A.; Platonov, V.B. Method for Preparing 4,5,6,7-Tetrahydroindole. RU Patent 2297410, 20 April 2007. [Google Scholar]
  19. Rappoport, Z.; Liebman, J.F. (Eds.) The Chemistry of Hydroxylamines, Oximes and Hydroxamic Acids; PATAI’S Chemistry of Functional Groups; Wiley: Hoboken, NJ, USA, 2008; ISBN 9780470512616. [Google Scholar]
  20. Wang, Z. Comprehensive Organic Name Reactions and Reagents; John Wiley & Sons, Inc.: Hoboken, NJ, USA, 2010; ISBN 9780470638859. [Google Scholar]
  21. Trofimov, B.A.; Mikhaleva, A.I.; Shmidt, E.Y.; Ryapolov, O.A.; Platonov, V.B. Method for Preparing 4,5,6,7-Etrahydroindole. RU Patent 2307830, 10 October 2007. [Google Scholar]
  22. Trofimov, B.A.; Mikhaleva, A.I.; Shmidt, E.Y.; Vasil’tsov, A.M.; Ivanov, A.V.; Protsuk, N.I.; Ryapolov, O.A. A new technology for the synthesis of 4,5,6,7-tetrahydroindole. Dokl. Chem. 2010, 435, 307–310. [Google Scholar] [CrossRef]
  23. Merkulov, V.V.; Ryapolov, O.A.; Mantler, S.N. Tetrahydroindole: Its industrial synthesis and ways of using. Fundam. Res. 2017, 3, 67–71. [Google Scholar]
  24. Gulcin, İ.; Petrova, O.V.; Taslimi, P.; Malysheva, S.F.; Schmidt, E.Y.; Sobenina, L.N.; Gusarova, N.K.; Trofimov, B.A.; Tuzun, B.; Farzaliyev, V.M.; et al. Synthesis, Characterization, Molecular Docking, Acetylcholinesterase and α-Glycosidase Inhibition Profiles of Nitrogen-Based Novel Heterocyclic Compounds. ChemistrySelect 2022, 7, e202200370. [Google Scholar] [CrossRef]
  25. Polozhentseva, I.A.; Koval’skaya, A.V.; Tsypyshev, D.O.; Lobov, A.N.; Nazarov, A.M.; Danilko, K.V.; Kataev, V.A. Synthesis and cytotoxity of some tetrahydroindole derivetives. Bashkir Chem. J. 2018, 25, 59. [Google Scholar] [CrossRef]
  26. Vonderscher, J.; De Chassey, B.; Meyniel-Schicklin, L.; Miege, F. Preparation of Pyrrole-Type Compounds for Treatment of Viral Infections and Cancer. WO2022117697 (A1) 9 June 2022. [Google Scholar]
  27. Zack, D.; Bannister, T.; Voykovsky, T.; Yang, Z.; Berlinicke, C. Compositions and Methods for Treatment of Neurodegenerative Disease. WO2011/119777 A2 24 November 2011. [Google Scholar]
  28. Afroz, S.; Afrose, F.; Alam, A.K.M.M.; Khan, R.A.; Alam, M.A. Synthesis and characterization of polyethylene oxide (PEO)—N,N-dimethylacrylamide (DMA) hydrogel by gamma radiation. Adv. Compos. Hybrid Mater. 2019, 2, 133–141. [Google Scholar] [CrossRef]
  29. Mahdy, A.; Helal, R.H.; Abdel Moneam, Y.K.; Senna, M.M.H. Electron beam radiation synthesis of hydrogel based on biodegradable starch/ poly(ethylene oxide) (ST/PEO) blend and its application in controlled release of parasitic worm’s drugs. J. Drug Deliv. Sci. Technol. 2022, 74, 103531. [Google Scholar] [CrossRef]
  30. Barteau, K.P.; Wolffs, M.; Lynd, N.A.; Fredrickson, G.H.; Kramer, E.J.; Hawker, C.J. Allyl Glycidyl Ether-Based Polymer Electrolytes for Room Temperature Lithium Batteries. Macromolecules 2013, 46, 8988–8994. [Google Scholar] [CrossRef]
  31. Syromyatnikov, V.G.; Paskal’, L.P.; Mashkin, O.A. Polymeric electrolytes for lithium chemical power sources. Russ. Chem. Rev. 1995, 64, 249–257. [Google Scholar] [CrossRef]
  32. Lynd, N.A.; Fredrickson, G.H.; Hawker, C.J.; Kramer, E.J.; Barteau, K. Polymer Electrolytes Based on Poly(glycidyl ether)s. US Patent 8911639-B2, 16 December 2014. [Google Scholar]
  33. Kulova, T.L.; Skundin, A.M. Polymer electrolytes for sodium-ion batteries. Electrochem. Energy 2018, 18, 26–47. [Google Scholar] [CrossRef]
  34. Markova, M.V.; Morozova, L.V.; Schmidt, E.Y.; Mikhaleva, A.I.; Protsuk, N.I.; Trofimov, B.A. An alkylation of 4,5,6,7-tetrahydroindole with chloromethyloxirane in the presence of alkaline metal hydroxides. Arkivoc 2008, 2009, 57–63. [Google Scholar] [CrossRef] [Green Version]
  35. Trofimov, B.A. Heteroatomic Derivatives of Acetylene: New Polyfunctional Monomers, Reagents, and Intermediates; Nauka: Moscow, Russia, 1981. [Google Scholar]
  36. Oudian, J. Fundamentals of Polymer Chemistry; Mir: Moscow, Russia, 1974. [Google Scholar]
  37. Entelis, S.G. Reactive oligomers and their distribution by the type of functionality. Soros Educ. J. 1996, 7, 59–66. [Google Scholar]
  38. Sutyagin, V.M.; Bondaletova, L.I. Chemistry and Physics of Polymers; TPU: Tomsk, Russia, 2005. [Google Scholar]
  39. Labbé, A.; Carlotti, S.; Deffieux, A.; Hirao, A. Controlled Polymerization of Glycidyl Methyl Ether Initiated by Onium Salt/Triisobutylaluminum and Investigation of the Polymer LCST. Macromol. Symp. 2007, 249–250, 392–397. [Google Scholar] [CrossRef]
Polymers 14 04467 sch001 550
Scheme 1. Synthesis of N-(2,3-epoxypropyl)-4,5,6,7-tetrahydroindole.
Scheme 1. Synthesis of N-(2,3-epoxypropyl)-4,5,6,7-tetrahydroindole.
Polymers 14 04467 sch001
Polymers 14 04467 sch002 550
Scheme 2. Synthesis of ethylene glycol methylglycidyl ether.
Scheme 2. Synthesis of ethylene glycol methylglycidyl ether.
Polymers 14 04467 sch002
Polymers 14 04467 sch003 550
Scheme 3. Anionic ring-opening polymerization of N-(2,3-epoxypropyl)-4,5,6,7-tetrahydroindole.
Scheme 3. Anionic ring-opening polymerization of N-(2,3-epoxypropyl)-4,5,6,7-tetrahydroindole.
Polymers 14 04467 sch003
Polymers 14 04467 g001 550
Figure 1. Typical curves of the molecular weight distribution (e.g., homopolymer P7).
Figure 1. Typical curves of the molecular weight distribution (e.g., homopolymer P7).
Polymers 14 04467 g001
Polymers 14 04467 g002 550
Figure 2. 1H NMR spectra of EPTHI (a), polymer P8 (b) and polymer P7 (c).
Figure 2. 1H NMR spectra of EPTHI (a), polymer P8 (b) and polymer P7 (c).
Polymers 14 04467 g002
Polymers 14 04467 sch004 550
Scheme 4. Formation of cis-propenyl end groups.
Scheme 4. Formation of cis-propenyl end groups.
Polymers 14 04467 sch004
Polymers 14 04467 sch005 550
Scheme 5. Formation of allyl-propenyl end groups.
Scheme 5. Formation of allyl-propenyl end groups.
Polymers 14 04467 sch005
Polymers 14 04467 sch006 550
Scheme 6. Anionic ring-opening copolymerization of EPTHI with EGMGE and EGVGE.
Scheme 6. Anionic ring-opening copolymerization of EPTHI with EGMGE and EGVGE.
Polymers 14 04467 sch006
Polymers 14 04467 g003 550
Figure 3. FT-IR spectra of copolymers PM3 (a) and PV3 (b).
Figure 3. FT-IR spectra of copolymers PM3 (a) and PV3 (b).
Polymers 14 04467 g003
Polymers 14 04467 g004 550
Figure 4. Chromatograms (curves) of the molecular weight distribution of copolymers PM1, PM3, PM5 (a) and copolymers PV1, PV3, PV5 (b).
Figure 4. Chromatograms (curves) of the molecular weight distribution of copolymers PM1, PM3, PM5 (a) and copolymers PV1, PV3, PV5 (b).
Polymers 14 04467 g004
Polymers 14 04467 g005 550
Figure 5. Thermal analysis of homopolymer poly-N-(2,3-epoxypropyl)-4,5,6,7-tetrahydroindole P7.
Figure 5. Thermal analysis of homopolymer poly-N-(2,3-epoxypropyl)-4,5,6,7-tetrahydroindole P7.
Polymers 14 04467 g005
Polymers 14 04467 g006 550
Figure 6. Thermal analysis of copolymers poly-N-(2,3-epoxypropyl)-4,5,6,7-tetrahydroindole with ethylene glycol methylglycidyl ether (PM1, PM3, PM5) (a), copolymers poly-N-(2,3-epoxypropyl)-4,5,6,7-tetrahydroindole with ethylene glycol vinylglycidyl ether (PV1, PV3, PV5) (b).
Figure 6. Thermal analysis of copolymers poly-N-(2,3-epoxypropyl)-4,5,6,7-tetrahydroindole with ethylene glycol methylglycidyl ether (PM1, PM3, PM5) (a), copolymers poly-N-(2,3-epoxypropyl)-4,5,6,7-tetrahydroindole with ethylene glycol vinylglycidyl ether (PV1, PV3, PV5) (b).
Polymers 14 04467 g006
Table
Table 1. Synthesis conditions of N-(2,3-epoxypropyl)-4,5,6,7-tetrahydroindole.
Table 1. Synthesis conditions of N-(2,3-epoxypropyl)-4,5,6,7-tetrahydroindole.
PolymerCatalyst, wt.%T, °CYield, %
P1KOH, 2502
P2KOH, 0.5703
P3KOH, 1705
P4KOH, 27014
P5KOH, 0.5904
P6KOH, 19012
P7KOH, 29061
P8Et3N, 27030
Table
Table 2. Anionic copolymerization of EPTHI (M1) with EGMGE and EGVGE.
Table 2. Anionic copolymerization of EPTHI (M1) with EGMGE and EGVGE.
CopolymerRatio of Monomers, mol.%Yield,
%		Content
N, %		Composition of Copolymers, mol.%Mn,
kDa		Mw,
kDa		Mw/Mn
M1M2M1M2
EGMGE (M2) *
PM11090840.5059514.218.41.29
PM22575652.79297112.116.11.33
PM35050504.28475310.013.71.37
PM47525344.3253477.911.31.43
PM59010254.8856445.68.91.59
EGVGE (M2) **
PV11090581.08118912.316.51.34
PV22575631.87208010.312.21.19
PV35050653.2536647.810.21.32
PV47525674.0646546.48.51.33
PV59010774.4651496.48.61.34
* 2 wt.% KOH, 90 °C, 14 h; ** 2 wt.% KOH, 90 °C, 49 h.
Publisher’s Note: MDPI stays neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Share and Cite

MDPI and ACS Style

Markova, M.; Emel’yanov, A.; Tatarinova, I.; Pozdnyakov, A. Synthesis of Functional Polyesters N-(2,3-epoxypropyl)-4,5,6,7-tetrahydroindole by Anionic Ring-Opening Polymerization. Polymers 2022, 14, 4467. https://doi.org/10.3390/polym14204467

AMA Style

Markova M, Emel’yanov A, Tatarinova I, Pozdnyakov A. Synthesis of Functional Polyesters N-(2,3-epoxypropyl)-4,5,6,7-tetrahydroindole by Anionic Ring-Opening Polymerization. Polymers. 2022; 14(20):4467. https://doi.org/10.3390/polym14204467

Chicago/Turabian Style

Markova, Marina, Artem Emel’yanov, Inna Tatarinova, and Alexander Pozdnyakov. 2022. "Synthesis of Functional Polyesters N-(2,3-epoxypropyl)-4,5,6,7-tetrahydroindole by Anionic Ring-Opening Polymerization" Polymers 14, no. 20: 4467. https://doi.org/10.3390/polym14204467

APA Style

Markova, M., Emel’yanov, A., Tatarinova, I., & Pozdnyakov, A. (2022). Synthesis of Functional Polyesters N-(2,3-epoxypropyl)-4,5,6,7-tetrahydroindole by Anionic Ring-Opening Polymerization. Polymers, 14(20), 4467. https://doi.org/10.3390/polym14204467

Note that from the first issue of 2016, this journal uses article numbers instead of page numbers. See further details here.

Article Metrics

Back to TopTop