WO2022269245A1 - Catalyseurs d'hydrosilylation - Google Patents

Catalyseurs d'hydrosilylation Download PDF

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WO2022269245A1
WO2022269245A1 PCT/GB2022/051574 GB2022051574W WO2022269245A1 WO 2022269245 A1 WO2022269245 A1 WO 2022269245A1 GB 2022051574 W GB2022051574 W GB 2022051574W WO 2022269245 A1 WO2022269245 A1 WO 2022269245A1
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formula
nhc
nhr
atoms
linear
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PCT/GB2022/051574
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Laura ASHFIELD
Simon Benedict Duckett
Helena Grace LANCASTER
Robin Noel Perutz
Andrew St John WELLER
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Johnson Matthey Public Limited Company
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0834—Compounds having one or more O-Si linkage
    • C07F7/0838—Compounds with one or more Si-O-Si sequences
    • C07F7/0872—Preparation and treatment thereof
    • C07F7/0876—Reactions involving the formation of bonds to a Si atom of a Si-O-Si sequence other than a bond of the Si-O-Si linkage
    • C07F7/0878—Si-C bond
    • C07F7/0879—Hydrosilylation reactions
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0834—Compounds having one or more O-Si linkage
    • C07F7/0838—Compounds with one or more Si-O-Si sequences
    • C07F7/087—Compounds of unknown structure containing a Si-O-Si sequence
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/12—Polysiloxanes containing silicon bound to hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
    • B01J2231/323—Hydrometalation, e.g. bor-, alumin-, silyl-, zirconation or analoguous reactions like carbometalation, hydrocarbation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/824—Palladium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/828—Platinum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/845—Cobalt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/847—Nickel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2217—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/226—Sulfur, e.g. thiocarbamates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/0086—Platinum compounds

Definitions

  • the present invention relates to hydrosilylation reactions carried out using certain catalysts which are activated by UV radiation, and catalysts for use in such reactions.
  • Hydrosilylation is an industrially important addition reaction between a compound containing silicon-bonded hydrogen and a compound containing aliphatic unsaturation.
  • the result of hydrosilylation is the addition of the Si-H bond across the unsaturated bond.
  • the reaction is often catalysed by a complex of a transition metal such as Co, Rh, Ni, Pd or Pt. These catalysts are usually activated, either by thermal energy or UV radiation.
  • Pt-cured silicones that is silicones which have been cured by a platinum catalysed hydrosilylation reaction.
  • Silicones are commonly used in products such as sealants and oils, with Pt-cured silicones being generally used in two main areas, namely release liners and elastomers. Release liners are often used for label backing or in the food industry in baking. Elastomers have a variety of uses from medical wound healing to air bag coatings. Platinum cured silicones are typically used when the end product is in contact with food or is for a medical application. Platinum cured silicones are also used to make transparent tubing and other objects, because clarity cannot be obtained with alternative methods such as peroxide curing.
  • Platinum cured silicones may also be used when high detail is required, for example in prototype models. Platinum curing is much faster than other techniques such as peroxide or tin, which are no longer favoured in the industry and are generally being phased out.
  • Platinum complexes used as hydrosilylation curing catalysts may be photoactivatable.
  • the platinum complex is photoactivatable if it is capable of acting as or is transformed into an active catalyst upon irradiation with UV or visible electromagnetic radiation.
  • Photoactivatable platinum complexes may be used in the preparation of silicones such as elastomers, release liners, adhesives (US2010/256300) the coating or encapsulation of electronic chips, dental impressions (EP0398701) or the preparation of LED lenses (EP2617791).
  • Additive layer manufacturing (ALM) or “3D printing” may also be used to prepare cured silicone products. Generally, layers of uncured material including the Pt catalyst are printed and subjected to UV curing after the printing of each layer (WO 2016/044547). This method can be used to prepare any silicone product, incuding products with a complex shape.
  • (MeCp)PtMe3 is one available catalyst which has a high activity under UV- activation and a low activity without UV-activation (see EP 0146307 A2 and EP 2617791 A1). These properties of a hydrosilylation catalyst are desirable to ensure that the initiation of the reaction can be properly controlled.
  • (MeCp)PtMe3 is volatile, toxic, expensive and very difficult to produce (Z Xue, M J Strouse, D K Shuh, C B Knobler, H D Kaesz, R F Hicks, R S Williams, Journal of the American Chemical Society, 111, 8779 (1989)).
  • Pt(acac)2 Another known platinum complex for use in UV-activated hydrosilylation is Pt(acac)2 (see US 2003/235383 A1 and EP 0398701 A2). This is used as a less expensive and less volatile alternative to (MeCp)PtMe3 but is not as soluble in siloxane substrates, has lower activity when UV-activated and higher activity without exposure to UV light.
  • the complexes include Pt(ll) coordinated to two aldehyde-containing ligands.
  • a preferred complex is Pt(ll) bis- salicaldehyde.
  • Figure 1a shows the 1 H NMR spectra for hexamethylsiloxymethylsilane and vinyltrimethylsilane as selected silane and alkene substrates (600 MHz, CD2CI2, 298 K).
  • Figure 1b shows the 29 Si ⁇ 1 H ⁇ NMR spectra for hexamethylsiloxymethylsilane and vinyltrimethylsilane as selected silane and alkene substrates (119.2 MHz, CD2CI2, 298 K).
  • Figure 1c shows the 1 H NMR spectrum of the reaction mixture at the beginning of catalysis using [Pt(ppy)(/ ⁇ /-H2-PhSal)] (E3) at 2 mol% with expansions showing silane, vinyltrimethylsilane and catalyst (400 MHz, CD2CI2, 298 K).
  • Figure 1d shows the 1 H NMR spectrum of the reaction mixture at the beginning of catalysis using [Pt(ppy)(/ ⁇ /-H2-PhSal)] (E3) at 2 mol% with expansions showing silane, vinyltrimethylsilane and catalyst (400 MHz, CD2CI2, 298 K).
  • Figure 1e shows stacked 1 H NMR spectra with reaction mixture at the beginning (bottom) and end of (top) catalysis using spectrum of the reaction mixture at the end of catalysis using [Pt(ppy)(/ ⁇ /-H2-PhSal)] (E3) at 2 mol%.
  • the expansions show the formation of the anti- Markownikov (beta) hydrosilylation product, consumption of silane (bottom-right), consumption of alkene (top-left) and the catalyst (bottom-left) (400 MHz, CD2CI2, 298 K).
  • Figure 2a and 2b are a concentration-time plot showing the profile for the formation of the anti-Markownikov (beta) hydrosilylation product, catalysed by [Pt(ppy)CI(dmso)] (E1) at 2 mol% ( Figure 2a) or 1 mol% ( Figure 2b).
  • the left profile shows the product formation under thermal conditions.
  • the right profile shows the product formation under thermal conditions and with 1 min irradiation.
  • Figure 3a and 3b are a concentration-time plot showing the profile for the reaction between 1 -hexene and tetramethyldisiloxane with UV irradiation (Figure 3a) or under thermal conditions ( Figure 3b).
  • Figure 4 is a concentration-time plot showing the profile for the formation of the anti- Markownikov (beta) hydrosilylation product, catalysed by [Pt(ppy)(/ ⁇ /-H2-Sal-H)] (E3) at 2 mol%.
  • the left profile shows the product formation under thermal conditions and with 2.5 min irradiation.
  • the right profile shows the product formation with 2.5- and 5-min irradiation.
  • Figure 5 is a concentration-time plot showing the profile for the formation of the anti- Markownikov (beta) hydrosilylation product, catalysed by [Pt(ppy)(/ ⁇ /-H2-Sal-OMe)] (E4) at 2 mol%.
  • the left profile shows the product formation under thermal conditions and with 3.5 min irradiation.
  • the right profile shows the product formation with 3.5- and 5-min irradiation.
  • Figure 6 is a concentration-time plot showing the profile for the formation of the anti- Markownikov (beta) hydrosilylation product, catalysed by [Pt(ppy)(/ ⁇ /-F2-Sal-OMe)] (E5) at 2 mol%.
  • the left profile shows the product formation under thermal conditions.
  • the right profile shows the product formation under thermal conditions and with 10 min irradiation.
  • R 9 to R 11 are each independently selected from H, CF 3 , CCI 3 or a C1-6 linear or branched alkyl group which may be a hydrocarbon group, perfluorinated or partially fluorinated.
  • the invention in a second aspect relates to a method of reacting together a substrate comprising hydrosilyl groups and a substrate comprising alkenyl groups in the presence of a hydrosilylation catalyst and in the presence of UV light, wherein the hydrosilylation catalyst is of formula (lb):
  • the invention relates to a method of reacting together a substrate comprising hydrosilyl groups and a substrate comprising alkenyl groups in the presence of a hydrosilylation catalyst and in the presence of UV light, wherein the hydrosilylation catalyst is of Formula (lc):
  • the invention relates to a method of reacting together a substrate comprising hydrosilyl groups and a substrate comprising alkenyl groups in the presence of a hydrosilylation catalyst and in the presence of UV light, wherein the hydrosilylation catalyst is of formula (Id):
  • the invention relates to the use of a catalyst of Formula (la), Formula (lb), Formula (lc) or Formula (Id) as a photoactivatable catalyst in a hydrosilylation reaction.
  • the hydrosilylation may be carried out with UV activation.
  • a curable composition comprising a complex according to Formula (la), Formula (lb), Formula (lc) or Formula (Id).
  • the complex of Formula (la) is:
  • M is Pt.
  • R 1 to R 8 is a C1-6 linear or branched alkyl group
  • the group is methyl, ethyl, n-propyl or isopropyl.
  • the substituted position is R 5 or R 7 .
  • R 10 H.
  • Complexes of Formula (la) are shown herein to have varying activity depending on substrate. As is described in more detail in the examples, catalyst E2 does not show photoactivation in the reaction between hexamethylsiloxymethylsilane and vinyltrimethylsilane vinylsiloxane. However, catalyst E2 does show photoactivation in the reaction between tetramethyldisiloxane and 1-hexene.
  • the component comprising alkenyl groups is a hydrocarbon, such as a hydrocarbon containing vinyl groups, such as a hydrocarbon with at least one terminal vinyl group.
  • M is Pt.
  • R 1 to R 8 is a C1-6 linear or branched alkyl group
  • the group is methyl, ethyl, n-propyl or isopropyl.
  • the substituted position is R 5 or R 7 .
  • X is a o ligand.
  • the nature of X is not believed to be particularly important. Without wishing to be bound by theory, it is thought that X can dissociate from the metal centre leaving a vacant site site on the M(ll) centre for silane and alkene binding.
  • Suitable examples of X include: H, linear or branched C1-6 alkyl, F, Cl, Br, k ⁇ -acac, OR and SR, where R is a C1- 6 linear or branched alkyl group which may be a hydrocarbon group, or may be perfluorinated or partially fluorinated.
  • X is Cl.
  • M is Pt.
  • R 1 to R 12 is a C1-6 linear or branched alkyl group
  • the group is methyl, ethyl, n-propyl or isopropyl.
  • the substituted position is R 5 or R 7 .
  • the complex has the Formula (lc’):
  • R 14 to R 16 take the same definition as R 1 to R 12 above.
  • R 14 to R 16 take the same definition as R 1 to R 12 above and wherein R 1 1 is H or OMe.
  • the complex of Formula (Id) is:
  • M is Pt.
  • the invention also relates to a complex according to Formula (la), Formula (lb), Formula (lc) or Formula (Id) as defined herein.
  • the invention relates to a curable composition
  • a curable composition comprising a catalyst according to Formula (la), Formula (lb), Formula (lc) or Formula (Id) as defined herein. While the composition may show slow background curing, curing is accelerated by the presence of UV light.
  • the curable composition generally comprises a compent comprising alkenyl groups and a component comprising hydrosilyl groups.
  • a hydrosiyl group is a Si-H group.
  • the alkenyl groups and hydrosilyl groups may originate from the same component or may be provided by separate components.
  • the substrate comprising hydrosilyl groups comprises terminal and/or in-chain Si-H groups.
  • the substrate comprising hydrosilyl groups is a siloxane comprising terminal and/or in-chain Si-H groups.
  • This is especially preferred in the case of catalysts of Formula (lb), (lc) and (Id).
  • Hexamethylsiloxymethylsilane (0.0408 g, 1.83 x 10 ⁇ 1 mmol, 0.261 mol dm -3 ), vinyltrimethylsilane (0.0183 g, 1.83 x 10 ⁇ 1 mmol, 0.261 mol dm -3 ) and the integration standard, mesitylene (8.64 mg, 0.072 mmol, 0.1027 mol dm -3 ) were transferred to the NMR tube from a stock solution. The mixture was shaken vigorously to afford a homogenous solution, inserted into a Phillips 125 W medium pressure Hg-arc lamp for a set time period, and then shaken again.
  • the NMR tube was then inserted into the NMR spectrometer and quickly locked, tuned and shimmed.
  • An array of 100 1 H NMR spectra was acquired at 10 min intervals with a relaxation delay of 45 s to ensure quantitative analysis.
  • concentrations of hexamethylsiloxymethylsilane, vinyltrimethylsilane and the anti-Markovnikov hydrosilylation product were calculated from the concentration of the integration standard and the NMR integrals of the Si-H (d 4.6), olefinic (d 6.2) and S1-CH2- CH2-S1 (d 0.40) resonances.
  • thermal curing examples, the same procedure was followed but without irradiation under the Hg-arc lamp.
  • the target complex was synthesised according to a procedure modified from that reported in the literature ( Chem Mater., 2009, 21 , 3871-3882).
  • the Pt(ll) m-dichloro-bridged dimer was synthesised by adding a solution of ⁇ [PtCU] (1.6 g, 3.85 mmol) dissolved in hot water to a solution of 2-phenylpyridine (1.1 ml_, 7.7 mmol) in acetic acid.
  • 2-phenylpyridine 1.1 ml_, 7.7 mmol
  • catalyst [Pt(ppy)CI(dmso)] (E1) was tested at 1 mol% and 2 mol%, in each case without irradiation (thermal) or with irradiation for 1 minute. The results are shown in Figures 2a (2 mol%) and 2b (1 mol%). The rate of curing was approximately the same as the background thermal curing when 1 mol% was used, but a significant increase in curing rate was observed on moving to 2 mol%.
  • catalyst [Pt(ppy)(acac)] (E2) was tested at 2 mol% without irradiation (thermal) and with irradiation for 5 mins. Irradiation with UV did not increase the rate of curing (results not shown).
  • Catalyst E2 was also tested for its activity in the reaction between 1 -hexene and tetramethyldisiloxane.
  • An NMR tube was equipped with 1-hexene (168.1 mI_, 1.34 mmol), tetramethyldisiloxane (118.2 mI_, 0.67 mmol) and 500 mI_ of dcm-d 2 .
  • catalysis was started by injection of the catalyst at 5mol-% in 200 mI_ of dcm-d 2 .
  • the reaction was monitored by in situ 1 H NMR both in the presence of UV-irradation (Figure 2a) and absence of UV-irradiation ( Figure 2b). The data suggests that in this system the rate of catalysis is accelerated when the catalyst is exposed to UV irradiation.
  • Catalysts E3, E4 and E5 were prepared by reaction between [Pt(ppy)CI(dmso)] (E1) and the respective Schiff base following a procedure reported by Brooks et al. Inorg. Chem., 2002, 41, 3055-3066.
  • the E1 complex (0.645 g, 1.39 mmol), 3 equiv of the Schiff base ligand (0.823 g, 4.17 mmol) and 5 equiv of Na 2 CC>3 (0.736 g, 6.95 mmol) in 2-methoxyethanol were heated to reflux for 20 h.
  • the Schiff base ligands were synthesized according to a modified procedure based on Shin et al. Dalton Trans., 2009, 6476-6479. Generally, an ethanol solution of salicylaldehyde (2.69 g, 22.0 mmol) was added to a stirred ethanol solution of aniline (2.05 g, 22.0 mmol) and heated to reflux overnight. Removal of the solvent in vacuo and washing with hexane gave the corresponding ligand as a yellow solid inexcellent yield (4.16 g, 21.1 mmol, 96%). Hydrosilylation using E3, E4 and E5
  • catalyst [Pt(ppy)(N-H2-Sal-H)] (E3) was tested at 2 mol% without irradiation (thermal) or with irradiation for 2.5 or 5 minutes. The results are shown in Figure 4. In both cases there was a significant acceleration in the rate of curing relative to the thermal example.
  • catalyst [Pt(ppy)(/ ⁇ /-H2-Sal-OMe)] (E4) was tested at 2 mol% without irradiation (thermal) or with irradiation for 3.5 or 5 minutes. The results are shown in Figure 5. In both cases there was a significant acceleration in the rate of curing relative to the thermal example.
  • catalyst [Pt(ppy)(N-F2-Sal-H)] (E5) was tested at 2 mol% without irradiation (thermal) or with irradiation for 10 minutes. The results are shown in Figure 6. There was a significant acceleration in the rate of curing relative to the thermal example.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)

Abstract

L'invention concerne des catalyseurs d'hydrosilylation de formule (Ia), (Ib), (Ic) et (Id). Ces catalyseurs présentent une activité d'hydrosilylation accélérée en présence d'UV. L'invention concerne également l'utilisation de tels catalyseurs dans une réaction d'hydrosilylation, ainsi qu'une composition durcissable comprenant le catalyseur.
PCT/GB2022/051574 2021-06-23 2022-06-21 Catalyseurs d'hydrosilylation WO2022269245A1 (fr)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0146307A2 (fr) 1983-12-06 1985-06-26 Minnesota Mining And Manufacturing Company Hydrosilylation activée par irradiation
EP0398701A2 (fr) 1989-05-19 1990-11-22 Minnesota Mining And Manufacturing Company Réaction d'hydrosilation activée par irradiation
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