A method for catalyzing hydrosilylation reaction of ruthenium dichloride dimer of p-cymene

Abstract

The present invention relates to a method for catalyzing hydrosilylation reaction of p-cymene ruthenium dichloride dimer, comprising the following steps: using p-cymene ruthenium dichloride dimer as a catalyst, carrying out hydrosilylation reaction of hydrogen-containing siloxane and unsaturated hydrocarbon to obtain an alpha addition product. The present invention can realize catalysis of multiple hydrosilylation reactions by one catalyst, and the catalyst has very good universality; compared with traditional platinum catalysts, ruthenium catalysts have the advantages of low cost, and the catalytic reaction has fewer side reactions, high yield, short reaction time, high safety, and is suitable for industrial production.

Description

Technical Field

[0001] The invention relates to the technical field of organic chemistry, and in particular to a method for catalyzing hydrosilylation reaction of p-cymene ruthenium dichloride dimer. Background Art

[0002] Introducing special structures into silicone molecules can give silicone products new properties. For example, after introducing long-chain alkyl groups, they can be used as silicone coupling agents, glass anti-fogging agents, cultural relic protection agents, fabric finishing agents, etc. The introduction of long-chain polyether groups can improve the surface tension of polysiloxanes, making them useful as fabric treatment agents and silicone penetrants. The introduction of olefins can be used as special surfactants.

[0003] The hydrosilylation reaction is one of the main means to introduce special structures into organosilicon molecules. Among them, the hydrosilylation reaction with transition metal compounds as catalysts occupies an important position in synthetic chemistry and is the main way to synthesize organosilicon coupling agents, functional organosilicon compounds and polymers.

[0004] Chinese patent CN101787045B discloses a method for ruthenium compound catalyzed hydrosilylation reaction, which specifically discloses that α-olefin, alkoxyhydrosilane and catalyst ruthenium compound are reacted in a reaction system at 0-55° C. Although this method has the characteristics of low reaction temperature, few by-products and high yield, the reaction time is too long (30-433h), which is not conducive to improving production efficiency. Summary of the invention

[0005] In view of this, it is necessary to provide a method for catalyzing the hydrosilylation reaction of ruthenium dichloride dimer of p-cymene to solve the technical problems of long hydrosilylation reaction time and excessive self-polymerization of olefins in the prior art.

[0006] The present invention provides a method for catalyzing the hydrosilylation reaction of p-cymene ruthenium dichloride dimer, comprising the following steps:

[0007] Using p-cymene dichloride ruthenium dimer as catalyst, hydrogen-containing siloxane and unsaturated hydrocarbon undergo hydrosilylation reaction to obtain alpha addition product.

[0008] Compared with the prior art, the present invention has the following beneficial effects:

[0009] The present invention can realize a catalyst catalyzing multiple hydrosilylation reactions, and the catalyst has very good universality; compared with traditional platinum catalysts, ruthenium catalysts have the advantage of low cost, and the catalytic reaction has fewer side reactions, high yield, short reaction time, high safety, and is suitable for industrial production. BRIEF DESCRIPTION OF THE DRAWINGS

[0010] Figure 1 is the hydrosilylation product obtained in Example 1 of the present invention1 H NMR spectra. DETAILED DESCRIPTION

[0011] In order to make the purpose, technical solution and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention.

[0012] The present invention provides a method for catalyzing the hydrosilylation reaction of p-cymene ruthenium dichloride dimer, comprising the following steps:

[0013] Using p-cymene dichloride ruthenium dimer as a catalyst, hydrogen-containing siloxane and unsaturated hydrocarbon undergo alpha addition reaction to obtain a hydrosilylation product.

[0014] In the present invention, all hydrosilylation reactions catalyzed by p-cymene dichloride ruthenium dimer are solvent-free reactions, simple to operate, and convenient to separate products. The method of the present invention has the advantages of high raw material conversion rate, short reaction time, small amount of catalyst, wide range of catalyst application, good product quality, and can realize industrial production.

[0015] In the present invention, the unsaturated hydrocarbons include α-olefins and alkynes.

[0016] Taking α-olefin as unsaturated hydrocarbon, the reaction formula of hydrosilylation is:

[0017]

[0018] Taking alkynes as unsaturated hydrocarbons, the reaction formula for hydrosilylation is:

[0019]

[0020] In some specific embodiments of the present invention, the α-olefin is at least one of an alkyl terminal olefin, an aromatic vinyl, and a polyethylene glycol monoallyl ether; and the alkyne is an intermediate alkyne with symmetry at both ends. 1 ~C 20 The olefins are specifically 1-dodecene, 1-octadecene, etc.; the aromatic vinyl can be styrene, etc.; the intermediate alkynes symmetrical at both ends are butynediol diethoxy ether, butynediol ethoxy ether, butynediol diisopropoxy ether, etc.

[0021] In the present invention, the hydrogen-containing siloxane is at least one of triethoxysilane, heptamethyltrisiloxane and hydrogen-containing silicone oil.

[0022] In the present invention, the reaction temperature is 20-130° C. according to the catalytic reaction of different substrates. The hydrosilylation reaction temperature of polyethylene glycol monoallyl ether and hydrogen-containing siloxane is relatively low, at 20-90° C., preferably 80-90° C., and impurities will be generated when the temperature is higher than 90° C.; the addition reaction temperature of alkynes, aromatic vinyls and alkyl terminal olefins and hydrogen-containing siloxane is slightly higher, at 100-130° C., preferably 110° C.

[0023] In the present invention, the reaction time is 1-8 hours according to the catalytic reaction of different substrates. The hydrosilylation reaction time of aromatic vinyl and alkyl terminal olefin is relatively long, requiring 5-8 hours to complete, preferably 6 hours; the hydrosilylation reaction time of alkyne and polyethylene glycol monoallyl ether is relatively short, completing within 1-6 hours, preferably 3-4 hours.

[0024] In the present invention, the catalyst can be directly added to the reaction system, or it can be pre-dissolved in an organic solvent to form a catalyst solution, and then the catalyst solution is added to the reaction system to further improve the dispersion effect of the catalyst in the reaction system. In some preferred embodiments of the present invention, the catalyst is pre-dissolved in methanol, and then the methanol solution of the catalyst is added to the reaction system. Furthermore, the mass fraction of the methanol solution of the catalyst is 0.1%-2%.

[0025] In the present invention, the amount of catalyst used is 5-200ppm of the total mass of the feed according to the catalytic reaction of different substrates. The amount of catalyst used for the hydrosilylation reaction of aryl vinyl and alkyl terminal olefins is the smallest, between 5-30ppm, preferably 20ppm; the amount of catalyst used for the hydrosilylation reaction of polyethylene glycol monoallyl ether is 25-50ppm, preferably 30ppm; the amount of catalyst required for the hydrosilylation reaction of alkynes is 100-200ppm, preferably 100ppm.

[0026] In the present invention, the equivalent ratio of the unsaturated hydrocarbon to the hydrogen-containing siloxane is 1 to 1.3:1, preferably 1 to 1.2:1.

[0027] In the present invention, the reaction atmosphere is argon.

[0028] In the present invention, p-cymene dichloride ruthenium dimer is obtained by the following process:

[0029] Using oxygen-free Schlenk vacuum technology, under the protection of high-purity argon, and using alcohol solvents, hydrated ruthenium trichloride and α-phellandrene were heated under reflux to synthesize p-cymene dichlororuthenium dimer ([Ru(p-cymene)Cl 2 ] 2) compound. In the process, the molar ratio of hydrated ruthenium chloride to α-phellandrene is 1:(4-6), the dosage ratio of hydrated ruthenium chloride to alcohol solvent is 1g:(20-40ml); the alcohol solvent is at least one of ethylene glycol, ethanol and isopropanol; the reflux reaction time is 2-4h.

[0030] Specifically, the reaction formula for synthesizing p-cymene dichloride ruthenium dimer is as follows:

[0031]

[0032] To avoid redundant description, in the following embodiments of the present invention, the preparation process of p-cymene ruthenium dichloride dimer is as follows:

[0033] 10 g of ruthenium trichloride trihydrate was added to a Schlenk bottle, and the air in the bottle was replaced by a double-row tube; then 300 mL of anhydrous ethanol and 33 g of phellandrene were introduced into the bottle; the reaction was refluxed for 3 hours under an argon atmosphere, part of the solvent was removed under reduced pressure, and then the temperature was lowered to precipitate a reddish-brown solid, which was p-cymene ruthenium dichloride, with a yield of 95%.

[0034] Example 1

[0035] Add 55.6 g of low hydrogen silicone oil (n(Si-H) = 100 mmol, hydrogen content 0.18%, viscosity 130 mm 2 / s), 151mg of p-cymene ruthenium dichloride catalyst (20ppm, methanol as solvent, mass fraction of 1%), heated to 110℃ under Ar atmosphere and stirred for 15min, then slowly added 20.2g of 1-dodecene (n(C=C)=120mmol), and kept warm for 6h; after the reaction, the product cooled to room temperature and filtered to obtain a colorless transparent oily liquid. TLC showed that the low hydrogen silicone oil raw material disappeared. The conversion rate of low hydrogen silicone oil was 98% calculated by the integral area of ​​characteristic peaks of hydrogen nuclear magnetic resonance spectrum, and the α addition product was selectively obtained with a yield of 83%. The product nuclear magnetic resonance data are as follows: 1 H NMR (400 MHz, CDCl 3 )δ1.28(m,20H),0.88(m,3H),0.56–0.44(m,2H),0.17–-0.12(m,42H).

[0036] The obtained product was used as a demoulding agent for polyurethane foam materials, and the reaction was carried out at 60°C. The demoulding force was 12N / 100cm. 17 H 35 ) When used as a release agent, the release force is 35N / 100cm 2 ; If no release agent is used, the demoulding force is 40N / 100cm 2It shows a good demoulding effect. When the polyurethane reaction is molded, 1% (mass fraction) of the product is mixed in as a demoulding agent, and the molding can be continued for 25 times without any product sticking to the mold.

[0037] Example 2

[0038] Add 44.5g (0.2mol) of heptamethyltrisiloxane and 44.9g (0.22mol) of polyethylene glycol monoallyl ether (chain segment 3) to the reaction bottle, add 268mg of p-cymene dichloride ruthenium catalyst (30ppm, methanol as solvent, mass fraction 1%) under Ar atmosphere, heat to 90℃ and stir to react for 3.5h; after the reaction, the product cools to room temperature and is filtered to obtain a colorless transparent oily liquid. TLC shows that the low hydrogen silicone oil raw material disappears, and the characteristic peak of silicon hydrogen disappears completely through the integral calculation of the characteristic peak area of ​​the nuclear magnetic resonance hydrogen spectrum, and the α addition product is selectively obtained with a yield of 88%. The product nuclear magnetic resonance data are as follows: 1 H NMR (600 MHz, CDCl 3 )δ3.62(m,12H),3.37(m,2H),3.34(s,3H),1.61–1.51(m,2H),0.43–0.35(m,2H),0.00(m,21H).

[0039] The product was used as a surfactant for application research. 10 μL of 0.1% aqueous solution and pure water were respectively taken with a microsyringe and dropped onto a PE plastic film. The liquid was allowed to air dry naturally. After the liquid was air dried, the plastic paper with traces was cut off and placed on a coordinate paper with squares. The spread area was calculated by counting the number of covered squares on the coordinate paper. The operation was repeated five times to obtain the average value. The results showed that the spread area of ​​the 0.1% aqueous solution was 81.2 mm 2 , while the spreading area of ​​pure water is 13.4mm 2 The spreading area is 6 times that of pure water, showing excellent surface activity.

[0040] Example 3

[0041] Add 44.5g (0.2mol) of heptamethyltrisiloxane and 40.0g (0.23mol) of butynediol diethoxy ether (2 times EO) to the reaction bottle, and add 845mg of p-cymene ruthenium dichloride catalyst (100ppm, methanol as solvent, mass fraction of 1%) under Ar atmosphere. Keep the reaction at 110℃ for 3 hours, and monitor the disappearance of heptamethyltrisiloxane by TLC. Stop the reaction, degas under reduced pressure for 10min, and cool the reaction solution to room temperature to obtain 77.3g of yellow transparent liquid with a yield of 97%. The product NMR data are as follows: 1 HNMR (600MHz, CDCl 3)δ6.08(m,1H),4.23(m,4H),3.93-3.87(m,4H),3.65-3.55(m,4H),3.33-3.29(m,2H),0.00(m,21H).

[0042] The specific reaction formula is as follows:

[0043]

[0044] The product was used as a surfactant for application research. 10 μL of 0.1% aqueous solution and pure water were respectively taken with a microsyringe and dropped onto a PE plastic film. The liquid was allowed to air dry naturally. After the liquid was air dried, the plastic paper with traces was cut off and placed in a coordinate paper with squares. The spread area was calculated by counting the number of covered squares on the coordinate paper. The operation was repeated five times to obtain the average value. The results showed that the spread area of ​​the 0.1% aqueous solution was 77.5 mm 2 , while the spreading area of ​​pure water is 13.4mm 2 The spreading area is 5.7 times that of pure water, showing excellent surface activity.

[0045] The above description is only a preferred specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any changes or substitutions that can be easily conceived by any technician familiar with the technical field within the technical scope disclosed by the present invention should be covered within the protection scope of the present invention.

Claims

1. A method for catalyzing the hydrosilylation reaction of ruthenium dichloride dimer of p-cymene, It is characterized in that The following steps are involved: Using p-cymene dichloride ruthenium dimer as a catalyst, a hydrogen-containing siloxane and an unsaturated hydrocarbon are subjected to a hydrosilylation reaction to obtain an addition product; wherein, The hydrogen-containing siloxane is at least one of heptamethyltrisiloxane and hydrogen-containing silicone oil; The temperature of the hydrosilylation reaction is 20-130° C., the reaction time is 1-8 hours, and the amount of the catalyst is 5-200 ppm of the total mass of the feed; The unsaturated hydrocarbon is an α-olefin, and the α-olefin is at least one of 1-dodecene, 1-octadecene, arylethylene, and polyethylene glycol monoallyl ether; the reaction formula of hydrosilylation is: ； Or, the unsaturated hydrocarbon is an alkyne, and the alkyne is an intermediate alkyne with symmetry at both ends; the intermediate alkyne with symmetry at both ends is at least one of butynediol diethoxy ether and butynediol diisopropoxy ether; the reaction formula of hydrosilylation is: 。 2. The method for catalyzing the hydrosilylation reaction of p-cymene ruthenium dichloride dimer according to claim 1, It is characterized in that The unsaturated hydrocarbon is 1-dodecene, 1-octadecene or arylethylene, the temperature of the hydrosilylation reaction is 100-130° C., the reaction time is 5-8 hours, and the amount of the catalyst is 5-30 ppm of the total mass of the feed; Or, the unsaturated hydrocarbon is polyethylene glycol monoallyl ether, the temperature of the hydrosilylation reaction is 20-90° C., the reaction time is 1-6 hours, and the amount of the catalyst is 25-50 ppm of the total mass of the feed; Alternatively, the unsaturated hydrocarbon is alkyne, the temperature of the hydrosilylation reaction is 100-130° C., the reaction time is 1-6 hours, and the amount of the catalyst used is 100-200 ppm of the total mass of the feed.

3. The method for catalyzing the hydrosilylation reaction of p-cymene ruthenium dichloride dimer according to claim 1, It is characterized in that The catalyst is added in the following manner: the catalyst is preliminarily dissolved in methanol, and then the methanol solution of the catalyst is added into the reaction system.

4. The method for catalyzing the hydrosilylation reaction of p-cymene ruthenium dichloride dimer according to claim 1, It is characterized in that The equivalent ratio of unsaturated hydrocarbon to hydrogen-containing siloxane is 1~1.3:

1.

5. The method for catalyzing the hydrosilylation reaction of p-cymene ruthenium dichloride dimer according to claim 1, It is characterized in that The p-cymene dichlororuthenium dimer is obtained by the following process: using oxygen-free Schlenk vacuum technology, under the protection of high-purity argon, using alcohol solvents, heating hydrated ruthenium trichloride and α-phellandrene to reflux and react to synthesize the p-cymene dichlororuthenium dimer compound.

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