STUDY OF THE SYNTHESIS MECHANISM AND SOME PROPERTIES OF OLIGOMERS BASED ON EPICHLOROHYDRIN AND DIPHENYLGUANIDINE

Ismailov   Rovshan  Israilovich; Edgarov  Normuhamad; Ismailov  Alisher

In this work, the synthesis and the scheme for obtaining an oligomer based on
epiiodhydrin with diphenylguanidine were studied, the proportions of epiiodhydrin in the initial
mixture, the yield of oligomers, and the reduced viscosity were studied. The results of spectroscopic
and elemental analyzes are obtained, which show that changes in the ratio of monomers have almost
no effect on the iodine content in the oligomer. This is apparently due to the fact that epiiodhydrin is
much more active in reactions than amino compounds. By studying the degree of conversion on the
viscosity of the oligomerization products, the effects on the intrinsic viscosity of the oligomer were
determined. The use of epiiodhydrin is due to its high reactivity due to the activity of the epoxy group
and the mobility of the iodine atom of the iodomethyl group. In addition, based on a study of literary
sources, we found that most of the substances intended to stabilize and slow down the combustion of
polymer compositions contain ionically or covalently bound iodine, which gives them such valuable
specific properties. The properties of surfactants are formed in the process of their synthesis, since
the mechanism and patterns of synthesis are interrelated with the properties of the compounds. We
have studied the interaction of epiiodhydrin with diphenylguanidine and found that spontaneous
oligomerization occurs at a sufficient rate in bulk at room temperature. Spontaneous polymerization
of epiiodhydrin with diphenylguanidine was studied by the dilatometric method, and the contraction
coefficient, which determines the degree of change in the volume of the monomer mixture, was also
studied. The mechanism of synthesis, the structure of the final product, technological and kinetic
regularities of the process make it possible to predict the physical and colloid-chemical properties of
oligomers. Determining the properties of products in conjunction with mathematical modeling of
synthesis is the subject of further research.

Name of journalTechnical science and innovation
Number of edition2024№3
View count 22

Web Address

DOI

Date of creation in the UzSCI system 12-11-2024

Read count 22

Date of publication 08-11-2024

Main LanguageIngliz

Pages6-11

Tags

synthesis

kinetics

spectroscopy

oligomer

epiodhydrin

diphenylguanidine

English

In this work, the synthesis and the scheme for obtaining an oligomer based on
epiiodhydrin with diphenylguanidine were studied, the proportions of epiiodhydrin in the initial
mixture, the yield of oligomers, and the reduced viscosity were studied. The results of spectroscopic
and elemental analyzes are obtained, which show that changes in the ratio of monomers have almost
no effect on the iodine content in the oligomer. This is apparently due to the fact that epiiodhydrin is
much more active in reactions than amino compounds. By studying the degree of conversion on the
viscosity of the oligomerization products, the effects on the intrinsic viscosity of the oligomer were
determined. The use of epiiodhydrin is due to its high reactivity due to the activity of the epoxy group
and the mobility of the iodine atom of the iodomethyl group. In addition, based on a study of literary
sources, we found that most of the substances intended to stabilize and slow down the combustion of
polymer compositions contain ionically or covalently bound iodine, which gives them such valuable
specific properties. The properties of surfactants are formed in the process of their synthesis, since
the mechanism and patterns of synthesis are interrelated with the properties of the compounds. We
have studied the interaction of epiiodhydrin with diphenylguanidine and found that spontaneous
oligomerization occurs at a sufficient rate in bulk at room temperature. Spontaneous polymerization
of epiiodhydrin with diphenylguanidine was studied by the dilatometric method, and the contraction
coefficient, which determines the degree of change in the volume of the monomer mixture, was also
studied. The mechanism of synthesis, the structure of the final product, technological and kinetic
regularities of the process make it possible to predict the physical and colloid-chemical properties of
oligomers. Determining the properties of products in conjunction with mathematical modeling of
synthesis is the subject of further research.

Tags

synthesis

kinetics

spectroscopy

oligomer

epiodhydrin

diphenylguanidine

№ Author name position Name of organisation

1 Ismailov R. . Professor, DSc, Tashkent State Technical University

2 Edgarov N.. Professor, DSc, Institute of General and Inorganic Chemistry of the Academy of Sciences

3 Ismailov A.. PhD Tashkent State Technical University

№ Name of reference

1 1. L.Belyaev, Yu.Alexandrova, V.Alexandrov. (2007). Modern plain bearings based on furan polymers // In the world of equipment. 3, – P. 70-72.

2 2. V.M.Balakin, E.Yu.Polishchuk, A.V.Rukavishnikov, A.M.Seleznev. (2010). Fire-retardant compositions and coatings based on aminoaldehyde oligomers. Pozharovzryvobezopasnost. 4, – P. 22-27.

3 3. A.B.Leonardi, L.A.Fasce, I.Zucchi, C.E.Hoppe, E.R.Soulуе, C.J.Perez, R.J.Williams. (2011). Shape memory epoxies based on networks with chemical and physical crosslinks. Eur. Polym. 47, – P. 362-369.

4 4. V.F.Valiev, A.R.Khismatullina, A.A.Mukhamedyanova, S.M.Mirakyan, G.Z.Raskildina. Synthesis of tertiary amines with inhibitory activity. Advances in synthesis and complexing: The book of abstracts of the Fourth International scientific conference. – Moscow. 2017. – P. 220.

5 5. K.Sashidhara, A.Kumar, K.Bhaskara Rao, V.Kushwaha, K.Saxena, P.Murthy. (2012). In vitro and in vivo antifilarial activity evaluation of 3,6- epoxy [1,5] dioxins: A new class of antifilarial agents. Bioorganic & Medicinal Chemistry Letters. 22, 4, – P. 1527-1532.

6 6. G.N.Merrill. (2004). The gas-phase reactivity of epichlorohydrin with hydroxide. Journal Phys. Org. Chem. 17, 3, – P. 241-248. ISSN:0894-3230 / 1099-1395.

7 7. J.Yu, J.Li, X.Gao, Sh.Zeng, H.Zhang, J.Liu, Q.Jiao. (2019). Dynamic Kinetic Resolution for Asymmetric Synthesis of L-Noncanonical Amino Acids from D-Ser Using Tryptophan Synthase and Alanine Racemase. European journal of organic chemistry.

8 8. H.Wang, M.Jiang, F.Sun, S.Li, C.Hse, C.Jin. (2018). Screening, Synthesis, and QSAR Research on Cinnamaldehyde-Amino Acid Schiff Base Compounds as Antibacterial Agents. Molecules.

9 9. Novoselov N.V., Matveenko V.N. (2007). New surfactants - quaternary ammonium compounds: dependence of colloid-chemical and rheological properties on the structure. Nanotechnology. 5, – P. 103-113.

10 10. V.V.Kireev, Y.V.Bilichenko, R.S.Borisov, J.Mu, D.A.Kuznetsov, A.V.Eroshenko, S.N.Filatov, I.S.Sirotin. (2019). Synthesis of Bisphenol A Based Phosphazene-Containing Epoxy Resin with Reduced Viscosity. Polymers (Basel).

11 11. D.S.McGuinness. (2011). Olefin oligomerizatoin via metallacycles: dimerization, trimerization, tetramerization, and beyond. Chem. Rev. 111, 3, – P. 2321-2341.

12 12. Levanova E.P., Vilms A.I., Bezborodov V.A., Babenko I.A., Sosnovskaya N.G., Istomina N.V., Albanov A.I., Russavskaya N.V., Rozentsveig I.B. (2017). Synthesis of poly-dentate chalcogen-containing ligands using the system hydrazine hydrate-base. Russ. J. Gen. Chem. 87,.3, – P. 396-401.

13 13. M.Izadi, H.Mardani, H.Roghani-Mamaqani, M.Salami-Kalajahi, K.Khezri. (2021). Hyperbranched Poly(amidoamine)-Grafted Graphene Oxide as a Multifunctional Curing Agent for Epoxy-Terminated Polyurethane Composites. Chemistry Select. 6, – P. 2692- 2699.

14 14. G.Papava, M.Gurgenishvili, I.Chitrekashvili, Z.Chubinishvili, Z.Tabukashvili. (2018). Synthesis of thermoreactive oligomers on the basis of polycyclic bisphenols. Journal World science. 10(38), – P. 42-49.

15 15. Shailja Data, Jeffery Leung Wai, Saawan Kumar, Alan J. Cameron, (2021). Manon Trehet, Emeka J. Itumoh, Joey Feld, Prof. Tilo Söhnel, Dr. Erin M. Leitao. The Step-Wise Synthesis of Oligomeric Phosphoramidates. Journal Chemistry-europe.

16 16. S.Martens, J.Begin, A.Madder, F.Prez, P.Espeel. (2016). Automated Synthesis of Monodisperse Oligomers, Featuring Sequence Control and Tailored Functionalization. Journal American Chemical Society. 138, 43, – P. 14182-14185.

17 17. A.I.Ismailov, N.Edgorov, N.S.Amirkulov. (2014). Synthesis and study of the properties of oligomeric surfactants based on epichlorohydrin with nitrogen- and silicon-containing furan compounds. Republic. scientificpractical conf. “Current state and prospects for the development of colloidal chemistry and nanochemistry in Uzbekistan”, Tashkent. – P. 126-127.

18 18. R.I.Ismailov, T.A.Azizov, B.B.Khasanov, M.Kh.Usmanov. (2010). Study of the mechanism of synthesis of oligomeric flame retardant based on 3-chloro- 2-hydroxypropane with 2,4,6-triamino-1,3,5-triazine. Problems of textiles. -Tashkent, – P. 45-49.

19 19. R.Ismailov, Sh.Jalilov, A.Ismailov, U.Mirzayev, M.Ayupova. (2020). Research of polymeric and oligomeric ionites with branched structure. Journal of critical reviews, Kuala Lumpur, 7, 6, – P. 1273-1281.

20 20. R.I.Ismailov, U.M.Eshmukhamedov, I.N.Khaidarov, R.M.Ismailova. (2023). Technology for obtaining and studying the properties of fire retailers based on epichlorhydrin with nitrogen-containing compounds for polyacrylonitrile fibers//News of higher educational institutions. Tech. textil industrie. 3(405), – P. 162-168.

Waiting

№	Author name	position	Name of organisation
1	Ismailov R. .	Professor, DSc,	Tashkent State Technical University
2	Edgarov N..	Professor, DSc,	Institute of General and Inorganic Chemistry of the Academy of Sciences
3	Ismailov A..	PhD	Tashkent State Technical University

№	Name of reference
1	1. L.Belyaev, Yu.Alexandrova, V.Alexandrov. (2007). Modern plain bearings based on furan polymers // In the world of equipment. 3, – P. 70-72.
2	2. V.M.Balakin, E.Yu.Polishchuk, A.V.Rukavishnikov, A.M.Seleznev. (2010). Fire-retardant compositions and coatings based on aminoaldehyde oligomers. Pozharovzryvobezopasnost. 4, – P. 22-27.
3	3. A.B.Leonardi, L.A.Fasce, I.Zucchi, C.E.Hoppe, E.R.Soulуе, C.J.Perez, R.J.Williams. (2011). Shape memory epoxies based on networks with chemical and physical crosslinks. Eur. Polym. 47, – P. 362-369.
4	4. V.F.Valiev, A.R.Khismatullina, A.A.Mukhamedyanova, S.M.Mirakyan, G.Z.Raskildina. Synthesis of tertiary amines with inhibitory activity. Advances in synthesis and complexing: The book of abstracts of the Fourth International scientific conference. – Moscow. 2017. – P. 220.
5	5. K.Sashidhara, A.Kumar, K.Bhaskara Rao, V.Kushwaha, K.Saxena, P.Murthy. (2012). In vitro and in vivo antifilarial activity evaluation of 3,6- epoxy [1,5] dioxins: A new class of antifilarial agents. Bioorganic & Medicinal Chemistry Letters. 22, 4, – P. 1527-1532.
6	6. G.N.Merrill. (2004). The gas-phase reactivity of epichlorohydrin with hydroxide. Journal Phys. Org. Chem. 17, 3, – P. 241-248. ISSN:0894-3230 / 1099-1395.
7	7. J.Yu, J.Li, X.Gao, Sh.Zeng, H.Zhang, J.Liu, Q.Jiao. (2019). Dynamic Kinetic Resolution for Asymmetric Synthesis of L-Noncanonical Amino Acids from D-Ser Using Tryptophan Synthase and Alanine Racemase. European journal of organic chemistry.
8	8. H.Wang, M.Jiang, F.Sun, S.Li, C.Hse, C.Jin. (2018). Screening, Synthesis, and QSAR Research on Cinnamaldehyde-Amino Acid Schiff Base Compounds as Antibacterial Agents. Molecules.
9	9. Novoselov N.V., Matveenko V.N. (2007). New surfactants - quaternary ammonium compounds: dependence of colloid-chemical and rheological properties on the structure. Nanotechnology. 5, – P. 103-113.
10	10. V.V.Kireev, Y.V.Bilichenko, R.S.Borisov, J.Mu, D.A.Kuznetsov, A.V.Eroshenko, S.N.Filatov, I.S.Sirotin. (2019). Synthesis of Bisphenol A Based Phosphazene-Containing Epoxy Resin with Reduced Viscosity. Polymers (Basel).
11	11. D.S.McGuinness. (2011). Olefin oligomerizatoin via metallacycles: dimerization, trimerization, tetramerization, and beyond. Chem. Rev. 111, 3, – P. 2321-2341.
12	12. Levanova E.P., Vilms A.I., Bezborodov V.A., Babenko I.A., Sosnovskaya N.G., Istomina N.V., Albanov A.I., Russavskaya N.V., Rozentsveig I.B. (2017). Synthesis of poly-dentate chalcogen-containing ligands using the system hydrazine hydrate-base. Russ. J. Gen. Chem. 87,.3, – P. 396-401.
13	13. M.Izadi, H.Mardani, H.Roghani-Mamaqani, M.Salami-Kalajahi, K.Khezri. (2021). Hyperbranched Poly(amidoamine)-Grafted Graphene Oxide as a Multifunctional Curing Agent for Epoxy-Terminated Polyurethane Composites. Chemistry Select. 6, – P. 2692- 2699.
14	14. G.Papava, M.Gurgenishvili, I.Chitrekashvili, Z.Chubinishvili, Z.Tabukashvili. (2018). Synthesis of thermoreactive oligomers on the basis of polycyclic bisphenols. Journal World science. 10(38), – P. 42-49.
15	15. Shailja Data, Jeffery Leung Wai, Saawan Kumar, Alan J. Cameron, (2021). Manon Trehet, Emeka J. Itumoh, Joey Feld, Prof. Tilo Söhnel, Dr. Erin M. Leitao. The Step-Wise Synthesis of Oligomeric Phosphoramidates. Journal Chemistry-europe.
16	16. S.Martens, J.Begin, A.Madder, F.Prez, P.Espeel. (2016). Automated Synthesis of Monodisperse Oligomers, Featuring Sequence Control and Tailored Functionalization. Journal American Chemical Society. 138, 43, – P. 14182-14185.
17	17. A.I.Ismailov, N.Edgorov, N.S.Amirkulov. (2014). Synthesis and study of the properties of oligomeric surfactants based on epichlorohydrin with nitrogen- and silicon-containing furan compounds. Republic. scientificpractical conf. “Current state and prospects for the development of colloidal chemistry and nanochemistry in Uzbekistan”, Tashkent. – P. 126-127.
18	18. R.I.Ismailov, T.A.Azizov, B.B.Khasanov, M.Kh.Usmanov. (2010). Study of the mechanism of synthesis of oligomeric flame retardant based on 3-chloro- 2-hydroxypropane with 2,4,6-triamino-1,3,5-triazine. Problems of textiles. -Tashkent, – P. 45-49.
19	19. R.Ismailov, Sh.Jalilov, A.Ismailov, U.Mirzayev, M.Ayupova. (2020). Research of polymeric and oligomeric ionites with branched structure. Journal of critical reviews, Kuala Lumpur, 7, 6, – P. 1273-1281.
20	20. R.I.Ismailov, U.M.Eshmukhamedov, I.N.Khaidarov, R.M.Ismailova. (2023). Technology for obtaining and studying the properties of fire retailers based on epichlorhydrin with nitrogen-containing compounds for polyacrylonitrile fibers//News of higher educational institutions. Tech. textil industrie. 3(405), – P. 162-168.