CN113563589B - Application of rhodium catalyst in organic silicon addition reaction - Google Patents
Application of rhodium catalyst in organic silicon addition reaction Download PDFInfo
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- CN113563589B CN113563589B CN202110944283.5A CN202110944283A CN113563589B CN 113563589 B CN113563589 B CN 113563589B CN 202110944283 A CN202110944283 A CN 202110944283A CN 113563589 B CN113563589 B CN 113563589B
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- catalyst
- rhodium
- addition reaction
- polyether
- silicone oil
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- 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
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
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- 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
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
- B01J31/30—Halides
Abstract
An application of rhodium catalyst in organosilicon addition reaction, the application process of the catalyst is as follows: (1) Dissolving rhodium chloride (triphenylphosphine) with an organic solvent to obtain a catalyst solution for standby; (2) And uniformly mixing hydrogen-containing silicone oil and unsaturated polyether, heating to 40-50 ℃, adding the catalyst solution, continuously heating to 100-110 ℃, and reacting for 2 hours to obtain polyether modified silicone oil. The catalyst has better reaction activity than a platinum catalyst, can completely replace (or partially replace) the platinum catalyst in the hydrosilylation reaction, is relatively cheap compared with the platinum catalyst, and can properly reduce the production cost.
Description
Technical Field
The invention belongs to the technical field of organosilicon fine chemistry, and particularly relates to application of a rhodium catalyst in an organosilicon addition reaction.
Background
The production process of the organosilicon polyether silicone oil is often accompanied by the execution of organosilicon hydrogen addition reaction, and the catalyst commonly used in the general reaction is a platinum-series catalyst such as hexa-hydrated chloroplatinic acid, a zero-valence platinum ligand complex and the like, so that the cost of the platinum catalyst is low, and the production cost is increased.
Therefore, how to provide an organosilicon addition reaction catalyst with high catalytic efficiency and low cost is a problem to be solved by the research and development technicians in the field.
Disclosure of Invention
In view of the above, the invention provides an application of rhodium catalyst in organosilicon addition reaction, the catalyst has better reactivity than platinum catalyst, and can completely replace (or partially replace) platinum catalyst in hydrosilylation reaction, in addition, the catalyst is relatively cheap than platinum catalyst, and the production cost can be properly reduced.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the application of a rhodium catalyst in an organosilicon addition reaction is provided, wherein the rhodium catalyst is tris (triphenylphosphine) rhodium chloride.
In the invention, in the organosilicon addition reaction, the equivalent doses of the Wilkinson (triphenylphosphine) rhodium chloride type rhodium catalyst and the platinum catalyst are used for catalyzing the hydrosilylation reaction under the same reaction conditions, and the rhodium catalyst shows higher reaction activity than the platinum catalyst, so that the Wilkinson catalyst can be used for replacing the traditional platinum catalyst in actual production, and meanwhile, the production cost can be reduced.
Preferably, the concentration of the rhodium-based catalyst is 3ppm.
At an addition level of 3ppm, the rhodium-based catalyst showed higher reactivity than the platinum-based catalyst.
Preferably, the organosilicon addition reaction refers to the addition reaction process of polyether modified silicone oil.
Preferably, the preparation process of the polyether modified silicone oil comprises the following steps:
(1) Dissolving rhodium chloride (triphenylphosphine) with an organic solvent to obtain a catalyst solution for standby;
(2) And uniformly mixing hydrogen-containing silicone oil and unsaturated polyether, heating to 40-50 ℃, adding the catalyst solution, continuously heating to 100-110 ℃, and reacting for 2 hours to obtain polyether modified silicone oil.
In a common platinum catalytic system, the reaction temperature is at least 120 ℃ and above, and the rhodium catalyst is adopted in the invention, so that the reaction temperature is reduced, and the rhodium catalyst has higher reaction activity than the platinum catalyst.
Preferably, the organic solvent in step (1) is tetrahydrofuran and/or toluene.
The solvent can be tetrahydrofuran, toluene or tetrahydrofuran and toluene which are mixed in any proportion, and the solvent can fully dissolve the rhodium catalyst, and the rhodium catalyst is added into a reaction kettle for rapid dispersion, so that the reaction rate is improved.
Preferably, the mass percentage of the tris (triphenylphosphine) rhodium chloride to the organic solvent in the step (1) is 1-10% to 90-99%.
Preferably, in step (2), the hydrogen-containing silicone oil and the unsaturated polyether are mixed in a molar ratio of hydrogen to unsaturated bonds of 1:1.2 to 1.4.
The invention adopts the proportion to thoroughly react the hydrogen-containing silicone oil, and the unreacted Si-H bond is not remained, thereby being beneficial to the later storage.
Preferably, the hydrogen content of the hydrogen-containing silicone oil in step (2) is 0.1 to 0.2mol/100g.
After the hydrogen content is adopted, the invention can ensure that the reaction condition is mild, and the crosslinking phenomenon can be generated when the reaction is severely exothermic if the hydrogen content is too high.
Preferably, the unsaturated polyether in step (2) is any one of allyl alcohol polyether, methyl end capped allyl polyether, and alkynol polyether.
The polyether adopted by the invention contains unsaturated bonds, and can be subjected to addition reaction with Si-H.
Compared with the prior art, the invention has the following beneficial effects: the invention provides an application of rhodium catalyst in organic silicon addition reaction, the catalyst has better reaction activity than platinum catalyst, and can completely replace (or partially replace) platinum catalyst in the silicon hydrogen addition reaction, in addition, the catalyst is relatively cheap than platinum catalyst, and the production cost can be properly reduced.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The application of rhodium catalyst in organosilicon addition reaction includes the following steps:
(1) 1g of rhodium tri (triphenylphosphine) chloride is stirred at normal temperature for 10min to be dissolved by using 99g of tetrahydrofuran, so as to obtain a catalyst solution for standby;
(2) Uniformly mixing hydrogen-containing silicone oil and allyl alcohol polyether (unsaturated double bond 0.97 mmol/g), heating to 40 ℃, adding the catalyst solution, continuously heating to 100 ℃, and reacting for 2 hours to obtain polyether modified silicone oil; wherein the hydrogen content of the hydrogen-containing silicone oil is 0.1mol/100g, the hydrogen-containing silicone oil and the allyl alcohol polyether are mixed according to the mol ratio of hydrogen to unsaturated bonds of 1:1.2, and the concentration of the tris (triphenylphosphine) rhodium chloride is 3ppm.
Example 2
The application of rhodium catalyst in organosilicon addition reaction includes the following steps:
(3) 10g of rhodium tri (triphenylphosphine) chloride is stirred at normal temperature for 15min to be dissolved by using 90g of toluene, so as to obtain a catalyst solution for standby;
(4) Uniformly mixing hydrogen-containing silicone oil and alkynol polyether (unsaturated double bond 0.97 mmol/g), heating to 40 ℃, adding the catalyst solution, continuously heating to 100 ℃, and reacting for 2 hours to obtain polyether modified silicone oil; wherein the hydrogen content of the hydrogen-containing silicone oil is 0.1mol/100g, the hydrogen-containing silicone oil and the alkynol polyether are mixed according to the mol ratio of hydrogen to unsaturated bonds of 1:1.4, and the concentration of the tris (triphenylphosphine) rhodium chloride is 3ppm.
Examples 3 to 5
Wherein the concentration of rhodium chloride tris (triphenylphosphine) in examples 3 to 5 was 1ppm, 5ppm and 7ppm in this order.
Comparative examples 1 to 4
In the step (1), 1g of chloroplatinic acid hexahydrate was dissolved by ultrasonic with 99g of isopropyl alcohol, and the concentrations of the solution were 1ppm, 3ppm, 5ppm and 7ppm in this order, and the other steps were exactly the same as in example 1.
The results of the final products of examples 1, 3-5 and comparative examples 1-4 are shown in tables 1 and 2,
TABLE 1 results for the final products of examples 1, 3-5
TABLE 1 results for comparative examples 1-4 end products
As can be seen from tables 1 and 2, the rhodium-based catalyst exhibits higher reactivity than the platinum-based catalyst at the addition amount of 3ppm, compared with the hydrosilylation reaction catalyzed by the wilkinson-type rhodium-based catalyst and the platinum-based catalyst at the same reaction conditions in the production of polyether silicone oil, indicating that the wilkinson-based catalyst can be used instead of the conventional platinum-based catalyst in actual production, and that the production cost can be reduced appropriately.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (6)
1. The application of the rhodium catalyst in the organic silicon addition reaction is characterized in that the rhodium catalyst is tris (triphenylphosphine) rhodium chloride, the concentration of the rhodium catalyst is 3ppm, and the organic silicon addition reaction refers to the addition reaction process of polyether modified silicone oil;
the preparation process of the polyether modified silicone oil comprises the following steps:
(1) Dissolving rhodium chloride (triphenylphosphine) with an organic solvent to obtain a catalyst solution for standby;
(2) And uniformly mixing hydrogen-containing silicone oil and unsaturated polyether, heating to 40-50 ℃, adding the catalyst solution, continuously heating to 100-110 ℃, and reacting for 2 hours to obtain polyether modified silicone oil.
2. The use of a rhodium-based catalyst according to claim 1 in a silicone addition reaction, wherein the organic solvent in step (1) is tetrahydrofuran and/or toluene.
3. The use of a rhodium catalyst according to claim 1 in an organosilicon addition reaction, wherein the mass percentage of the tris (triphenylphosphine) rhodium chloride to the organic solvent in step (1) is 1-10% to 90-99%.
4. The use of a rhodium catalyst according to claim 1 in a silicone addition reaction, wherein in step (2) the hydrogen-containing silicone oil and the unsaturated polyether are mixed in a molar ratio of hydrogen to unsaturated bonds of 1:1.2 to 1.4.
5. The use of a rhodium-based catalyst according to claim 1 in a silicone addition reaction, wherein the hydrogen content of the hydrogen-containing silicone oil in step (2) is 0.1 to 0.2mol/100g.
6. The use of a rhodium-based catalyst according to claim 1 in a silicone addition reaction, wherein the unsaturated polyether in step (2) is any one of allyl alcohol polyether, methyl-terminated allyl polyether, and alkynol polyether.
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| US5484950A (en) * | 1992-12-21 | 1996-01-16 | Polyset Company, Inc. | Process for selective monoaddition to silanes containing two silicon-hydrogen bonds and products thereof |
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| CN103288863B (en) * | 2013-04-07 | 2015-07-22 | 杭州师范大学 | Method for hydrosilylation |
| CN104907096B (en) * | 2015-04-21 | 2017-05-31 | 广州天赐高新材料股份有限公司 | A kind of MOFs loaded catalysts and preparation method thereof and the application in hydrosilylation of olefins |
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