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With erbium(III) triflate; In ethanol-d6; water-d2;Conversion of starting material; |
Example 5: Effect of Lanthanide Series Catalyst on Hydrolysis. Deuterated water (d2-water), deuterated ethanol and a series of lanthanide catalysts were mixed together according to the mass ratios in Table 5. A known quantity of [Y-GLYCIDOXYPROPYLTRIMETHOXYSILANE] was added to the solution and the reaction was followed using proton NMR spectroscopy. The time to 83% conversion was between 25 minutes and 272 minutes. All the lanthanide (III) (trifluoromethanesulfonate) 3 catalysts were active in hydrolysing [Y-GLYCIDOXYPROPYLTRIMETHOXYSILANE.] Table 5 Catalyst Mol ratio Mol ratio Mol ratio Concentration Mass %. Mass % Mass % Mass % Minutes to Water Silane catalyst silane Water Solvent Silane Catalyst 83% / g dm-3 Conversion LaTFMS 10 0.2 0.01 8.60 4.1 89.8 0.96 0.12 272 PrTFMS 10 0.2 0.01 8.60 4.1 89. 8 0.96 0.12 58 NdTFMS 10 0.2 0.01 8.60 4.1 89.8 0.96 0.12 63 SmTFMS 10 0.2 0.01 8.60 4.1 89.8 0.96 0.12 59 EuTFMS 10 0.2 0.01 8.60 4.1 89.8 0.96 0.12 43 GaTFMS 10 0.2 0.01 8.60 4.1 89.8 0.96 0.12 89 DyTFMS 10 0.2 0.01 8.60 4.1 89.8 0.96 0.12 61 ErTFMS 10 0.2 0.01 8.60 4.1 89.8 0.96 0.12 57 TmTFMS 10 0.2 0.01 8.60 4.1 89.8 0.96 0.12 63 YbTFMS 10 0.2 0.01 8.60 4.1 89.8 0.96 0.13 29 YbTFMS 10 0.2 0.01 8.60 4.1 89.8 0.96 0.13 25 [LA=LANTHANUM,] [PR=PRAESEODYMIUM,] Nd=neodymium, [SM=SAMARIUM,] [EU=EUROPIUM, GA=GADOIMIUM,] Dy=dysprosium, [ER=ERBIUM,] [TM=THULIUM,] Yb=ytterbium [TFMS=TRIFLUROMETHYLSULFONATE] |
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With erbium(III) triflate; In ethanol-d6; water-d2;Conversion of starting material; |
Example 6: Effect of Lanthanide Series Catalyst on Oligomerisation Deuterated water (d2-water), deuterated ethanol (d6-ethanol) and catalyst were mixed together according to the mass ratios in Table 6. A known quantity of y- glycidoxypropyltrimethoxysilane was added to the solution and the oligomerisation reaction was followed using silicon-29 NMR spectroscopy (measured by the rate of loss of monomeric species). Europium (III) and samarium [(III)] [TRIFLUOROMETHANESULFONATE,, WERE] the least effective oligomerisation catalysts and are the preferred catalysts where it is desired to avoid or to minimise oligomerisation, as, for example, in metal surface treatment processes. Ytterbium and erbium [(III)] tend to promote oligomerisation and hence these catalysts are more suitable for use in crosslinked gel formation processes, such as the generation of solgels, aerogels, xerogels and alcogels. Silicon-29 NMR measurements were performed at higher concentrations of silane and lower concentrations of water. The rate of oligomerisation at 1% mass of the silane (measured by proton NMR) is lower than the rate for 10% mass of silane when catalysed by Eu (III) trifluoromethanesulfonate (Table 6). This may also be the case for oligomerisation reactions catalysed by other metals in the lanthanide series. Table 6 Catalyst Mol ratio Mol ratio Mol ratio Concentration Mass % Mass % Mass % Mass % Half life of Water Silane catalyst Silane Water Solvent Silane Catalyst Silanetriol I g dm-3/mins EuTFMS 5 0. 2 0. 01 94. 20 21. 2 48. 9 10. 00 1. 27 141 EuTFMS 10 0.2 0.01 8.60 4.1 89.9 1.07 0.14 2143 YbTFMS 5 0.2 0.01 94.24 21.2 48.8 10.00 1.31 84 ErTFMS 5 0.2 0.01 94.20 21.2 48.9 10.00 1.30 131 SmTFMS 5 0.2 0.01 94.20 21.2 48.9 10.00 1.26 102 LaTFMS 5 0.2 0. 01 94.20 21. 2 48. 9 10. 00 1. 24 <80 |
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With thulium(III) trifluoromethanesulfonate; In ethanol-d6; water-d2;Conversion of starting material; |
Example 5: Effect of Lanthanide Series Catalyst on Hydrolysis. Deuterated water (d2-water), deuterated ethanol and a series of lanthanide catalysts were mixed together according to the mass ratios in Table 5. A known quantity of [Y-GLYCIDOXYPROPYLTRIMETHOXYSILANE] was added to the solution and the reaction was followed using proton NMR spectroscopy. The time to 83% conversion was between 25 minutes and 272 minutes. All the lanthanide (III) (trifluoromethanesulfonate) 3 catalysts were active in hydrolysing [Y-GLYCIDOXYPROPYLTRIMETHOXYSILANE.] Table 5 Catalyst Mol ratio Mol ratio Mol ratio Concentration Mass %. Mass % Mass % Mass % Minutes to Water Silane catalyst silane Water Solvent Silane Catalyst 83% / g dm-3 Conversion LaTFMS 10 0.2 0.01 8.60 4.1 89.8 0.96 0.12 272 PrTFMS 10 0.2 0.01 8.60 4.1 89. 8 0.96 0.12 58 NdTFMS 10 0.2 0.01 8.60 4.1 89.8 0.96 0.12 63 SmTFMS 10 0.2 0.01 8.60 4.1 89.8 0.96 0.12 59 EuTFMS 10 0.2 0.01 8.60 4.1 89.8 0.96 0.12 43 GaTFMS 10 0.2 0.01 8.60 4.1 89.8 0.96 0.12 89 DyTFMS 10 0.2 0.01 8.60 4.1 89.8 0.96 0.12 61 ErTFMS 10 0.2 0.01 8.60 4.1 89.8 0.96 0.12 57 TmTFMS 10 0.2 0.01 8.60 4.1 89.8 0.96 0.12 63 YbTFMS 10 0.2 0.01 8.60 4.1 89.8 0.96 0.13 29 YbTFMS 10 0.2 0.01 8.60 4.1 89.8 0.96 0.13 25 [LA=LANTHANUM,] [PR=PRAESEODYMIUM,] Nd=neodymium, [SM=SAMARIUM,] [EU=EUROPIUM, GA=GADOIMIUM,] Dy=dysprosium, [ER=ERBIUM,] [TM=THULIUM,] Yb=ytterbium [TFMS=TRIFLUROMETHYLSULFONATE] |
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With dysprosium(III) trifluoromethanesulfonate; In ethanol-d6; water-d2;Conversion of starting material; |
Example 5: Effect of Lanthanide Series Catalyst on Hydrolysis. Deuterated water (d2-water), deuterated ethanol and a series of lanthanide catalysts were mixed together according to the mass ratios in Table 5. A known quantity of [Y-GLYCIDOXYPROPYLTRIMETHOXYSILANE] was added to the solution and the reaction was followed using proton NMR spectroscopy. The time to 83% conversion was between 25 minutes and 272 minutes. All the lanthanide (III) (trifluoromethanesulfonate) 3 catalysts were active in hydrolysing [Y-GLYCIDOXYPROPYLTRIMETHOXYSILANE.] Table 5 Catalyst Mol ratio Mol ratio Mol ratio Concentration Mass %. Mass % Mass % Mass % Minutes to Water Silane catalyst silane Water Solvent Silane Catalyst 83% / g dm-3 Conversion LaTFMS 10 0.2 0.01 8.60 4.1 89.8 0.96 0.12 272 PrTFMS 10 0.2 0.01 8.60 4.1 89. 8 0.96 0.12 58 NdTFMS 10 0.2 0.01 8.60 4.1 89.8 0.96 0.12 63 SmTFMS 10 0.2 0.01 8.60 4.1 89.8 0.96 0.12 59 EuTFMS 10 0.2 0.01 8.60 4.1 89.8 0.96 0.12 43 GaTFMS 10 0.2 0.01 8.60 4.1 89.8 0.96 0.12 89 DyTFMS 10 0.2 0.01 8.60 4.1 89.8 0.96 0.12 61 ErTFMS 10 0.2 0.01 8.60 4.1 89.8 0.96 0.12 57 TmTFMS 10 0.2 0.01 8.60 4.1 89.8 0.96 0.12 63 YbTFMS 10 0.2 0.01 8.60 4.1 89.8 0.96 0.13 29 YbTFMS 10 0.2 0.01 8.60 4.1 89.8 0.96 0.13 25 [LA=LANTHANUM,] [PR=PRAESEODYMIUM,] Nd=neodymium, [SM=SAMARIUM,] [EU=EUROPIUM, GA=GADOIMIUM,] Dy=dysprosium, [ER=ERBIUM,] [TM=THULIUM,] Yb=ytterbium [TFMS=TRIFLUROMETHYLSULFONATE] |
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With lanthanum(lll) triflate; In ethanol-d6; water-d2;Conversion of starting material; |
Example 5: Effect of Lanthanide Series Catalyst on Hydrolysis. Deuterated water (d2-water), deuterated ethanol and a series of lanthanide catalysts were mixed together according to the mass ratios in Table 5. A known quantity of [Y-GLYCIDOXYPROPYLTRIMETHOXYSILANE] was added to the solution and the reaction was followed using proton NMR spectroscopy. The time to 83% conversion was between 25 minutes and 272 minutes. All the lanthanide (III) (trifluoromethanesulfonate) 3 catalysts were active in hydrolysing [Y-GLYCIDOXYPROPYLTRIMETHOXYSILANE.] Table 5 Catalyst Mol ratio Mol ratio Mol ratio Concentration Mass %. Mass % Mass % Mass % Minutes to Water Silane catalyst silane Water Solvent Silane Catalyst 83% / g dm-3 Conversion LaTFMS 10 0.2 0.01 8.60 4.1 89.8 0.96 0.12 272 PrTFMS 10 0.2 0.01 8.60 4.1 89. 8 0.96 0.12 58 NdTFMS 10 0.2 0.01 8.60 4.1 89.8 0.96 0.12 63 SmTFMS 10 0.2 0.01 8.60 4.1 89.8 0.96 0.12 59 EuTFMS 10 0.2 0.01 8.60 4.1 89.8 0.96 0.12 43 GaTFMS 10 0.2 0.01 8.60 4.1 89.8 0.96 0.12 89 DyTFMS 10 0.2 0.01 8.60 4.1 89.8 0.96 0.12 61 ErTFMS 10 0.2 0.01 8.60 4.1 89.8 0.96 0.12 57 TmTFMS 10 0.2 0.01 8.60 4.1 89.8 0.96 0.12 63 YbTFMS 10 0.2 0.01 8.60 4.1 89.8 0.96 0.13 29 YbTFMS 10 0.2 0.01 8.60 4.1 89.8 0.96 0.13 25 [LA=LANTHANUM,] [PR=PRAESEODYMIUM,] Nd=neodymium, [SM=SAMARIUM,] [EU=EUROPIUM, GA=GADOIMIUM,] Dy=dysprosium, [ER=ERBIUM,] [TM=THULIUM,] Yb=ytterbium [TFMS=TRIFLUROMETHYLSULFONATE] |
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With lanthanum(lll) triflate; In ethanol-d6; water-d2;Conversion of starting material; |
Example 6: Effect of Lanthanide Series Catalyst on Oligomerisation Deuterated water (d2-water), deuterated ethanol (d6-ethanol) and catalyst were mixed together according to the mass ratios in Table 6. A known quantity of y- glycidoxypropyltrimethoxysilane was added to the solution and the oligomerisation reaction was followed using silicon-29 NMR spectroscopy (measured by the rate of loss of monomeric species). Europium (III) and samarium [(III)] [TRIFLUOROMETHANESULFONATE,, WERE] the least effective oligomerisation catalysts and are the preferred catalysts where it is desired to avoid or to minimise oligomerisation, as, for example, in metal surface treatment processes. Ytterbium and erbium [(III)] tend to promote oligomerisation and hence these catalysts are more suitable for use in crosslinked gel formation processes, such as the generation of solgels, aerogels, xerogels and alcogels. Silicon-29 NMR measurements were performed at higher concentrations of silane and lower concentrations of water. The rate of oligomerisation at 1% mass of the silane (measured by proton NMR) is lower than the rate for 10% mass of silane when catalysed by Eu (III) trifluoromethanesulfonate (Table 6). This may also be the case for oligomerisation reactions catalysed by other metals in the lanthanide series. Table 6 Catalyst Mol ratio Mol ratio Mol ratio Concentration Mass % Mass % Mass % Mass % Half life of Water Silane catalyst Silane Water Solvent Silane Catalyst Silanetriol I g dm-3/mins EuTFMS 5 0. 2 0. 01 94. 20 21. 2 48. 9 10. 00 1. 27 141 EuTFMS 10 0.2 0.01 8.60 4.1 89.9 1.07 0.14 2143 YbTFMS 5 0.2 0.01 94.24 21.2 48.8 10.00 1.31 84 ErTFMS 5 0.2 0.01 94.20 21.2 48.9 10.00 1.30 131 SmTFMS 5 0.2 0.01 94.20 21.2 48.9 10.00 1.26 102 LaTFMS 5 0.2 0. 01 94.20 21. 2 48. 9 10. 00 1. 24 <80 |
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With praseodymium(III) trifluoromethanesulfonate; In ethanol-d6; water-d2;Conversion of starting material; |
Example 5: Effect of Lanthanide Series Catalyst on Hydrolysis. Deuterated water (d2-water), deuterated ethanol and a series of lanthanide catalysts were mixed together according to the mass ratios in Table 5. A known quantity of [Y-GLYCIDOXYPROPYLTRIMETHOXYSILANE] was added to the solution and the reaction was followed using proton NMR spectroscopy. The time to 83% conversion was between 25 minutes and 272 minutes. All the lanthanide (III) (trifluoromethanesulfonate) 3 catalysts were active in hydrolysing [Y-GLYCIDOXYPROPYLTRIMETHOXYSILANE.] Table 5 Catalyst Mol ratio Mol ratio Mol ratio Concentration Mass %. Mass % Mass % Mass % Minutes to Water Silane catalyst silane Water Solvent Silane Catalyst 83% / g dm-3 Conversion LaTFMS 10 0.2 0.01 8.60 4.1 89.8 0.96 0.12 272 PrTFMS 10 0.2 0.01 8.60 4.1 89. 8 0.96 0.12 58 NdTFMS 10 0.2 0.01 8.60 4.1 89.8 0.96 0.12 63 SmTFMS 10 0.2 0.01 8.60 4.1 89.8 0.96 0.12 59 EuTFMS 10 0.2 0.01 8.60 4.1 89.8 0.96 0.12 43 GaTFMS 10 0.2 0.01 8.60 4.1 89.8 0.96 0.12 89 DyTFMS 10 0.2 0.01 8.60 4.1 89.8 0.96 0.12 61 ErTFMS 10 0.2 0.01 8.60 4.1 89.8 0.96 0.12 57 TmTFMS 10 0.2 0.01 8.60 4.1 89.8 0.96 0.12 63 YbTFMS 10 0.2 0.01 8.60 4.1 89.8 0.96 0.13 29 YbTFMS 10 0.2 0.01 8.60 4.1 89.8 0.96 0.13 25 [LA=LANTHANUM,] [PR=PRAESEODYMIUM,] Nd=neodymium, [SM=SAMARIUM,] [EU=EUROPIUM, GA=GADOIMIUM,] Dy=dysprosium, [ER=ERBIUM,] [TM=THULIUM,] Yb=ytterbium [TFMS=TRIFLUROMETHYLSULFONATE] |
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With samarium(III) trifluoromethanesulfonate; In ethanol-d6; water-d2;Conversion of starting material; |
Example 5: Effect of Lanthanide Series Catalyst on Hydrolysis. Deuterated water (d2-water), deuterated ethanol and a series of lanthanide catalysts were mixed together according to the mass ratios in Table 5. A known quantity of [Y-GLYCIDOXYPROPYLTRIMETHOXYSILANE] was added to the solution and the reaction was followed using proton NMR spectroscopy. The time to 83% conversion was between 25 minutes and 272 minutes. All the lanthanide (III) (trifluoromethanesulfonate) 3 catalysts were active in hydrolysing [Y-GLYCIDOXYPROPYLTRIMETHOXYSILANE.] Table 5 Catalyst Mol ratio Mol ratio Mol ratio Concentration Mass %. Mass % Mass % Mass % Minutes to Water Silane catalyst silane Water Solvent Silane Catalyst 83% / g dm-3 Conversion LaTFMS 10 0.2 0.01 8.60 4.1 89.8 0.96 0.12 272 PrTFMS 10 0.2 0.01 8.60 4.1 89. 8 0.96 0.12 58 NdTFMS 10 0.2 0.01 8.60 4.1 89.8 0.96 0.12 63 SmTFMS 10 0.2 0.01 8.60 4.1 89.8 0.96 0.12 59 EuTFMS 10 0.2 0.01 8.60 4.1 89.8 0.96 0.12 43 GaTFMS 10 0.2 0.01 8.60 4.1 89.8 0.96 0.12 89 DyTFMS 10 0.2 0.01 8.60 4.1 89.8 0.96 0.12 61 ErTFMS 10 0.2 0.01 8.60 4.1 89.8 0.96 0.12 57 TmTFMS 10 0.2 0.01 8.60 4.1 89.8 0.96 0.12 63 YbTFMS 10 0.2 0.01 8.60 4.1 89.8 0.96 0.13 29 YbTFMS 10 0.2 0.01 8.60 4.1 89.8 0.96 0.13 25 [LA=LANTHANUM,] [PR=PRAESEODYMIUM,] Nd=neodymium, [SM=SAMARIUM,] [EU=EUROPIUM, GA=GADOIMIUM,] Dy=dysprosium, [ER=ERBIUM,] [TM=THULIUM,] Yb=ytterbium [TFMS=TRIFLUROMETHYLSULFONATE] |
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With samarium(III) trifluoromethanesulfonate; In ethanol-d6; water-d2;Conversion of starting material; |
Example 6: Effect of Lanthanide Series Catalyst on Oligomerisation Deuterated water (d2-water), deuterated ethanol (d6-ethanol) and catalyst were mixed together according to the mass ratios in Table 6. A known quantity of y- glycidoxypropyltrimethoxysilane was added to the solution and the oligomerisation reaction was followed using silicon-29 NMR spectroscopy (measured by the rate of loss of monomeric species). Europium (III) and samarium [(III)] [TRIFLUOROMETHANESULFONATE,, WERE] the least effective oligomerisation catalysts and are the preferred catalysts where it is desired to avoid or to minimise oligomerisation, as, for example, in metal surface treatment processes. Ytterbium and erbium [(III)] tend to promote oligomerisation and hence these catalysts are more suitable for use in crosslinked gel formation processes, such as the generation of solgels, aerogels, xerogels and alcogels. Silicon-29 NMR measurements were performed at higher concentrations of silane and lower concentrations of water. The rate of oligomerisation at 1% mass of the silane (measured by proton NMR) is lower than the rate for 10% mass of silane when catalysed by Eu (III) trifluoromethanesulfonate (Table 6). This may also be the case for oligomerisation reactions catalysed by other metals in the lanthanide series. Table 6 Catalyst Mol ratio Mol ratio Mol ratio Concentration Mass % Mass % Mass % Mass % Half life of Water Silane catalyst Silane Water Solvent Silane Catalyst Silanetriol I g dm-3/mins EuTFMS 5 0. 2 0. 01 94. 20 21. 2 48. 9 10. 00 1. 27 141 EuTFMS 10 0.2 0.01 8.60 4.1 89.9 1.07 0.14 2143 YbTFMS 5 0.2 0.01 94.24 21.2 48.8 10.00 1.31 84 ErTFMS 5 0.2 0.01 94.20 21.2 48.9 10.00 1.30 131 SmTFMS 5 0.2 0.01 94.20 21.2 48.9 10.00 1.26 102 LaTFMS 5 0.2 0. 01 94.20 21. 2 48. 9 10. 00 1. 24 <80 |
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With europium(III) trifluoromethanesulfonate; In ethanol-d6; water-d2;Conversion of starting material; |
Example 5: Effect of Lanthanide Series Catalyst on Hydrolysis. Deuterated water (d2-water), deuterated ethanol and a series of lanthanide catalysts were mixed together according to the mass ratios in Table 5. A known quantity of [Y-GLYCIDOXYPROPYLTRIMETHOXYSILANE] was added to the solution and the reaction was followed using proton NMR spectroscopy. The time to 83% conversion was between 25 minutes and 272 minutes. All the lanthanide (III) (trifluoromethanesulfonate) 3 catalysts were active in hydrolysing [Y-GLYCIDOXYPROPYLTRIMETHOXYSILANE.] Table 5 Catalyst Mol ratio Mol ratio Mol ratio Concentration Mass %. Mass % Mass % Mass % Minutes to Water Silane catalyst silane Water Solvent Silane Catalyst 83% / g dm-3 Conversion LaTFMS 10 0.2 0.01 8.60 4.1 89.8 0.96 0.12 272 PrTFMS 10 0.2 0.01 8.60 4.1 89. 8 0.96 0.12 58 NdTFMS 10 0.2 0.01 8.60 4.1 89.8 0.96 0.12 63 SmTFMS 10 0.2 0.01 8.60 4.1 89.8 0.96 0.12 59 EuTFMS 10 0.2 0.01 8.60 4.1 89.8 0.96 0.12 43 GaTFMS 10 0.2 0.01 8.60 4.1 89.8 0.96 0.12 89 DyTFMS 10 0.2 0.01 8.60 4.1 89.8 0.96 0.12 61 ErTFMS 10 0.2 0.01 8.60 4.1 89.8 0.96 0.12 57 TmTFMS 10 0.2 0.01 8.60 4.1 89.8 0.96 0.12 63 YbTFMS 10 0.2 0.01 8.60 4.1 89.8 0.96 0.13 29 YbTFMS 10 0.2 0.01 8.60 4.1 89.8 0.96 0.13 25 [LA=LANTHANUM,] [PR=PRAESEODYMIUM,] Nd=neodymium, [SM=SAMARIUM,] [EU=EUROPIUM, GA=GADOIMIUM,] Dy=dysprosium, [ER=ERBIUM,] [TM=THULIUM,] Yb=ytterbium [TFMS=TRIFLUROMETHYLSULFONATE] |
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With europium(III) trifluoromethanesulfonate; In ethanol-d6; water-d2;Conversion of starting material; |
Example 6: Effect of Lanthanide Series Catalyst on Oligomerisation Deuterated water (d2-water), deuterated ethanol (d6-ethanol) and catalyst were mixed together according to the mass ratios in Table 6. A known quantity of y- glycidoxypropyltrimethoxysilane was added to the solution and the oligomerisation reaction was followed using silicon-29 NMR spectroscopy (measured by the rate of loss of monomeric species). Europium (III) and samarium [(III)] [TRIFLUOROMETHANESULFONATE,, WERE] the least effective oligomerisation catalysts and are the preferred catalysts where it is desired to avoid or to minimise oligomerisation, as, for example, in metal surface treatment processes. Ytterbium and erbium [(III)] tend to promote oligomerisation and hence these catalysts are more suitable for use in crosslinked gel formation processes, such as the generation of solgels, aerogels, xerogels and alcogels. Silicon-29 NMR measurements were performed at higher concentrations of silane and lower concentrations of water. The rate of oligomerisation at 1% mass of the silane (measured by proton NMR) is lower than the rate for 10% mass of silane when catalysed by Eu (III) trifluoromethanesulfonate (Table 6). This may also be the case for oligomerisation reactions catalysed by other metals in the lanthanide series. Table 6 Catalyst Mol ratio Mol ratio Mol ratio Concentration Mass % Mass % Mass % Mass % Half life of Water Silane catalyst Silane Water Solvent Silane Catalyst Silanetriol I g dm-3/mins EuTFMS 5 0. 2 0. 01 94. 20 21. 2 48. 9 10. 00 1. 27 141 EuTFMS 10 0.2 0.01 8.60 4.1 89.9 1.07 0.14 2143 YbTFMS 5 0.2 0.01 94.24 21.2 48.8 10.00 1.31 84 ErTFMS 5 0.2 0.01 94.20 21.2 48.9 10.00 1.30 131 SmTFMS 5 0.2 0.01 94.20 21.2 48.9 10.00 1.26 102 LaTFMS 5 0.2 0. 01 94.20 21. 2 48. 9 10. 00 1. 24 <80 |
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With europium(III) trifluoromethanesulfonate; In ethanol-d6; water-d2; at 25 - 90℃; for 1h;Conversion of starting material; |
Example 8 Effect of La Series Catalyst on metal Surface Condensation Deuterated water (d2-water), deuterated ethanol (d6-ethanol), europium (III) trifluoromethanesulfonate) 3 (catalyst) and GPS were mixed together according to the mass ratio of 30.1 : 695: 1: 7.9 respectively. The solution was hydrolysed at [25C] for one hour. The hydrolysed silane solution was dripped onto degreased, grit- blasted stainless steel and the surface was air dried to remove volatile solvent leaving a thin coating (0.1 to 10 microns) of monomeric hydrolysed silane. The condensation reaction was followed by diffuse reflectance infrared spectroscopy at temperatures in the range [OF 30C] to [90C.] For comparative purposes, a condensation reaction according to a current state of the art silane treatment system was carried out. The hydrolysis of GPS in water and ethanol (mass ratio of 1: 2: 18) was catalysed by the addition of acid (pH of 3.7). The solution'was hydrolysed for one hour at [25C] before applying onto degreased, grit-blasted stainless steel. The residual solvent was evaporated from the surface by air drying. The condensation reaction was followed by diffuse reflectance infrared spectroscopy at temperatures in the range [OF 30C] to [90C.] The results are shown in Table 8. The disappearance of the hydroxyl band in the infrared spectroscopy (band centred around 3375 [CM-L)] gave a measure at which the monomeric hydroxyl silane condensed to form a highly crosslinked siloxane film. The kinetic curves are complex and are not first, second or simple n order rate processes. A measure of the reaction rate, in Table 8, is given by the peak ratio of the OH band to CH band (centered at [2800CM~L)] at a time interval of 50 minutes. At equivalent temperatures, the condensation reaction has progressed to a greater extent for the europium (III) trifluoromethanesulphonate catalysed system relative to the acid catalysed system. Near the end of the condensation reaction the OH content forms an equilibrium, as there appears to be no further change with time. This suggests that the condensation process is limited either by diffusion processes or by the chemistry of the structure (eg. steric hindrance). However, at equivalent temperatures, the europium (III) trifluoromethane sulphonate catalysed system contains less OH than the acid catalysed system suggesting that the lanthanide salt catalyses the condensation process to a greater extent than the acid catalysed system. A comparison of the rare earth metal catalysed reaction process with that of the current state of the art methodology therefore indicates that the lanthanide catalysts not only increases the rate at which the silane condenses to a highly crosslinked film but also it increases the extent of the reaction. Table 8 Catalyst Temperature C Peak ratio at Peak ratio at 50 mins measurement end EuTFMS 30 2.03 1.75 EuTFMS 40 1.89 1.68 EuTFMS 50 1.81 1.31 EuTFMS 60 1.52 0.91 EuTFMS 70 1.04 0.71 EuTFMS 80 1. 26 1.22 EuTFMS 90 0.81 0.82 Acid catalyst 30 2.53 1.99 Acid catalyst 40 2.24 1.96 Acid catalyst 50 2.01 1.84 Acid catalyst 70 1.69 1.61 Acid catalyst 80 1. 51 1.44 Acid catalyst 90 1.53 1.43 |
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With europium(III) trifluoromethanesulfonate; In ethanol-d6; water-d2; at 20 - 35℃;Conversion of starting material; |
Example 7: Effect of Europium Salt and Temperature on Silane Hydrolysis Unless otherwise specified, deuterated water (d2-water), deuterated ethanol (d6-ethanol) and catalyst were mixed together according to the mass ratios in Table 7. A known quantity of y-glycidoxypropyltrimethoxysilane was added to the solution and the hydrolysis reaction was followed using proton NMR spectroscopy (measured by the rate of formation of methanol). The time to 83% conversion typically took between 11 minutes and more than 2500 minutes. Europium perchlorate was the best catalyst for silane hydrolysis. The activation energy for GPS hydrolysis was calculated to be 57 kJ per mole. Using the same mol ratio of reactants and solvents, there is found to be little difference between the hydrolysis rates in protic solvents (sample [EUTFMS] (1), Table 7) and in deuterated solvents. Table 7 Catalyst Concentration Mass % Mass % Mass % Mass % Temperature Minutes to Silane Water Solvent Silane catalyst/C 83% /g dm-3 Conversion EuTFMS 8. 60 4. 06 94. 86 0. 96 0. 12 30 44 EuTFMS 8.60 4.06 94.86 0.96 0.12 35 21 EuTFMS 8.60 4.06 94.86 0.96 0.12 20 116 EuOxalate. XH20 8.60 4.06 94.87 0.96 0.12 25 >5000 Eu perchlorate 8.55 4.04 94.92 0.95 0.09 25 11 Eu nitrate 8.60 4.06 94.89 0.96 0.09 25 2574 pentahydrate EuTFMS (1) # 7.64 3.64 95.28 0.96 0.12 25 44 # solvent was protonated ethanol and water (ie. non-deuterated) |
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With europium(III) oxalate; In ethanol-d6; water-d2;Conversion of starting material; |
Example 7: Effect of Europium Salt and Temperature on Silane Hydrolysis Unless otherwise specified, deuterated water (d2-water), deuterated ethanol (d6-ethanol) and catalyst were mixed together according to the mass ratios in Table 7. A known quantity of y-glycidoxypropyltrimethoxysilane was added to the solution and the hydrolysis reaction was followed using proton NMR spectroscopy (measured by the rate of formation of methanol). The time to 83% conversion typically took between 11 minutes and more than 2500 minutes. Europium perchlorate was the best catalyst for silane hydrolysis. The activation energy for GPS hydrolysis was calculated to be 57 kJ per mole. Using the same mol ratio of reactants and solvents, there is found to be little difference between the hydrolysis rates in protic solvents (sample [EUTFMS] (1), Table 7) and in deuterated solvents. Table 7 Catalyst Concentration Mass % Mass % Mass % Mass % Temperature Minutes to Silane Water Solvent Silane catalyst/C 83% /g dm-3 Conversion EuTFMS 8. 60 4. 06 94. 86 0. 96 0. 12 30 44 EuTFMS 8.60 4.06 94.86 0.96 0.12 35 21 EuTFMS 8.60 4.06 94.86 0.96 0.12 20 116 EuOxalate. XH20 8.60 4.06 94.87 0.96 0.12 25 >5000 Eu perchlorate 8.55 4.04 94.92 0.95 0.09 25 11 Eu nitrate 8.60 4.06 94.89 0.96 0.09 25 2574 pentahydrate EuTFMS (1) # 7.64 3.64 95.28 0.96 0.12 25 44 # solvent was protonated ethanol and water (ie. non-deuterated) |
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With europium(III) perchlorate; In ethanol-d6; water-d2;Conversion of starting material; |
Example 7: Effect of Europium Salt and Temperature on Silane Hydrolysis Unless otherwise specified, deuterated water (d2-water), deuterated ethanol (d6-ethanol) and catalyst were mixed together according to the mass ratios in Table 7. A known quantity of y-glycidoxypropyltrimethoxysilane was added to the solution and the hydrolysis reaction was followed using proton NMR spectroscopy (measured by the rate of formation of methanol). The time to 83% conversion typically took between 11 minutes and more than 2500 minutes. Europium perchlorate was the best catalyst for silane hydrolysis. The activation energy for GPS hydrolysis was calculated to be 57 kJ per mole. Using the same mol ratio of reactants and solvents, there is found to be little difference between the hydrolysis rates in protic solvents (sample [EUTFMS] (1), Table 7) and in deuterated solvents. Table 7 Catalyst Concentration Mass % Mass % Mass % Mass % Temperature Minutes to Silane Water Solvent Silane catalyst/C 83% /g dm-3 Conversion EuTFMS 8. 60 4. 06 94. 86 0. 96 0. 12 30 44 EuTFMS 8.60 4.06 94.86 0.96 0.12 35 21 EuTFMS 8.60 4.06 94.86 0.96 0.12 20 116 EuOxalate. XH20 8.60 4.06 94.87 0.96 0.12 25 >5000 Eu perchlorate 8.55 4.04 94.92 0.95 0.09 25 11 Eu nitrate 8.60 4.06 94.89 0.96 0.09 25 2574 pentahydrate EuTFMS (1) # 7.64 3.64 95.28 0.96 0.12 25 44 # solvent was protonated ethanol and water (ie. non-deuterated) |
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With europium(III) nitrate; In ethanol-d6; water-d2;Conversion of starting material; |
Example 7: Effect of Europium Salt and Temperature on Silane Hydrolysis Unless otherwise specified, deuterated water (d2-water), deuterated ethanol (d6-ethanol) and catalyst were mixed together according to the mass ratios in Table 7. A known quantity of y-glycidoxypropyltrimethoxysilane was added to the solution and the hydrolysis reaction was followed using proton NMR spectroscopy (measured by the rate of formation of methanol). The time to 83% conversion typically took between 11 minutes and more than 2500 minutes. Europium perchlorate was the best catalyst for silane hydrolysis. The activation energy for GPS hydrolysis was calculated to be 57 kJ per mole. Using the same mol ratio of reactants and solvents, there is found to be little difference between the hydrolysis rates in protic solvents (sample [EUTFMS] (1), Table 7) and in deuterated solvents. Table 7 Catalyst Concentration Mass % Mass % Mass % Mass % Temperature Minutes to Silane Water Solvent Silane catalyst/C 83% /g dm-3 Conversion EuTFMS 8. 60 4. 06 94. 86 0. 96 0. 12 30 44 EuTFMS 8.60 4.06 94.86 0.96 0.12 35 21 EuTFMS 8.60 4.06 94.86 0.96 0.12 20 116 EuOxalate. XH20 8.60 4.06 94.87 0.96 0.12 25 >5000 Eu perchlorate 8.55 4.04 94.92 0.95 0.09 25 11 Eu nitrate 8.60 4.06 94.89 0.96 0.09 25 2574 pentahydrate EuTFMS (1) # 7.64 3.64 95.28 0.96 0.12 25 44 # solvent was protonated ethanol and water (ie. non-deuterated) |
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With neodymium(III) trifluoromethanesufonate; In ethanol-d6; water-d2;Conversion of starting material; |
Example 5: Effect of Lanthanide Series Catalyst on Hydrolysis. Deuterated water (d2-water), deuterated ethanol and a series of lanthanide catalysts were mixed together according to the mass ratios in Table 5. A known quantity of [Y-GLYCIDOXYPROPYLTRIMETHOXYSILANE] was added to the solution and the reaction was followed using proton NMR spectroscopy. The time to 83% conversion was between 25 minutes and 272 minutes. All the lanthanide (III) (trifluoromethanesulfonate) 3 catalysts were active in hydrolysing [Y-GLYCIDOXYPROPYLTRIMETHOXYSILANE.] Table 5 Catalyst Mol ratio Mol ratio Mol ratio Concentration Mass %. Mass % Mass % Mass % Minutes to Water Silane catalyst silane Water Solvent Silane Catalyst 83% / g dm-3 Conversion LaTFMS 10 0.2 0.01 8.60 4.1 89.8 0.96 0.12 272 PrTFMS 10 0.2 0.01 8.60 4.1 89. 8 0.96 0.12 58 NdTFMS 10 0.2 0.01 8.60 4.1 89.8 0.96 0.12 63 SmTFMS 10 0.2 0.01 8.60 4.1 89.8 0.96 0.12 59 EuTFMS 10 0.2 0.01 8.60 4.1 89.8 0.96 0.12 43 GaTFMS 10 0.2 0.01 8.60 4.1 89.8 0.96 0.12 89 DyTFMS 10 0.2 0.01 8.60 4.1 89.8 0.96 0.12 61 ErTFMS 10 0.2 0.01 8.60 4.1 89.8 0.96 0.12 57 TmTFMS 10 0.2 0.01 8.60 4.1 89.8 0.96 0.12 63 YbTFMS 10 0.2 0.01 8.60 4.1 89.8 0.96 0.13 29 YbTFMS 10 0.2 0.01 8.60 4.1 89.8 0.96 0.13 25 [LA=LANTHANUM,] [PR=PRAESEODYMIUM,] Nd=neodymium, [SM=SAMARIUM,] [EU=EUROPIUM, GA=GADOIMIUM,] Dy=dysprosium, [ER=ERBIUM,] [TM=THULIUM,] Yb=ytterbium [TFMS=TRIFLUROMETHYLSULFONATE] |
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With ytterbium(III) triflate; In d(4)-methanol; water-d2;Conversion of starting material; |
Example 4: Effect of silane on Yb [(OTF) 3] catalysed system Deuterated water (d2-water), deuterated methanol and ytterbium trifluoromethanesulfonate were mixed together according to the mass ratios in Table 4. A'known quantity of silane was added to the solution and the reaction was followed using proton NMR spectroscopy. The time to 83% conversion was between 6 minutes and 425 minutes. All the silanes underwent hydrolysis; however, vinyl trimethoxysilane and [3-] trimethoxysilylpropylacrylate reacted rapidly within 15 minutes. The 3- [AMINOPROPYLTRIETHOXYSILANE] rapidly crosslinked within an hour to form a gel like material. The kinetics of this reaction could not be followed by proton NMR spectroscopy. This example shows that the non hydrolysable group attached to the silicon atom has a great effect on the reactivity of the silane. However, for surface coating solutions it will generally be desired that the side chain should have certain specific properties and for this reason the coatings industry tends to be directed towards the use of particular silanes. Table 4 Mol Mol Mol Concn. Mass % Mass % Mass Mass % Minutes to Silane ratio ratio ratio % Water silane Catalyst Silane Water Solvent Silane catalyst 83% Conversion /g dm-3 Vinyl trimethoxy silane 10 0. 2 0. 01 8. 6 6. 4 92. 4 0. 95 0. 20 11. 3 3- (trimethoxysilyl) propyl 10 0.2 0.01 8.6 4.1 94.8 0.96 0.13 6.1 acrylate GPS 10 0.2 0.01 8.6 4.1 94.9 0.96 0.13 28.8 Triethoxyvinylsilane 10 0.2 0.01 8.6 5.0 93.8 0.96 0.16 25.4 Triethoxysilylpropylethylen 10 0.2 0.01 8.6 4.3 94.6 0.96 0.13 31.3 diamine dc 3-10 0.2 0.01 8.6 4.3 94.6 0.96 0.13 Gel aminopropyltriethoxysilane dc 3- (triethoxysilyl) propyl 10 0.2 0.01 8.6 3.9 95.0 0.96 0.12 425.5 isocyanate GPS (SipB) 10 0.2 0.01 8.6 4.1 94.9 0. 96 0.13 16.4 |
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With ytterbium(III) triflate; In tetrahydrofuran-d8; water-d2;Conversion of starting material; |
Example 3: Effect of solvent on Yb (OTf) 3 catalysed system Deuterated water (d2-water), deuterated solvent and ytterbium trifluoromethanesulfonate were mixed together according to the mass ratios in Table 3. A known quantity [OF Y-GLYCIDOXYPROPYLTRIMETHOXYSILANE] was added to the solution and the reaction was followed using proton NMR spectroscopy. The time taken to 83% conversion was between 23 minutes and 182752 minutes. Although the reaction was shown to take place in THF and dioxane, for industrial purposes, high concentrations of THF and dioxane are impracticable. It should be noted that the reaction proceeds faster in a more polar solvent and the best results are in protic solvents such as ethanol and methanol. Table 3 Mol ratio Mol ratio Mol ratio Concentration Solvent Mass Mass Mass Mass % Minutes to water silane catalyst silane % % % 83% /g dm-3 Water Solvent Silane Catalyst Conversion 10 0. 1 0. 01 12. 9 EtOD 12. 0 86.3 1.4 0. 37 47 10 0.2 0.01 8.6 EtOD 4.1 94.9 1.0 0.13 29 10 0.1 0.01 12.9 MeOD 12.0 86.3 1.4 0.37 58 10 0.2 0.01 8.6 MeOD 4.1 94.9 1.0 0.13 23 10 0.1 0.01 12.9 THF 10.9 87.4 1.3 0.34 416 10 0.2 0.01 8.6 THF 3.7 95.3 0.9 0.11 2682 10 0.1 0.01 12.9 D6-Acetone 12.2 86.0 1.4 0.38 173 10 0.2 0.01 8.6 D6-Acetone 4.1 94.8 1.0 0.13 267 10 0.1 0.01 12.9 ACN 12.5 85.6 1.5 0.39 142 10 0.2 0.01 8.6 ACN 4.3 94.6 1.0 0.13 124 10 0.1 0.01 12.9 dioxane 9.7 88.9 1.1 0.30 2084 10 0.2 0.01 8.6 dioxane 3. 2 95.9 0.8 0. 10 18272 |
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With ytterbium(III) triflate; In deuteromethanol; water-d2;Conversion of starting material; |
Example 3: Effect of solvent on Yb (OTf) 3 catalysed system Deuterated water (d2-water), deuterated solvent and ytterbium trifluoromethanesulfonate were mixed together according to the mass ratios in Table 3. A known quantity [OF Y-GLYCIDOXYPROPYLTRIMETHOXYSILANE] was added to the solution and the reaction was followed using proton NMR spectroscopy. The time taken to 83% conversion was between 23 minutes and 182752 minutes. Although the reaction was shown to take place in THF and dioxane, for industrial purposes, high concentrations of THF and dioxane are impracticable. It should be noted that the reaction proceeds faster in a more polar solvent and the best results are in protic solvents such as ethanol and methanol. Table 3 Mol ratio Mol ratio Mol ratio Concentration Solvent Mass Mass Mass Mass % Minutes to water silane catalyst silane % % % 83% /g dm-3 Water Solvent Silane Catalyst Conversion 10 0. 1 0. 01 12. 9 EtOD 12. 0 86.3 1.4 0. 37 47 10 0.2 0.01 8.6 EtOD 4.1 94.9 1.0 0.13 29 10 0.1 0.01 12.9 MeOD 12.0 86.3 1.4 0.37 58 10 0.2 0.01 8.6 MeOD 4.1 94.9 1.0 0.13 23 10 0.1 0.01 12.9 THF 10.9 87.4 1.3 0.34 416 10 0.2 0.01 8.6 THF 3.7 95.3 0.9 0.11 2682 10 0.1 0.01 12.9 D6-Acetone 12.2 86.0 1.4 0.38 173 10 0.2 0.01 8.6 D6-Acetone 4.1 94.8 1.0 0.13 267 10 0.1 0.01 12.9 ACN 12.5 85.6 1.5 0.39 142 10 0.2 0.01 8.6 ACN 4.3 94.6 1.0 0.13 124 10 0.1 0.01 12.9 dioxane 9.7 88.9 1.1 0.30 2084 10 0.2 0.01 8.6 dioxane 3. 2 95.9 0.8 0. 10 18272 |
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With ytterbium(III) triflate; In 1,4-dioxane-d8; water-d2;Conversion of starting material; |
Example 3: Effect of solvent on Yb (OTf) 3 catalysed system Deuterated water (d2-water), deuterated solvent and ytterbium trifluoromethanesulfonate were mixed together according to the mass ratios in Table 3. A known quantity [OF Y-GLYCIDOXYPROPYLTRIMETHOXYSILANE] was added to the solution and the reaction was followed using proton NMR spectroscopy. The time taken to 83% conversion was between 23 minutes and 182752 minutes. Although the reaction was shown to take place in THF and dioxane, for industrial purposes, high concentrations of THF and dioxane are impracticable. It should be noted that the reaction proceeds faster in a more polar solvent and the best results are in protic solvents such as ethanol and methanol. Table 3 Mol ratio Mol ratio Mol ratio Concentration Solvent Mass Mass Mass Mass % Minutes to water silane catalyst silane % % % 83% /g dm-3 Water Solvent Silane Catalyst Conversion 10 0. 1 0. 01 12. 9 EtOD 12. 0 86.3 1.4 0. 37 47 10 0.2 0.01 8.6 EtOD 4.1 94.9 1.0 0.13 29 10 0.1 0.01 12.9 MeOD 12.0 86.3 1.4 0.37 58 10 0.2 0.01 8.6 MeOD 4.1 94.9 1.0 0.13 23 10 0.1 0.01 12.9 THF 10.9 87.4 1.3 0.34 416 10 0.2 0.01 8.6 THF 3.7 95.3 0.9 0.11 2682 10 0.1 0.01 12.9 D6-Acetone 12.2 86.0 1.4 0.38 173 10 0.2 0.01 8.6 D6-Acetone 4.1 94.8 1.0 0.13 267 10 0.1 0.01 12.9 ACN 12.5 85.6 1.5 0.39 142 10 0.2 0.01 8.6 ACN 4.3 94.6 1.0 0.13 124 10 0.1 0.01 12.9 dioxane 9.7 88.9 1.1 0.30 2084 10 0.2 0.01 8.6 dioxane 3. 2 95.9 0.8 0. 10 18272 |
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With ytterbium(III) triflate; In [D3]acetonitrile; water-d2;Conversion of starting material; |
Example 3: Effect of solvent on Yb (OTf) 3 catalysed system Deuterated water (d2-water), deuterated solvent and ytterbium trifluoromethanesulfonate were mixed together according to the mass ratios in Table 3. A known quantity [OF Y-GLYCIDOXYPROPYLTRIMETHOXYSILANE] was added to the solution and the reaction was followed using proton NMR spectroscopy. The time taken to 83% conversion was between 23 minutes and 182752 minutes. Although the reaction was shown to take place in THF and dioxane, for industrial purposes, high concentrations of THF and dioxane are impracticable. It should be noted that the reaction proceeds faster in a more polar solvent and the best results are in protic solvents such as ethanol and methanol. Table 3 Mol ratio Mol ratio Mol ratio Concentration Solvent Mass Mass Mass Mass % Minutes to water silane catalyst silane % % % 83% /g dm-3 Water Solvent Silane Catalyst Conversion 10 0. 1 0. 01 12. 9 EtOD 12. 0 86.3 1.4 0. 37 47 10 0.2 0.01 8.6 EtOD 4.1 94.9 1.0 0.13 29 10 0.1 0.01 12.9 MeOD 12.0 86.3 1.4 0.37 58 10 0.2 0.01 8.6 MeOD 4.1 94.9 1.0 0.13 23 10 0.1 0.01 12.9 THF 10.9 87.4 1.3 0.34 416 10 0.2 0.01 8.6 THF 3.7 95.3 0.9 0.11 2682 10 0.1 0.01 12.9 D6-Acetone 12.2 86.0 1.4 0.38 173 10 0.2 0.01 8.6 D6-Acetone 4.1 94.8 1.0 0.13 267 10 0.1 0.01 12.9 ACN 12.5 85.6 1.5 0.39 142 10 0.2 0.01 8.6 ACN 4.3 94.6 1.0 0.13 124 10 0.1 0.01 12.9 dioxane 9.7 88.9 1.1 0.30 2084 10 0.2 0.01 8.6 dioxane 3. 2 95.9 0.8 0. 10 18272 |
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With ytterbium(III) triflate; In ethanol-d6; water-d2;Conversion of starting material; |
Example 2: Effect of Water to Ethanol ratio on Yb (OTf) 3 catalysed system Deuterated water (d2-water), deuterated ethanol (d6-ethanol) and ytterbium trifluoromethanesulfonate were mixed together according to the mass ratios in Table 2. A known quantity [OF Y-GLYCIDOXYPROPYLTRIMETHOXYSILANE] was added to the solution and the reaction was followed using proton nuclear magnetic resonance (NMR) spectroscopy. The time taken to 83% conversion was between 4 minutes and 174 minutes. There is a clear trend that for a given catalyst, with a fixed concentration of silane, for example [0.] 10 mol ratio, as the water percentage increases the reaction time increases. However, at near 100% water content, the reaction times decrease. Further experiments were carried out using 0.20 mol ratio, effectively doubling the silane concentration, and the same effects were observed. The apparent decrease in reaction time at near 100% water content implies that a different hydrolysis mechanism could be occurring. Table 2 Mol ratio Mol ratio Mol ratio Concentration Mass % Mass % Mass % Mass % Minutes to Water Silane Catalyst silane dm-3 Water Ethanol Silane catalyst 83% Conversion 5. 00 0. 10 0. 01 12. 91 6. 05 92.14 1.43 0. 37 4 10.00 0.10 0.01 12.91 11.96 86.26 1.41 0.37 47 25.00 0.10 0.01 12.91 28.88 69.40 1.36 0.36 159 50.00 0.10 0.01 12.91 54.64 43.73 1.29 0.34 174 99.89 0.10 0.01 12.91 98.53 0.00 1.16 0.31 81 10.00 0.20 0.01 8.60 4.06 94.86 0.96 0.13 29 50.00 0.20 0.01 25.54 53.99 43.13 2.55'0. 33 167 99.79 0. 20 0. 01 25.55 97. 54 0. 00 2. 31 0. 15 131 |
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With ytterbium(III) triflate; In ethanol-d6; water-d2;Conversion of starting material; |
Example 5: Effect of Lanthanide Series Catalyst on Hydrolysis. Deuterated water (d2-water), deuterated ethanol and a series of lanthanide catalysts were mixed together according to the mass ratios in Table 5. A known quantity of [Y-GLYCIDOXYPROPYLTRIMETHOXYSILANE] was added to the solution and the reaction was followed using proton NMR spectroscopy. The time to 83% conversion was between 25 minutes and 272 minutes. All the lanthanide (III) (trifluoromethanesulfonate) 3 catalysts were active in hydrolysing [Y-GLYCIDOXYPROPYLTRIMETHOXYSILANE.] Table 5 Catalyst Mol ratio Mol ratio Mol ratio Concentration Mass %. Mass % Mass % Mass % Minutes to Water Silane catalyst silane Water Solvent Silane Catalyst 83% / g dm-3 Conversion LaTFMS 10 0.2 0.01 8.60 4.1 89.8 0.96 0.12 272 PrTFMS 10 0.2 0.01 8.60 4.1 89. 8 0.96 0.12 58 NdTFMS 10 0.2 0.01 8.60 4.1 89.8 0.96 0.12 63 SmTFMS 10 0.2 0.01 8.60 4.1 89.8 0.96 0.12 59 EuTFMS 10 0.2 0.01 8.60 4.1 89.8 0.96 0.12 43 GaTFMS 10 0.2 0.01 8.60 4.1 89.8 0.96 0.12 89 DyTFMS 10 0.2 0.01 8.60 4.1 89.8 0.96 0.12 61 ErTFMS 10 0.2 0.01 8.60 4.1 89.8 0.96 0.12 57 TmTFMS 10 0.2 0.01 8.60 4.1 89.8 0.96 0.12 63 YbTFMS 10 0.2 0.01 8.60 4.1 89.8 0.96 0.13 29 YbTFMS 10 0.2 0.01 8.60 4.1 89.8 0.96 0.13 25 [LA=LANTHANUM,] [PR=PRAESEODYMIUM,] Nd=neodymium, [SM=SAMARIUM,] [EU=EUROPIUM, GA=GADOIMIUM,] Dy=dysprosium, [ER=ERBIUM,] [TM=THULIUM,] Yb=ytterbium [TFMS=TRIFLUROMETHYLSULFONATE] |
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With ytterbium(III) triflate; In ethanol-d6; water-d2;Conversion of starting material; |
Example 6: Effect of Lanthanide Series Catalyst on Oligomerisation Deuterated water (d2-water), deuterated ethanol (d6-ethanol) and catalyst were mixed together according to the mass ratios in Table 6. A known quantity of y- glycidoxypropyltrimethoxysilane was added to the solution and the oligomerisation reaction was followed using silicon-29 NMR spectroscopy (measured by the rate of loss of monomeric species). Europium (III) and samarium [(III)] [TRIFLUOROMETHANESULFONATE,, WERE] the least effective oligomerisation catalysts and are the preferred catalysts where it is desired to avoid or to minimise oligomerisation, as, for example, in metal surface treatment processes. Ytterbium and erbium [(III)] tend to promote oligomerisation and hence these catalysts are more suitable for use in crosslinked gel formation processes, such as the generation of solgels, aerogels, xerogels and alcogels. Silicon-29 NMR measurements were performed at higher concentrations of silane and lower concentrations of water. The rate of oligomerisation at 1% mass of the silane (measured by proton NMR) is lower than the rate for 10% mass of silane when catalysed by Eu (III) trifluoromethanesulfonate (Table 6). This may also be the case for oligomerisation reactions catalysed by other metals in the lanthanide series. Table 6 Catalyst Mol ratio Mol ratio Mol ratio Concentration Mass % Mass % Mass % Mass % Half life of Water Silane catalyst Silane Water Solvent Silane Catalyst Silanetriol I g dm-3/mins EuTFMS 5 0. 2 0. 01 94. 20 21. 2 48. 9 10. 00 1. 27 141 EuTFMS 10 0.2 0.01 8.60 4.1 89.9 1.07 0.14 2143 YbTFMS 5 0.2 0.01 94.24 21.2 48.8 10.00 1.31 84 ErTFMS 5 0.2 0.01 94.20 21.2 48.9 10.00 1.30 131 SmTFMS 5 0.2 0.01 94.20 21.2 48.9 10.00 1.26 102 LaTFMS 5 0.2 0. 01 94.20 21. 2 48. 9 10. 00 1. 24 <80 |
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With ytterbium(III) triflate; In [(2)H6]acetone; water-d2;Conversion of starting material; |
Example 3: Effect of solvent on Yb (OTf) 3 catalysed system Deuterated water (d2-water), deuterated solvent and ytterbium trifluoromethanesulfonate were mixed together according to the mass ratios in Table 3. A known quantity [OF Y-GLYCIDOXYPROPYLTRIMETHOXYSILANE] was added to the solution and the reaction was followed using proton NMR spectroscopy. The time taken to 83% conversion was between 23 minutes and 182752 minutes. Although the reaction was shown to take place in THF and dioxane, for industrial purposes, high concentrations of THF and dioxane are impracticable. It should be noted that the reaction proceeds faster in a more polar solvent and the best results are in protic solvents such as ethanol and methanol. Table 3 Mol ratio Mol ratio Mol ratio Concentration Solvent Mass Mass Mass Mass % Minutes to water silane catalyst silane % % % 83% /g dm-3 Water Solvent Silane Catalyst Conversion 10 0. 1 0. 01 12. 9 EtOD 12. 0 86.3 1.4 0. 37 47 10 0.2 0.01 8.6 EtOD 4.1 94.9 1.0 0.13 29 10 0.1 0.01 12.9 MeOD 12.0 86.3 1.4 0.37 58 10 0.2 0.01 8.6 MeOD 4.1 94.9 1.0 0.13 23 10 0.1 0.01 12.9 THF 10.9 87.4 1.3 0.34 416 10 0.2 0.01 8.6 THF 3.7 95.3 0.9 0.11 2682 10 0.1 0.01 12.9 D6-Acetone 12.2 86.0 1.4 0.38 173 10 0.2 0.01 8.6 D6-Acetone 4.1 94.8 1.0 0.13 267 10 0.1 0.01 12.9 ACN 12.5 85.6 1.5 0.39 142 10 0.2 0.01 8.6 ACN 4.3 94.6 1.0 0.13 124 10 0.1 0.01 12.9 dioxane 9.7 88.9 1.1 0.30 2084 10 0.2 0.01 8.6 dioxane 3. 2 95.9 0.8 0. 10 18272 |
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With ytterbium(III) triflate; In ethyl [2]alcohol; water-d2;Conversion of starting material; |
Example 3: Effect of solvent on Yb (OTf) 3 catalysed system Deuterated water (d2-water), deuterated solvent and ytterbium trifluoromethanesulfonate were mixed together according to the mass ratios in Table 3. A known quantity [OF Y-GLYCIDOXYPROPYLTRIMETHOXYSILANE] was added to the solution and the reaction was followed using proton NMR spectroscopy. The time taken to 83% conversion was between 23 minutes and 182752 minutes. Although the reaction was shown to take place in THF and dioxane, for industrial purposes, high concentrations of THF and dioxane are impracticable. It should be noted that the reaction proceeds faster in a more polar solvent and the best results are in protic solvents such as ethanol and methanol. Table 3 Mol ratio Mol ratio Mol ratio Concentration Solvent Mass Mass Mass Mass % Minutes to water silane catalyst silane % % % 83% /g dm-3 Water Solvent Silane Catalyst Conversion 10 0. 1 0. 01 12. 9 EtOD 12. 0 86.3 1.4 0. 37 47 10 0.2 0.01 8.6 EtOD 4.1 94.9 1.0 0.13 29 10 0.1 0.01 12.9 MeOD 12.0 86.3 1.4 0.37 58 10 0.2 0.01 8.6 MeOD 4.1 94.9 1.0 0.13 23 10 0.1 0.01 12.9 THF 10.9 87.4 1.3 0.34 416 10 0.2 0.01 8.6 THF 3.7 95.3 0.9 0.11 2682 10 0.1 0.01 12.9 D6-Acetone 12.2 86.0 1.4 0.38 173 10 0.2 0.01 8.6 D6-Acetone 4.1 94.8 1.0 0.13 267 10 0.1 0.01 12.9 ACN 12.5 85.6 1.5 0.39 142 10 0.2 0.01 8.6 ACN 4.3 94.6 1.0 0.13 124 10 0.1 0.01 12.9 dioxane 9.7 88.9 1.1 0.30 2084 10 0.2 0.01 8.6 dioxane 3. 2 95.9 0.8 0. 10 18272 |
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With ytterbium(III) triflate; In water-d2;Conversion of starting material; |
Example 2: Effect of Water to Ethanol ratio on Yb (OTf) 3 catalysed system Deuterated water (d2-water), deuterated ethanol (d6-ethanol) and ytterbium trifluoromethanesulfonate were mixed together according to the mass ratios in Table 2. A known quantity [OF Y-GLYCIDOXYPROPYLTRIMETHOXYSILANE] was added to the solution and the reaction was followed using proton nuclear magnetic resonance (NMR) spectroscopy. The time taken to 83% conversion was between 4 minutes and 174 minutes. There is a clear trend that for a given catalyst, with a fixed concentration of silane, for example [0.] 10 mol ratio, as the water percentage increases the reaction time increases. However, at near 100% water content, the reaction times decrease. Further experiments were carried out using 0.20 mol ratio, effectively doubling the silane concentration, and the same effects were observed. The apparent decrease in reaction time at near 100% water content implies that a different hydrolysis mechanism could be occurring. Table 2 Mol ratio Mol ratio Mol ratio Concentration Mass % Mass % Mass % Mass % Minutes to Water Silane Catalyst silane dm-3 Water Ethanol Silane catalyst 83% Conversion 5. 00 0. 10 0. 01 12. 91 6. 05 92.14 1.43 0. 37 4 10.00 0.10 0.01 12.91 11.96 86.26 1.41 0.37 47 25.00 0.10 0.01 12.91 28.88 69.40 1.36 0.36 159 50.00 0.10 0.01 12.91 54.64 43.73 1.29 0.34 174 99.89 0.10 0.01 12.91 98.53 0.00 1.16 0.31 81 10.00 0.20 0.01 8.60 4.06 94.86 0.96 0.13 29 50.00 0.20 0.01 25.54 53.99 43.13 2.55'0. 33 167 99.79 0. 20 0. 01 25.55 97. 54 0. 00 2. 31 0. 15 131 |
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In ethanol; water;Reactivity (does not react); |
Example 1: (Comparative) Hydrolysis of GPS in water is catalysed by addition of acid or base, otherwise the rate of reaction is too slow to warrant use in an industrial process (see Table 1). Addition of ethanol or other solvent rapidly decreases the rate of hydrolysis to unacceptable levels. The addition of acetic acid to high ethanol to water ratio solutions, does not increase the rate of silane hydrolysis. Table 1 Mass % Mass % Mass % PH Minutes to Water Ethanol Silane 83% Conversion 99 0 1 Neutral 2200 99 0 1 4.3 68 99 0 1 9.0 381 4 95 1 Neutral >60000 59 40 1 Neutral 49000 |
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A 20 ml scintillation bottle was initially charged with 9.4 g of Dynasylan GLYMO, 0.188 g of boric acid were added with stirring (magnetic stirrer), the mixture was heated at 60 C. for 30 minutes and then 0.864 g of demineralized water was stirred in. The mixture was stirred at a bottom temperature of 60 to 70 C. for a further 24 hours.A colorless, clear, low-viscosity liquid was obtained with a content (GC-TCD) of silane monomer of 14 area % (FIG. 4). |