CN114317065B - Ferrocene group-based viscosity-controllable fluorosilicone oil and production method thereof - Google Patents
Ferrocene group-based viscosity-controllable fluorosilicone oil and production method thereof Download PDFInfo
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Abstract
The invention discloses ferrocene group-based viscosity-controllable fluorosilicone oil and a production method thereof. The viscosity-controllable fluorosilicone oil comprises modified silicon dioxide and silicone oil, wherein the modified silicon dioxide comprises ferrocene groups and perfluorooctanoic acid groups, and the silicone oil comprises dimethyl siloxane monomers. The production method is simple and easy to implement, low in cost and controllable in reaction conditions, and greatly improves the production safety. In addition, the lubricating performance of the fluorosilicone oil produced by the method is remarkably improved, and the viscosity can be adjusted according to needs. Therefore, the preparation method has good application prospect in producing the fluorosilicone oil which can be applied to different scenes.
Description
Technical Field
The invention relates to the technical field of chemical industry, in particular to ferrocene group-based viscosity-adjustable fluorosilicone oil and a production method thereof.
Background
The fluorosilicone oil combines the advantages of excellent thermal stability and chemical stability of the organic silicon material, and the like, has continuously become an important subject in the field of functional material research, and is widely applied in the fields of aviation, new energy, artificial intelligence and the like. The fluorosilicone oil has excellent oil resistance, solvent resistance and chemical corrosion resistance, and can meet the lubricating requirements of equipment operation in severe environments such as high temperature, high humidity, low temperature and the like. Compared with the traditional mineral lubricating oil, the fluorosilicone oil has higher viscosity-temperature coefficient, can not rapidly reduce the viscosity along with the temperature rise, and has unique advantages in the fields of aeroengines and the like due to the excellent high-temperature resistance.
The most commonly used fluorosilicone oil is short-chain fluorine alkyl silicone oil which has excellent lubricating property, low raw material price and simple preparation process. But also has the defects of general anti-shearing performance, low oxidation resistance, difficult regulation and control of viscosity and the like. The lubricating property of the short-chain fluorine alkyl silicone oil is improved by adding a functional assistant and improving the molecular structure of the fluorine alkyl silicone oil, wherein the addition of the functional assistant is the most convenient and effective method for improving the comprehensive performance of the fluorine silicone oil.
For example, chinese patent application CN104610549A discloses a modified fluorine-containing silicone oil and a preparation method thereof. The method comprises the steps of taking methyl hydrogen-containing dichlorosilane as an initial raw material, taking chloroplatinic acid as a catalyst, and reacting the methyl hydrogen-containing dichlorosilane with octavinyl cage-type silsesquioxane (POSS) to synthesize a vinyl cage-type silsesquioxane methyl dichlorosilane monomer; then the vinyl cage-type silsesquioxane side group silicone oil is prepared by hydrolysis and co-balancing with dimethyldichlorosilane and trimethylchlorosilane; and finally, carrying out single electron transfer reaction (SET) on vinyl and perfluoroiodoalkane in the vinyl cage-type silsesquioxane structure on the side group to prepare the modified fluorine-containing silicone oil.
For another example, chinese patent application CN112979953A discloses a preparation method of a high purity hydroxyl-terminated fluorosilicone oil with controllable viscosity. The method comprises the following steps: organic amine is used as a catalyst, a polar solvent is used as an accelerant, water is used as an end capping agent, and the three materials and trifluoropropyl methyl cyclotrisiloxane (D3F) are subjected to polymerization reaction.
At present, the demand of developing new modification auxiliary agents and fluorosilicone oil still exists, the lubricating property of the fluorosilicone oil is further improved, and the requirement of easy adjustment of the viscosity of the fluorosilicone oil on different occasions or different stages in the occasions is met.
Disclosure of Invention
Aiming at the technical problems in the prior art, the inventor carries out intensive research, prepares a modified auxiliary agent based on ferrocene groups, and obtains fluorosilicone oil with remarkably improved lubricating property and controllable viscosity based on the auxiliary agent. Specifically, the present invention includes the following.
In a first aspect of the present invention, there is provided a ferrocene group-based viscosity-controllable fluorosilicone oil, comprising:
a modified silica comprising a ferrocenyl group and a perfluorooctanoic acid group; and
a silicone oil comprising a dimethylsiloxane monomer.
The ferrocenyl based viscosity-controllable fluorosilicone oil according to the present invention preferably further comprises tetrafluoroethylene or a derivative thereof, wherein the tetrafluoroethylene or the derivative thereof comprises: polytetrafluoroethylene PTFE, fluorinated ethylene propylene FEP, meltable polytetrafluoroethylene PFA, F-40 resin ETFE, or combinations thereof.
The ferrocene group-based viscosity-controllable fluorosilicone oil preferably further comprises a reducing agent and/or an oxidizing agent, wherein the reducing agent comprises: sodium borohydride, hydrazine hydrate, hydroxylamine hydrochloride, or ascorbic acid, or a combination thereof;
the oxidizing agent comprises: ferric chloride, ferric sulfate, ferric stearate, or combinations thereof.
According to the ferrocene group-based viscosity-controllable fluorosilicone oil, the weight ratio of the modified silicon dioxide to the silicone oil is preferably 1.
According to the ferrocene-based viscosity-controllable fluorosilicone oil, preferably, the molar ratio of the added oxidant to the ferrocene groups is 1-2.
According to the ferrocene-based viscosity-controllable fluorosilicone oil, preferably, the molar ratio of the added reducing agent to the ferrocene group is 0.1-1.
In a second aspect of the present invention, there is provided a method for producing ferrocene group-based viscosity-controllable fluorosilicone oil, comprising:
(1) Dissolving ferrocenecarboxylic acid and perfluorooctanoic acid in a chlorine-containing solvent, heating and refluxing, adding fumed silica, reacting in an argon atmosphere, and drying in vacuum to obtain modified silica;
(2) And stirring the modified silicon dioxide, the tetrafluoroethylene or the derivative thereof and the silicone oil to react to obtain the fluorosilicone oil with adjustable and controllable viscosity.
The production method of the ferrocene-based viscosity-controllable fluorosilicone oil preferably further comprises the following steps:
(3) Adding the oxidizing agent, thereby reducing the viscosity of the fluorosilicone oil; and/or
(4) Adding the reducing agent, thereby increasing the viscosity of the fluorosilicone oil.
According to the production method of the ferrocene-based viscosity-controllable fluorosilicone oil, the weight ratio of ferrocenecarboxylic acid to perfluorooctanoic acid is preferably 1.
According to the production method of the ferrocene-based viscosity-controllable fluorosilicone oil, preferably, the weight ratio of the ferrocenecarboxylic acid to the fumed silica is 1:5-30.
According to the production method of the ferrocenyl-based viscosity-controllable fluorosilicone oil, preferably, the chlorine-containing solvent comprises dichloromethane and oxalyl chloride.
The production method is simple and easy to implement, low in cost and controllable in reaction conditions, and greatly improves the production safety. In addition, the lubricating property of the fluorosilicone oil produced by the method is obviously improved, and the viscosity can be adjusted according to needs. Therefore, the preparation method has good application prospect in producing the fluorosilicone oil which can be applied to different scenes.
Drawings
FIG. 1 shows ferrocene perfluorooctanoic acid-modified Silica (SiO) 2 -F-Fc).
FIG. 2 shows ferrocene perfluorooctanoic acid modified Silica (SiO) 2 -F-Fc).
FIG. 3 shows ferrocene perfluorooctanoic acid modified Silica (SiO) 2 -F-Fc).
FIG. 4 shows the viscosity change of the fluorosilicone oil system when the ferrocenyl moieties are in the oxidized and reduced states, respectively.
FIG. 5 shows ferrocene perfluorooctanoic acid modified Silica (SiO) 2 -F-Fc) of a redox transition structure.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that the upper and lower limits of the range, and each intervening value therebetween, is specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in that stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control. Unless otherwise indicated, "%" is percent by weight.
In the present invention, the viscosity-controllable type means that the viscosity of the fluorosilicone oil can be increased (increased) or decreased (decreased) as needed. The details are as follows.
Ferrocene group-based viscosity-controllable fluorosilicone oil
In the invention, the viscosity-controllable fluorosilicone oil comprises modified silicon dioxide and silicone oil, wherein the silicone oil is preferably methyl silicone oil or a derivative thereof, and is also preferably dimethyl silicone oil. Dimethicone as used herein refers to a homopolymer containing a dimethicone monomer and having the formula: [ (CH) 3 ) 2 SiO] n . The dimethyl silicone oil used in the invention contains inorganic siloxane framework and is added in each silicon atomThe molecule contains two methyl groups.
In the present invention, derivatives of methylsilicone oil include, but are not limited to: hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), dodecamethylcyclohexasiloxane (D6), or combinations thereof. The methylsilicone oil or its derivatives can be prepared by known methods or commercially available. Examples of dimethicone products include, but are not limited to, dimethicone having a model number PMX200 with a viscosity number of 100 to 10000cst.
In the invention, the modified silicon dioxide comprises a ferrocene group and a perfluoro caprylic acid group, and is prepared by the following steps: dissolving ferrocenecarboxylic acid and perfluorooctanoic acid in a chlorine-containing solvent, heating and refluxing, adding fumed silica, reacting under argon, and drying in vacuum to obtain modified silica. Preferably, the chlorine-containing solvent comprises 20-70ml of dichloromethane and 0.5-5ml of oxalyl chloride. Also preferably, the chlorine-containing solvent comprises 30-60ml of dichloromethane and 1-3ml of oxalyl chloride. The temperature of heating reflux is 35-45 deg.C, the reflux time is 2-8 hr, preferably heating to 38-42 deg.C, and refluxing for 3-8 hr.
In the present invention, the weight ratio of ferrocenecarboxylic acid to perfluorooctanoic acid is 1.
Adding the product obtained after heating and refluxing into dichloromethane containing fumed silica to react for 2-24 hours to obtain the modified silica. Preferably, the concentration of fumed silica in methylene chloride is from 10 to 200mg/ml, more preferably from 12 to 100mg/ml, even more preferably from 15 to 50mg/ml.
The structure of the modified silica may be confirmed and further characterized using methods known in the art, for example, infrared spectroscopy and thermogravimetric analysis may be used for confirmation and characterization of the structure.
In the present invention, the weight ratio of the modified silica to the silicone oil is 1.
The viscosity-controllable fluorosilicone oil of the present invention further comprises tetrafluoroethylene or a derivative thereof, wherein the tetrafluoroethylene or the derivative thereof comprises: polytetrafluoroethylene PTFE, fluorinated ethylene propylene FEP, meltable polytetrafluoroethylene PFA, F-40 resin ETFE, or combinations thereof, preferably polytetrafluoroethylene PTFE.
In the present invention, the weight ratio of the modified silica to the polytetrafluoroethylene is 1.
Production method of viscosity-adjustable fluorosilicone oil
In the production or preparation method of the invention, the modified silicon dioxide, the tetrafluoroethylene or the derivative thereof and the silicone oil are stirred to react to obtain the ferrocene group-based fluorosilicone oil with controllable viscosity, and the preparation method of the modified silicon dioxide is described in the above part and is not described again. The stirring parameters are not particularly limited, and are preferably 500 to 5000 rpm.
The method further comprises the step of adding an oxidizing agent and/or adding a reducing agent, so that the viscosity of the fluorosilicone oil is increased and/or decreased. Wherein the reducing agent comprises sodium borohydride, hydrazine hydrate, hydroxylamine hydrochloride or ascorbic acid, preferably ascorbic acid. The oxidizing agent comprises ferric chloride, ferric sulfate or ferric stearate, preferably ferric chloride.
In the present invention, the molar ratio of the oxidant to the ferrocenyl moiety added is 1. The molar ratio of the reducing agent to the ferrocenyl moiety added is 0.1 to 1, preferably 0.2 to 0.7.
In the ferrocene-based viscosity-controllable fluorosilicone oil, the ferrocenyl has two valence states, namely a reduction state and an oxidation state, and the ferrocenyl in the system can be reversibly converted in the reduction state and the oxidation state by adding an oxidant or a reducing agent. When the ferrocenyl is in a reduction state and an oxidation state respectively, the hydrophilicity and the hydrophobicity of the ferrocenyl are different, so that the viscosity of the whole system is influenced. Specifically, when the ferrocenyl is in a reduction state, the system is hydrophobic, and the viscosity is relatively high; when the ferrocenyl is in an oxidation state, the system becomes hydrophilic, the viscosity is reduced, and then the reversible conversion of the viscosity in the fluorosilicone oil to the redox agent is realized, namely the viscosity in the fluorosilicone oil system is adjustable.
It will be understood by those skilled in the art that other steps or operations, such as further optimization and/or improvement of the method of the present invention, can be included before, after, or between the steps (1) - (4) as long as the objective of the present invention is achieved. In a specific embodiment, the method further comprises the step of repeatedly adding the oxidizing agent and the reducing agent in sequence so as to enable the ferrocene perfluorooctanoic acid to modify the redox structure of the silica.
Examples
This example is a process for preparing ferrocene-based viscosity-controllable fluorosilicone oil.
1. Reagent
Hydrophilic fumed silica (Yingchuangdegussa) with primary particle average diameter of 7 nm and BET surface area of 380 +/-30 m 2 (iv) g. Perfluorooctanoic acid (PFOA, purity 96%), ferrocenecarboxylic acid (FcCOOH, purity 98%), oxalyl chloride (Cl (O) CC (O) Cl, purity 98%), iron trichloride (hexahydrate, purity 99%) were purchased from MACKLIN and used as received. Dow Corning PMX200 dimethyl silicone oil, viscosity 100-10000cst. Polytetrafluoroethylene fine powder of 3M company, usa, primary particle size: 120 nm, average particle size: 4 micron (DIN ISO 13321 test method), high purity (99.99%) methylene chloride, absolute ethanol, analytical grade, were purchased from Guangzhou chemical laboratories and used as received.
All experimental waters were Millipore ultrapure water.
2. Testing and characterization
Fourier transform Infrared Spectroscopy (FT-IR) was measured using a Fourier transform infrared spectrometer (ATR Total reflectance germanium crystals) of the Nicolet 6700 model of Thermo, USA.
The thermogravimetric curve (TGA) was measured using a TGA model 8000 thermogravimetric analyzer from Perkin Elmer, inc. (Perkinelmer) under a nitrogen atmosphere at a temperature rise rate of 10 degrees per minute.
The fluorosilicone oil viscosity was measured using a model NDJ-5S digital viscometer available from Shanghai, right instruments and technology Ltd.
3. Ferrocene perfluorooctanoic acid modified Silica (SiO) 2 -F-Fc) Synthesis
The synthetic route is shown in figure 1, 0.07-0.14 g of dry ferrocenecarboxylic acid (0.3-0.6 mmol), 0.20-0.50 g of perfluorooctanoic acid (0.48-1.2 mmol) and 30-60ml of anhydrous dichloromethane are weighed into a dry three-neck flask, the ferrocenecarboxylic acid is dissolved by stirring at room temperature for half an hour under the protection of argon, 1-3ml of oxalyl chloride (about 11.8-35.4 mmol) is rapidly added, and the mixture is heated and refluxed for 1-8 hours at 40 ℃.
The dichloromethane and excess oxalyl chloride were pumped out using a diaphragm pump, and 20 to 80 ml of dichloromethane were added to dissolve them, and then a reaction flask containing 0.5 to 2.0 g of hydrophilic fumed silica (vacuum dried at 80 ℃ for 12 hours) and 10 to 40 ml of dichloromethane was added, and the mixture was reacted at room temperature for 2 to 24 hours under magnetic stirring under argon atmosphere.
Stopping the reaction, performing suction filtration by using a 0.22 micron microporous filter membrane, washing twice with water and washing twice with absolute ethyl alcohol, and performing vacuum drying at 40-60 ℃ for 3-12 hours to obtain 1.20-2.0 g of ferrocene perfluorooctanoic acid modified silicon dioxide (SiO) 2 -F-Fc), yield about 65-85%.
4. Preparation of ferrocene group-based viscosity-adjustable fluorosilicone oil
1.0 to 4.0 grams of ferrocene perfluorooctanoic acid modified Silica (SiO) 2 -F-Fc), 10-80 g of polytetrafluoroethylene micro powder and 50-150 g of dimethyl silicone oil are added into a beaker and mechanically stirred (500-5000 r/min) for 10-100 minutes to obtain the ferrocene group-based fluorosilicone oil with adjustable and controllable viscosity. The viscosity of the fluorosilicone oil can be adjusted by mechanical stirring with an appropriate amount of added oxidizing agent such as ferric chloride or ferric sulfate or ferric stearate, or reducing agent ascorbic acid.
5. Results
5.1 Structural analysis of ferrocene perfluorooctanoic acid modified silica
FIG. 2 shows a synthesized functional additive (ferrocene perfluorooctanoic acid modified Silica (SiO) 2 F-Fc)) and unmodified silica, from which it can be seen that the auxiliary SiO is 2 F-Fc contained ferroceneformyl groups (wave number 1655,1475 cm) in addition to the characteristic infrared absorption peak of silica -1 ) Carbon-fluorine bond (wave number 1203 cm) -1 ) The infrared absorption peak proves that a certain amount of ferrocenyl and perfluorooctanoic acid organic molecular chains are successfully modified on the surface of the silicon dioxide.
FIG. 3 shows a synthetic functional additive (ferrocene perfluorooctanoic acid modified Silica (SiO) 2 F-Fc)) and unmodified silica, and the auxiliary SiO can be seen from the figure 2 The F-Fc has a weight loss of about 10% in the range of 200-500 ℃, which indirectly proves that a certain amount of ferrocenyl and perfluorooctanoic acid organic molecular chains are modified on the surface of the silicon dioxide.
5.2 Performance research of ferrocene group-based viscosity-controllable fluorosilicone oil
FIG. 4 is a graph showing the viscosity change of the fluorosilicone oil system when ferrocene groups are in an oxidized state and a reduced state, respectively. After adding iron chloride (oxidant, in order to oxidize the ferrocenyl group in the fluorosilicone oil to convert it into an oxidized state) in an equimolar amount to the ferrocenyl group contained in the system to the fluorosilicone oil (the ferrocenyl group in the system is in a reduced state), and mechanically stirring for 30 minutes, it was found that: the viscosity measured by the rotational viscosity meter is reduced from 12104 mPas to 7262 mPas, then ascorbic acid (reducing agent) with 0.5 time of mole amount of ferrocene group is further added (the ferrocene group in oxidation state in the silicon oxide fluoride oil is converted into reduction state), the mechanical stirring is carried out for 30 minutes, the viscosity of the silicon fluoride oil is increased to 11900 mPas again, and the further circulation can be carried out in turn. Ferrocene perfluorooctanoic acid modified Silica (SiO) 2 -F-Fc) is shown in FIG. 5.
While the present invention has been described with reference to exemplary embodiments, it is to be understood that the invention is not limited to the disclosed exemplary embodiments. Many modifications and variations may be made to the exemplary embodiments of the present description without departing from the scope or spirit of the present invention. The scope of the claims is to be accorded the broadest interpretation so as to encompass all modifications and equivalent structures and functions.
Claims (9)
1. A ferrocene group-based viscosity-controllable fluorosilicone oil is characterized by comprising:
modified silica comprising a ferrocenyl group and a perfluorooctanoic acid group; and
a silicone oil comprising a dimethylsiloxane monomer,
dissolving ferrocenecarboxylic acid and perfluorooctanoic acid in a chlorine-containing solvent, heating and refluxing, adding fumed silica, reacting in an argon atmosphere, and drying in vacuum to obtain modified silica;
further comprising a reducing agent and/or an oxidizing agent, wherein the reducing agent comprises: sodium borohydride, hydrazine hydrate, hydroxylamine hydrochloride, or ascorbic acid, or a combination thereof;
the oxidizing agent comprises: ferric chloride, ferric sulfate, or ferric stearate, or a combination thereof.
2. A ferrocenyl-based viscosity-modulatable fluorosilicone oil according to claim 1, further comprising a derivative of tetrafluoroethylene, wherein the derivative of tetrafluoroethylene comprises: polytetrafluoroethylene PTFE, fluorinated ethylene propylene FEP, meltable polytetrafluoroethylene PFA, or F-40 resin ETFE, or combinations thereof.
3. The ferrocenyl-group-based viscosity-controllable fluorosilicone oil as claimed in claim 1, wherein the weight ratio of the modified silica to the silicone oil is 1:10-200.
4. The ferrocenyl based viscosity-controllable fluorosilicone oil of claim 3, wherein a molar ratio of the oxidant to the ferrocenyl is 1:1-2.
5. The ferrocenyl-based viscosity-controllable fluorosilicone oil as claimed in claim 4, wherein a molar ratio of the reducing agent to the ferrocenyl moiety is 0.1-1:1.
6. A method for producing ferrocenyl based viscosity-controllable fluorosilicone oil according to any one of claims 1 to 5, comprising:
(1) Dissolving ferrocenecarboxylic acid and perfluorooctanoic acid in a chlorine-containing solvent, heating and refluxing, adding fumed silica, reacting in an argon atmosphere, and drying in vacuum to obtain modified silica;
(2) And stirring the modified silicon dioxide, the derivative of the tetrafluoroethylene and the silicone oil to react to obtain the fluorosilicone oil with adjustable and controllable viscosity.
7. A method for producing ferrocenyl-based viscosity-controllable fluorosilicone oil according to claim 6, further comprising:
(3) Adding an oxidant to reduce the viscosity of the fluorosilicone oil; and/or
(4) Adding a reducing agent, thereby increasing the viscosity of the fluorosilicone oil.
8. The method for producing ferrocenyl methyl methacrylate-based viscosity-controllable fluorosilicone oil as claimed in claim 7, wherein the weight ratio of ferrocenecarboxylic acid to perfluorooctanoic acid is 1:1-15.
9. The method for producing ferrocenyl methyl methacrylate-based viscosity-controllable fluorosilicone oil as claimed in claim 8, wherein the chlorine-containing solvent comprises dichloromethane and oxalyl chloride.
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