Rhodium(I)-catalysed cross-linking of polysiloxanes conducted at room temperature

Mikhail V. Dobrynin, Carla Pretorius, Kama Dumisani, Andreas Roodt, Vadim P. Boyarskiy, Regina M. Islamova

Research output

4 Citations (Scopus)

Abstract

Acetylacetonate and 4-arylimino-2-pentanonate carbonyl complexes of rhodium(I) [Rh(RC(O)C(R’)C(O)R“)(CO) 2] (1: R = Me, R’ = H, R'’ = Me; 2: R = Me, R’ = Cl, R'’ = Me; 3: R = Me, R’ = H, R'’ = CO 2Me; 4: R = Ph, R’ = H, R'’ = Me; 5: R = Ph, R’ = H, R'’ = Ph) and [Rh(MeC(NR’’’)CHC(O)Me)(CO) 2] (6: R’'’ = Ph; 7: R’'’ = 2,6-Me 2C 6H 3) were examined as hydrosilylation cross-linking catalysts at RT for the reaction of poly(dimethylsiloxane-co-ethylhydrosiloxane) copolymer with vinyl terminated poly(dimethylsiloxane) or vinyl terminated poly(dimethylsiloxane-co-styrene) copolymer. All complexes allow cross-linking of vinyl- and hydride-containing polysiloxanes and copolymers at RT without inhibitor addition. Complexes 1–7 possess catalytic activity comparable to the industrially used complex of Pt 0 and divinyltetramethyldisiloxane (Karstedt's catalyst). 1 is the most active among the studied rhodium complexes at 1.0 × 10 −4 mol⋅L −1 and 1.0 × 10 −5 mol⋅L −1. Silicone rubbers obtained with the rhodium catalysts compared to Karstedt's catalyst possess no visible defects (bubbles or cracks), and differed by improved elastic properties (the elongation at break increased from 160 to 255%) The activity and improved silicone rubber properties using 1 renders it one of the suitable alternatives to Karstedt's catalyst.

Original languageEnglish
Pages (from-to)193–200
Number of pages8
JournalJournal of Catalysis
Volume372
DOIs
Publication statusPublished - Apr 2019

Fingerprint

Siloxanes
polysiloxanes
Rhodium
rhodium
Silicones
catalysts
Polydimethylsiloxane
Carbon Monoxide
Catalysts
room temperature
silicone rubber
Silicone Elastomers
copolymers
Copolymers
Rubber
Temperature
Hydrosilylation
styrenes
Hydrides
inhibitors

Scopus subject areas

  • Materials Chemistry
  • Polymers and Plastics
  • Catalysis
  • Organic Chemistry
  • Physical and Theoretical Chemistry

Cite this

Dobrynin, Mikhail V. ; Pretorius, Carla ; Dumisani, Kama ; Roodt, Andreas ; Boyarskiy, Vadim P. ; Islamova, Regina M. / Rhodium(I)-catalysed cross-linking of polysiloxanes conducted at room temperature. In: Journal of Catalysis. 2019 ; Vol. 372. pp. 193–200.
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abstract = "Acetylacetonate and 4-arylimino-2-pentanonate carbonyl complexes of rhodium(I) [Rh(RC(O)C(R’)C(O)R“)(CO) 2] (1: R = Me, R’ = H, R'’ = Me; 2: R = Me, R’ = Cl, R'’ = Me; 3: R = Me, R’ = H, R'’ = CO 2Me; 4: R = Ph, R’ = H, R'’ = Me; 5: R = Ph, R’ = H, R'’ = Ph) and [Rh(MeC(NR’’’)CHC(O)Me)(CO) 2] (6: R’'’ = Ph; 7: R’'’ = 2,6-Me 2C 6H 3) were examined as hydrosilylation cross-linking catalysts at RT for the reaction of poly(dimethylsiloxane-co-ethylhydrosiloxane) copolymer with vinyl terminated poly(dimethylsiloxane) or vinyl terminated poly(dimethylsiloxane-co-styrene) copolymer. All complexes allow cross-linking of vinyl- and hydride-containing polysiloxanes and copolymers at RT without inhibitor addition. Complexes 1–7 possess catalytic activity comparable to the industrially used complex of Pt 0 and divinyltetramethyldisiloxane (Karstedt's catalyst). 1 is the most active among the studied rhodium complexes at 1.0 × 10 −4 mol⋅L −1 and 1.0 × 10 −5 mol⋅L −1. Silicone rubbers obtained with the rhodium catalysts compared to Karstedt's catalyst possess no visible defects (bubbles or cracks), and differed by improved elastic properties (the elongation at break increased from 160 to 255{\%}) The activity and improved silicone rubber properties using 1 renders it one of the suitable alternatives to Karstedt's catalyst.",
keywords = "Hydrosilylation, Cross-linking, Rhodium complexes, Silicones, Mechanical properties, Cross-linking, Hydrosilylation, Mechanical properties, Rhodium complexes, Silicones, RHODIUM, POLY(DIMETHYLSILOXANE), PLATINUM, CATALYTIC HYDROSILYLATION, FUNCTIONALIZATION, SILICONE-RUBBER, SURFACE, SYSTEMS, METAL-COMPLEXES, PDMS",
author = "Dobrynin, {Mikhail V.} and Carla Pretorius and Kama Dumisani and Andreas Roodt and Boyarskiy, {Vadim P.} and Islamova, {Regina M.}",
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Rhodium(I)-catalysed cross-linking of polysiloxanes conducted at room temperature. / Dobrynin, Mikhail V.; Pretorius, Carla; Dumisani, Kama; Roodt, Andreas; Boyarskiy, Vadim P.; Islamova, Regina M.

In: Journal of Catalysis, Vol. 372, 04.2019, p. 193–200.

Research output

TY - JOUR

T1 - Rhodium(I)-catalysed cross-linking of polysiloxanes conducted at room temperature

AU - Dobrynin, Mikhail V.

AU - Pretorius, Carla

AU - Dumisani, Kama

AU - Roodt, Andreas

AU - Boyarskiy, Vadim P.

AU - Islamova, Regina M.

PY - 2019/4

Y1 - 2019/4

N2 - Acetylacetonate and 4-arylimino-2-pentanonate carbonyl complexes of rhodium(I) [Rh(RC(O)C(R’)C(O)R“)(CO) 2] (1: R = Me, R’ = H, R'’ = Me; 2: R = Me, R’ = Cl, R'’ = Me; 3: R = Me, R’ = H, R'’ = CO 2Me; 4: R = Ph, R’ = H, R'’ = Me; 5: R = Ph, R’ = H, R'’ = Ph) and [Rh(MeC(NR’’’)CHC(O)Me)(CO) 2] (6: R’'’ = Ph; 7: R’'’ = 2,6-Me 2C 6H 3) were examined as hydrosilylation cross-linking catalysts at RT for the reaction of poly(dimethylsiloxane-co-ethylhydrosiloxane) copolymer with vinyl terminated poly(dimethylsiloxane) or vinyl terminated poly(dimethylsiloxane-co-styrene) copolymer. All complexes allow cross-linking of vinyl- and hydride-containing polysiloxanes and copolymers at RT without inhibitor addition. Complexes 1–7 possess catalytic activity comparable to the industrially used complex of Pt 0 and divinyltetramethyldisiloxane (Karstedt's catalyst). 1 is the most active among the studied rhodium complexes at 1.0 × 10 −4 mol⋅L −1 and 1.0 × 10 −5 mol⋅L −1. Silicone rubbers obtained with the rhodium catalysts compared to Karstedt's catalyst possess no visible defects (bubbles or cracks), and differed by improved elastic properties (the elongation at break increased from 160 to 255%) The activity and improved silicone rubber properties using 1 renders it one of the suitable alternatives to Karstedt's catalyst.

AB - Acetylacetonate and 4-arylimino-2-pentanonate carbonyl complexes of rhodium(I) [Rh(RC(O)C(R’)C(O)R“)(CO) 2] (1: R = Me, R’ = H, R'’ = Me; 2: R = Me, R’ = Cl, R'’ = Me; 3: R = Me, R’ = H, R'’ = CO 2Me; 4: R = Ph, R’ = H, R'’ = Me; 5: R = Ph, R’ = H, R'’ = Ph) and [Rh(MeC(NR’’’)CHC(O)Me)(CO) 2] (6: R’'’ = Ph; 7: R’'’ = 2,6-Me 2C 6H 3) were examined as hydrosilylation cross-linking catalysts at RT for the reaction of poly(dimethylsiloxane-co-ethylhydrosiloxane) copolymer with vinyl terminated poly(dimethylsiloxane) or vinyl terminated poly(dimethylsiloxane-co-styrene) copolymer. All complexes allow cross-linking of vinyl- and hydride-containing polysiloxanes and copolymers at RT without inhibitor addition. Complexes 1–7 possess catalytic activity comparable to the industrially used complex of Pt 0 and divinyltetramethyldisiloxane (Karstedt's catalyst). 1 is the most active among the studied rhodium complexes at 1.0 × 10 −4 mol⋅L −1 and 1.0 × 10 −5 mol⋅L −1. Silicone rubbers obtained with the rhodium catalysts compared to Karstedt's catalyst possess no visible defects (bubbles or cracks), and differed by improved elastic properties (the elongation at break increased from 160 to 255%) The activity and improved silicone rubber properties using 1 renders it one of the suitable alternatives to Karstedt's catalyst.

KW - Hydrosilylation

KW - Cross-linking

KW - Rhodium complexes

KW - Silicones

KW - Mechanical properties

KW - Cross-linking

KW - Hydrosilylation

KW - Mechanical properties

KW - Rhodium complexes

KW - Silicones

KW - RHODIUM

KW - POLY(DIMETHYLSILOXANE)

KW - PLATINUM

KW - CATALYTIC HYDROSILYLATION

KW - FUNCTIONALIZATION

KW - SILICONE-RUBBER

KW - SURFACE

KW - SYSTEMS

KW - METAL-COMPLEXES

KW - PDMS

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UR - http://www.mendeley.com/research/rhodiumicatalysed-crosslinking-polysiloxanes-conducted-room-temperature

U2 - 10.1016/j.jcat.2019.03.004

DO - 10.1016/j.jcat.2019.03.004

M3 - Article

VL - 372

SP - 193

EP - 200

JO - Journal of Catalysis

JF - Journal of Catalysis

SN - 0021-9517

ER -