Synthesis of Biobased Hydroxyl-Terminated Oligomers by Metathesis Degradation of Industrial Rubbers SBS and PB: Tailor-Made Unsaturated Diols and Polyols
Biobased hydroxyl-terminated polybutadiene (HTPB) was successfully synthesized in a one-pot reaction via metathesis degradation of industrial rubbers. Thus, polybutadiene (PB) and poly(styrene-butadiene-styrene) (SBS) were degraded via metathesis with high yields (>94%), using the fatty alcohol 1...
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MDPI AG
2022-11-01
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| Series: | Polymers |
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| Online Access: | https://www.mdpi.com/2073-4360/14/22/4973 |
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| author | Manuel Burelo Selena Gutiérrez Cecilia D. Treviño-Quintanilla Jorge A. Cruz-Morales Araceli Martínez Salvador López-Morales |
| author_facet | Manuel Burelo Selena Gutiérrez Cecilia D. Treviño-Quintanilla Jorge A. Cruz-Morales Araceli Martínez Salvador López-Morales |
| author_sort | Manuel Burelo |
| collection | DOAJ |
| description | Biobased hydroxyl-terminated polybutadiene (HTPB) was successfully synthesized in a one-pot reaction via metathesis degradation of industrial rubbers. Thus, polybutadiene (PB) and poly(styrene-butadiene-styrene) (SBS) were degraded via metathesis with high yields (>94%), using the fatty alcohol 10-undecen-1-ol as a chain transfer agent (CTA) and the second-generation Grubbs–Hoveyda catalyst. The identification of the hydroxyl groups (-OH) and the formation of biobased HTPB were verified by FT-IR and NMR. Likewise, the molecular weight and properties of the HTPB were controlled by changing the molar ratio of rubber to CTA ([C=C]/CTA) from 1:1 to 100:1, considering a constant molar ratio of the catalyst ([C=C]/Ru = 500:1). The number average molecular weight (<i>M<sub>n</sub></i>) ranged between 583 and 6580 g/mol and the decomposition temperatures between 134 and 220 °C. Moreover, the catalyst optimization study showed that at catalyst loadings as low as [C=C]/Ru = 5000:1, the theoretical molecular weight is in good agreement with the experimental molecular weight and the expected diols and polyols are formed. At higher ratios than those, the difference between theoretical and experimental molecular weight is wide, and there is no control over HTPB. Therefore, the rubber/CTA molar ratio and the amount of catalyst play an important role in PB degradation and HTPB synthesis. Biobased HTPB can be used to synthesize engineering design polymers, intermediates, fine chemicals, and in the polyurethane industry, and contribute to the development of environmentally friendly raw materials. |
| first_indexed | 2024-03-09T18:02:50Z |
| format | Article |
| id | doaj.art-3bb98fcb04c241fea7d91298880eb814 |
| institution | Directory Open Access Journal |
| issn | 2073-4360 |
| language | English |
| last_indexed | 2024-03-09T18:02:50Z |
| publishDate | 2022-11-01 |
| publisher | MDPI AG |
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| series | Polymers |
| spelling | doaj.art-3bb98fcb04c241fea7d91298880eb8142023-11-24T09:44:01ZengMDPI AGPolymers2073-43602022-11-011422497310.3390/polym14224973Synthesis of Biobased Hydroxyl-Terminated Oligomers by Metathesis Degradation of Industrial Rubbers SBS and PB: Tailor-Made Unsaturated Diols and PolyolsManuel Burelo0Selena Gutiérrez1Cecilia D. Treviño-Quintanilla2Jorge A. Cruz-Morales3Araceli Martínez4Salvador López-Morales5Institute of Advanced Materials for Sustainable Manufacturing, Tecnologico de Monterrey, Queretaro 76146, MexicoFacultad de Química, Universidad Nacional Autónoma de México, Ciudad Universitaria, Coyoacán, Ciudad de México 04510, MexicoInstitute of Advanced Materials for Sustainable Manufacturing, Tecnologico de Monterrey, Queretaro 76146, MexicoFacultad de Química, Universidad Nacional Autónoma de México, Ciudad Universitaria, Coyoacán, Ciudad de México 04510, MexicoEscuela Nacional de Estudios Superiores, Unidad Morelia, Universidad Nacional Autónoma de México, Antigua Carretera a Pátzcuaro No. 8701, Col. Ex. Hacienda de San José de la Huerta, Morelia 58190, Michoacán, MexicoInstituto de Investigaciones en Materiales, Universidad Nacional Autónoma de México, Ciudad Universitaria, Coyoacán, Ciudad de México 04510, MexicoBiobased hydroxyl-terminated polybutadiene (HTPB) was successfully synthesized in a one-pot reaction via metathesis degradation of industrial rubbers. Thus, polybutadiene (PB) and poly(styrene-butadiene-styrene) (SBS) were degraded via metathesis with high yields (>94%), using the fatty alcohol 10-undecen-1-ol as a chain transfer agent (CTA) and the second-generation Grubbs–Hoveyda catalyst. The identification of the hydroxyl groups (-OH) and the formation of biobased HTPB were verified by FT-IR and NMR. Likewise, the molecular weight and properties of the HTPB were controlled by changing the molar ratio of rubber to CTA ([C=C]/CTA) from 1:1 to 100:1, considering a constant molar ratio of the catalyst ([C=C]/Ru = 500:1). The number average molecular weight (<i>M<sub>n</sub></i>) ranged between 583 and 6580 g/mol and the decomposition temperatures between 134 and 220 °C. Moreover, the catalyst optimization study showed that at catalyst loadings as low as [C=C]/Ru = 5000:1, the theoretical molecular weight is in good agreement with the experimental molecular weight and the expected diols and polyols are formed. At higher ratios than those, the difference between theoretical and experimental molecular weight is wide, and there is no control over HTPB. Therefore, the rubber/CTA molar ratio and the amount of catalyst play an important role in PB degradation and HTPB synthesis. Biobased HTPB can be used to synthesize engineering design polymers, intermediates, fine chemicals, and in the polyurethane industry, and contribute to the development of environmentally friendly raw materials.https://www.mdpi.com/2073-4360/14/22/4973poly(styrene-butadiene-styrene) (SBS)tailor-made oligomershydroxyl-terminated polybutadieneunsaturated polyolunsaturated diolmetathesis degradation |
| spellingShingle | Manuel Burelo Selena Gutiérrez Cecilia D. Treviño-Quintanilla Jorge A. Cruz-Morales Araceli Martínez Salvador López-Morales Synthesis of Biobased Hydroxyl-Terminated Oligomers by Metathesis Degradation of Industrial Rubbers SBS and PB: Tailor-Made Unsaturated Diols and Polyols Polymers poly(styrene-butadiene-styrene) (SBS) tailor-made oligomers hydroxyl-terminated polybutadiene unsaturated polyol unsaturated diol metathesis degradation |
| title | Synthesis of Biobased Hydroxyl-Terminated Oligomers by Metathesis Degradation of Industrial Rubbers SBS and PB: Tailor-Made Unsaturated Diols and Polyols |
| title_full | Synthesis of Biobased Hydroxyl-Terminated Oligomers by Metathesis Degradation of Industrial Rubbers SBS and PB: Tailor-Made Unsaturated Diols and Polyols |
| title_fullStr | Synthesis of Biobased Hydroxyl-Terminated Oligomers by Metathesis Degradation of Industrial Rubbers SBS and PB: Tailor-Made Unsaturated Diols and Polyols |
| title_full_unstemmed | Synthesis of Biobased Hydroxyl-Terminated Oligomers by Metathesis Degradation of Industrial Rubbers SBS and PB: Tailor-Made Unsaturated Diols and Polyols |
| title_short | Synthesis of Biobased Hydroxyl-Terminated Oligomers by Metathesis Degradation of Industrial Rubbers SBS and PB: Tailor-Made Unsaturated Diols and Polyols |
| title_sort | synthesis of biobased hydroxyl terminated oligomers by metathesis degradation of industrial rubbers sbs and pb tailor made unsaturated diols and polyols |
| topic | poly(styrene-butadiene-styrene) (SBS) tailor-made oligomers hydroxyl-terminated polybutadiene unsaturated polyol unsaturated diol metathesis degradation |
| url | https://www.mdpi.com/2073-4360/14/22/4973 |
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