Synthesis of (Hyper)Branched Monohydroxyl Alkoxysilane Oligomers toward Silanized Urethane Prepolymers

The aim of this work was the synthesis of (hyper)branched oligomers based on trialkoxysilane in various conditions and further application of them in order to modify the urethane prepolymers. Hydroxyl-terminated trialkoxysilane was used as a monomer for homo-condensation. It was obtained by reaction...

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Main Authors: Sebastian Kowalczyk, Maciej Dębowski, Anna Iuliano, Sebastian Brzeski, Andrzej Plichta
Format: Article
Language:English
Published: MDPI AG 2022-04-01
Series:Molecules
Subjects:
Online Access:https://www.mdpi.com/1420-3049/27/9/2790
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author Sebastian Kowalczyk
Maciej Dębowski
Anna Iuliano
Sebastian Brzeski
Andrzej Plichta
author_facet Sebastian Kowalczyk
Maciej Dębowski
Anna Iuliano
Sebastian Brzeski
Andrzej Plichta
author_sort Sebastian Kowalczyk
collection DOAJ
description The aim of this work was the synthesis of (hyper)branched oligomers based on trialkoxysilane in various conditions and further application of them in order to modify the urethane prepolymers. Hydroxyl-terminated trialkoxysilane was used as a monomer for homo-condensation. It was obtained by reaction of 3-aminopropyl trialkoxysilane (APTES) with ethylene carbonate (EC). The reaction was based on the attack of amine at the carbonyl carbon atom followed by ring opening of the carbonate to give a urethane (carbamate) product. The next step was the condensation via substitution of ethoxy groups on silicon atom with the terminal hydroxyalkyl groups present in the primary product with the evolution of ethanol. Accordingly, the impact of temperature and type of catalyst on process efficiency was investigated. A quantitative analysis of reaction progress and products of the conversion of EC together with ethanol evolution was conducted by means of gas chromatography, which allowed us to determine the formation of monomeric product and, indirectly, of oligomeric products. It was found that at room temperature after 24 h, the majority of the monomeric product was isolated, whereas at elevated temperature in the presence of Ti-based catalyst, further condensation of the monomer into branched oligomers was preferred, and, moreover, the application of vacuum intensified that process. The obtained products were structurally characterized by <sup>1</sup>H and <sup>29</sup>Si NMR, MALDI-ToF and Gel Permeation Chromatography. Finally, two different alkoxysilane products, monomeric and oligomeric, were applied for modification of urethane prepolymer, forming silanized one (SPUR). The influence of the silanizing agent on the mechanical and thermal properties of the moisture-cured products was shown before and after additional conditioning in water.
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spelling doaj.art-35407e4df49d475ba6c1a5757ce22a4d2023-11-23T08:49:36ZengMDPI AGMolecules1420-30492022-04-01279279010.3390/molecules27092790Synthesis of (Hyper)Branched Monohydroxyl Alkoxysilane Oligomers toward Silanized Urethane PrepolymersSebastian Kowalczyk0Maciej Dębowski1Anna Iuliano2Sebastian Brzeski3Andrzej Plichta4Chair of Chemistry and Technology of Polymers, Faculty of Chemistry, Warsaw University of Technology, Noakowskiego 3, 00-664 Warsaw, PolandChair of Chemistry and Technology of Polymers, Faculty of Chemistry, Warsaw University of Technology, Noakowskiego 3, 00-664 Warsaw, PolandChair of Chemistry and Technology of Polymers, Faculty of Chemistry, Warsaw University of Technology, Noakowskiego 3, 00-664 Warsaw, PolandChair of Chemistry and Technology of Polymers, Faculty of Chemistry, Warsaw University of Technology, Noakowskiego 3, 00-664 Warsaw, PolandChair of Chemistry and Technology of Polymers, Faculty of Chemistry, Warsaw University of Technology, Noakowskiego 3, 00-664 Warsaw, PolandThe aim of this work was the synthesis of (hyper)branched oligomers based on trialkoxysilane in various conditions and further application of them in order to modify the urethane prepolymers. Hydroxyl-terminated trialkoxysilane was used as a monomer for homo-condensation. It was obtained by reaction of 3-aminopropyl trialkoxysilane (APTES) with ethylene carbonate (EC). The reaction was based on the attack of amine at the carbonyl carbon atom followed by ring opening of the carbonate to give a urethane (carbamate) product. The next step was the condensation via substitution of ethoxy groups on silicon atom with the terminal hydroxyalkyl groups present in the primary product with the evolution of ethanol. Accordingly, the impact of temperature and type of catalyst on process efficiency was investigated. A quantitative analysis of reaction progress and products of the conversion of EC together with ethanol evolution was conducted by means of gas chromatography, which allowed us to determine the formation of monomeric product and, indirectly, of oligomeric products. It was found that at room temperature after 24 h, the majority of the monomeric product was isolated, whereas at elevated temperature in the presence of Ti-based catalyst, further condensation of the monomer into branched oligomers was preferred, and, moreover, the application of vacuum intensified that process. The obtained products were structurally characterized by <sup>1</sup>H and <sup>29</sup>Si NMR, MALDI-ToF and Gel Permeation Chromatography. Finally, two different alkoxysilane products, monomeric and oligomeric, were applied for modification of urethane prepolymer, forming silanized one (SPUR). The influence of the silanizing agent on the mechanical and thermal properties of the moisture-cured products was shown before and after additional conditioning in water.https://www.mdpi.com/1420-3049/27/9/2790hyperbranched oligomerssilanepolyurethaneurethane prepolymerssilanized polyurethane3-aminopropyl trialkoxysilane
spellingShingle Sebastian Kowalczyk
Maciej Dębowski
Anna Iuliano
Sebastian Brzeski
Andrzej Plichta
Synthesis of (Hyper)Branched Monohydroxyl Alkoxysilane Oligomers toward Silanized Urethane Prepolymers
Molecules
hyperbranched oligomers
silane
polyurethane
urethane prepolymers
silanized polyurethane
3-aminopropyl trialkoxysilane
title Synthesis of (Hyper)Branched Monohydroxyl Alkoxysilane Oligomers toward Silanized Urethane Prepolymers
title_full Synthesis of (Hyper)Branched Monohydroxyl Alkoxysilane Oligomers toward Silanized Urethane Prepolymers
title_fullStr Synthesis of (Hyper)Branched Monohydroxyl Alkoxysilane Oligomers toward Silanized Urethane Prepolymers
title_full_unstemmed Synthesis of (Hyper)Branched Monohydroxyl Alkoxysilane Oligomers toward Silanized Urethane Prepolymers
title_short Synthesis of (Hyper)Branched Monohydroxyl Alkoxysilane Oligomers toward Silanized Urethane Prepolymers
title_sort synthesis of hyper branched monohydroxyl alkoxysilane oligomers toward silanized urethane prepolymers
topic hyperbranched oligomers
silane
polyurethane
urethane prepolymers
silanized polyurethane
3-aminopropyl trialkoxysilane
url https://www.mdpi.com/1420-3049/27/9/2790
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