CN111138864B - Fluorine-containing oil-resistant anti-swelling silicone rubber foam material and preparation method thereof - Google Patents
Fluorine-containing oil-resistant anti-swelling silicone rubber foam material and preparation method thereof Download PDFInfo
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- C08J2483/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
Abstract
The invention discloses a fluorine-containing oil-resistant anti-swelling silicone rubber foam material and a preparation method thereof. The preparation method comprises the following steps: (1) uniformly mixing hydrogen-containing fluorosilicone oil, perfluorinated silicone oil, a foaming agent and an inhibitor in a mass ratio of 1-2: 3-4: 0.01-0.5: 0.01-0.2 to obtain a component A, and uniformly mixing perfluorinated silicone oil and a platinum catalyst to obtain a component B; in the component A, the foaming agent is a mixture of a fluorine-silicon surfactant and a hydroxyl-containing reagent, the inhibitor is a silicon alkyne compound, and the structural formula is as follows:
wherein R is1、R2、R3Each independently selected from H, methyl or ethyl, R is selected from cyclohexyl or isopropyl; in the component B, the mass ratio of the perfluorinated silicone oil to Pt in the platinum catalyst is 100: 0.0001-0.01; (2) and mixing the component A and the component B according to the mass ratio of 1:1, uniformly stirring, reacting at room temperature for 5-30 min, and crosslinking and curing the obtained product at 50-125 ℃ for 10-60 min to obtain the high-performance polyurethane resin.
Description
Technical Field
The invention relates to the technical field of silicone rubber foam materials, in particular to a fluorine-containing oil-resistant anti-swelling silicone rubber foam material and a preparation method thereof.
Background
In recent years, with the rapid development of the fields of aerospace, rail transit, new energy automobiles and the like in China, the requirements on the silicon rubber foam material tend to be refined gradually, and the performance technical requirements are higher and higher. The silicon rubber foam has the advantages of light weight, good rebound resilience and the like of the traditional foam material, also has the advantages of high and low temperature resistance, weather resistance, solvent resistance, electrical insulation, radiation resistance, physiological inertia and the like of the silicon rubber, can be widely used for encapsulating electronic and electrical elements and mechanical parts, plays the roles of moisture prevention, dust prevention and vibration reduction, and can also be used for encapsulating or filling piping and lead through holes in building walls. In the actual service process, the silicon rubber foam material is not only in a high-temperature-compression and other complex environments for a long time, but also can face complex environments such as gasoline, solvent and the like. After a long-term complex service environment, the silicon rubber molecule Si-O main chain and the side group are easy to break and rearrange, the mechanical property of a molecule cross-linking network is deteriorated, and the phenomena of deformation, hole wall breakage and the like of a cellular structure can occur, so that the mechanical reliability of the structural member in the service life cycle is seriously influenced. The dimethyl siloxane of the conventional dimethyl silicone rubber foam has low polarity and small solubility parameter in a non-polar organic solvent, so that the dimethyl silicone rubber foam is very easy to swell, resist oil and resist organic medium in the non-polar organic solvent, which causes deformation, even damage and failure of a structural part and can cause catastrophic accidents in severe cases.
The fluorine element is introduced into the siloxane chain, not only has good heat resistance and weather resistance of common siloxane, but also has the performances of water resistance, oil resistance, solvent resistance and the like of fluorine-containing compounds,the elastomer is the only novel elastomer which can be used in a fuel medium at-68-230 ℃ at present. The structural formula of typical fluorine modified silicone oil is Me3SiO(Me2SiO)n[Me(CF3CH2CH2)SiO]mSiMe3It is insoluble in oils, non-polar solvents and water. It has excellent oil resistance, solvent resistance, chemical stability and other performance. The unique molecular structure of the fluorosilicone oil endows the fluorosilicone oil with excellent high and low temperature performance, excellent oxidation resistance and weather resistance. Because the atomic radii of fluorine atoms and hydrogen atoms are close, the fluorine atoms in the fluorosilicone oil have a unique pseudo effect after replacing methyl hydrogen atoms, the steric hindrance of trifluoromethyl and methyl is the same, meanwhile, the fluorine atoms with strong electronegativity are strongly bonded with carbon atoms, and chemically stable fluorine-containing side groups can play a role in shielding Si-O main chains in fluorosilicone oil molecules, so that the chemical resistance of the fluorosilicone oil is improved. The fluorine atoms on the side groups have a blocking effect on the attack of external chemical factors, and the blocking effect is mainly reflected in chemical action transfer caused by an electronic effect and plays a role in stabilizing a system through the chemical action transfer.
A research on preparation of the fluorine-containing silicone rubber foam is reported, T.M. tivier et al (Polymer, 2018, 146, 21-30) use supercritical carbon dioxide as a foaming agent, and prepare a non-perfluorinated chain-link dimethyl siloxane/fluorine-containing siloxane blended silicone rubber foam with uniform and fine pores through a physical foaming method, wherein the pore size of the foam can reach 65 mu m. However, the physical foaming technology has the defects of complex and time-consuming process, poor structure/performance stability and the like, and is difficult to realize large-scale preparation, so that the large-size application requirements in the fields of aerospace, high-speed rail and the like cannot be met.
The method for chemically foaming the silicon-containing rubber foam at room temperature has the characteristics of high foaming rate, high preparation efficiency, simple processing technology, suitability for off-site on-site forming and the like, and the preparation of the fluorine-containing silicone rubber foam is difficult to realize by adopting the traditional method for preparing the dimethyl silicone rubber foam when the room-temperature chemically foaming fluorine-containing rubber foam is required to be prepared. Because the fluorine-silicon rubber introduces trifluoropropyl on the molecular structure of the dimethyl silicon rubber, the steric hindrance of a lateral group of a silicon rubber chain segment is obviously increased, and the electronegativity is extremely high due to the existence of fluorine atoms on the lateral chain, so that the activity of a reaction group is influenced and the dispersion phase compatibility of a foaming agent reacted with the reaction group is poor, which causes difficulty in vulcanization crosslinking and foaming reaction among different system components, so that the foaming and the vulcanization are difficult to be well matched in the preparation process of the silicon rubber foam, the silicon rubber foam is often foamed before material vulcanization, the prepared silicon rubber foam has very uneven cells and larger average cells; or it is difficult to form a sufficient cell structure before crosslinking, and a stable foamed silicone rubber material cannot be prepared.
Disclosure of Invention
Aiming at the defects in the field, the invention provides a preparation method of a fluorine-containing oil-resistant anti-swelling silicone rubber foam material, and the obtained fluorine-containing oil-resistant anti-swelling silicone rubber foam material has the high-low temperature resistance and resilience of silicone rubber foam and the oil-resistant, solvent-resistant and saturated steam-resistant properties of fluororubber, and has the advantages of white foam color, fine and uniform foam pores, adjustable foaming ratio, light weight, greenness and environmental protection.
A preparation method of a fluorine-containing oil-resistant anti-swelling silicone rubber foam material comprises the following steps:
(1) uniformly mixing hydrogen-containing fluorosilicone oil, perfluorinated silicone oil, a foaming agent and an inhibitor in a mass ratio of 1-2: 3-4: 0.01-0.5: 0.01-0.2 to obtain a component A, and uniformly mixing perfluorinated silicone oil and a platinum catalyst to obtain a component B;
in the component A, the foaming agent is a mixture of a fluorine-silicon surfactant and a hydroxyl-containing reagent, the inhibitor is a silalkyne compound, and the structural formula is as follows:
wherein R is1、R2、R3Each independently selected from H, methyl or ethyl, R is selected from cyclohexyl or isopropyl;
in the component B, the mass ratio of the perfluorinated silicone oil to Pt in the platinum catalyst is 100: 0.0001-0.01;
(2) and mixing the component A and the component B according to the mass ratio of 1:1, uniformly stirring, reacting at room temperature for 5-30 min, and crosslinking and curing the obtained product at 50-125 ℃ for 10-60 min to obtain the fluorine-containing oil-resistant anti-swelling silicone rubber foam material.
The invention uses a hydroxyl-containing agent mixed with a fluorosilicone surfactant as a foaming agent. Due to the unique molecular structure of the fluorine-containing silicone oil, fluorine atoms in the side chains of the fluorine-containing silicone oil have very low surface energy, so that the fluorine-containing silicone oil has lower reactivity. And the compatibility of the foaming agent containing hydroxyl with silicone oil is poor, so that the compatibility of two-phase interfaces participating in foaming reaction is poor, and the reaction speed is greatly influenced. Therefore, the problems of the compatibility of the foaming agent and the system and the stability of the system are solved by adopting a strategy of introducing a special fluorine-containing surfactant. The introduction of the fluorine-containing surfactant has one end connected with the fluorine-containing silicone oil system and the other end connected with the foaming agent with hydroxyl, so that the compatibility of two-phase interfaces is greatly increased, the reaction rate between reactants can be effectively regulated and controlled, and the smooth operation of the foaming process is ensured.
The invention also uses a specific inhibitor, the structure of the silicon alkyne compound has alkynyl and silane structures, and the inhibitor used as the foaming silicon rubber has strong inhibition performance at low temperature and can provide enough operation time for the foaming silicon rubber; has high-efficiency catalytic activity at higher temperature, and can be quickly cured at the required temperature. Particularly, the alkynyl structure is easy to dissolve in hydroxyl-containing reagents, and the silane structure is easy to dissolve in fluorine-containing silicone oil systems, so that the problem of compatibility with a two-phase interface is easy to control, and the inhibiting effect of the fluorine-containing silicone oil can be fully exerted.
According to the invention, through the two improvement strategies, the problem of the matching of the cross-linking of the fluorine-silicon foaming silica gel and the foaming reaction activity can be successfully adjusted.
According to the invention, the hydrogen-containing fluorosilicone oil with a proper hydrogen content is selected, so that the foaming reaction can be ensured to be carried out while the crosslinking is ensured, and a stable foam structure is formed. Preferably, the viscosity of the hydrogen-containing fluorosilicone oil is 50-100 mPa · s, and the active hydrogen mass fraction is 0.1% -1.0%.
The invention selects the perfluoro silicone oil with proper vinyl content to ensure the progress of the crosslinking reaction so as to form a foam structure with good mechanical property. Preferably, in the step (1), the component A and the component B are respectively and independently prepared by adopting perfluoro silicone oil with the viscosity of 10-30 pas and the mass fraction of vinyl containing 0.1-1.0%. Further preferably, the component A and the component B are formulated using the same perfluorosilicone oil.
Tests show that the foaming agent has the best effect when the mass ratio of the fluorine-silicon surfactant to the hydroxyl-containing agent is 1: 1.
Preferably, the fluorosilicone surfactant is selected from one or more of models AC-805 (the optional manufacturer is Canoe (Buddha) chemical materials Co., Ltd.), BNK-4036 (the optional manufacturer is Changhui chemical technology (Shenzhen) Co., Ltd.), BNK-4046 (the optional manufacturer is Changhui chemical technology (Shenzhen) Co., Ltd.), 7250 (the optional manufacturer is Aurwima chemical industry Co., Ltd., Shenzhen).
Preferably, the hydroxyl containing agent is selected from water and/or a hydrophilic agent.
Further preferably, the hydrophilic agent is at least one selected from the group consisting of ethylene glycol, polyethylene glycol, and glycerol.
The platinum-group catalyst may be at least one of chloroplatinic acid, a platinum catkin catalyst, and the like.
In order to allow sufficient time for component A, B to mix thoroughly without interfering with the subsequent foaming and crosslinking reactions. Preferably, in the step (2), the stirring time is 30-120 s.
The fluorine-containing silicone rubber foam is prepared by adopting a green chemical foaming method, the preparation process is simple and efficient, and no three wastes are discharged in the preparation process.
The invention also provides the fluorine-containing oil-resistant anti-swelling silicone rubber foam material prepared by the preparation method. The invention adopts a simple mechanical blending method, utilizes the characteristics of low surface tension, oil resistance and solvent resistance of the fluorine modified silicone oil to prepare the oil-resistant and anti-swelling fluorine-containing silicone rubber foam, and simultaneously uses a specific inhibitor to ensure the matching of the foaming process and the vulcanization crosslinking process in the preparation process of the silicone rubber foam. The prepared foam has low density, uniform cell structure, excellent oil resistance and swelling resistance.
In a word, the invention adopts the hydroxyl-containing reagent mixed with the fluorosilicone surfactant as the foaming agent, so that the compatibility of the foaming agent and the two-phase interface of the fluorosilicone oil system is greatly increased, and simultaneously, a specific inhibitor is also used, and the introduction of the inhibitor solves the matching problem between vulcanization crosslinking and foaming. By simultaneously improving the two strategies, the fluorine-containing silicone rubber foam with oil resistance and swelling resistance is prepared, the problem that the conventional dimethyl silicon foam is easy to swell in a non-polar organic solvent is solved, and the prepared perfluoro silicone rubber foam material is light in weight and fine and uniform in foam pores.
Compared with the prior art, the invention has the main advantages that:
(1) the fluorine-containing oil-resistant swelling-resistant silicone rubber foam material disclosed by the invention has the high-low temperature resistance and resilience of silicone rubber foam and the oil-resistant, solvent-resistant and saturated steam-resistant characteristics of fluororubber, and is white in foam color, fine and uniform in foam pores, adjustable in foaming ratio, light in weight, green and environment-friendly.
(2) The fluorine-containing silicone rubber foam is prepared by adopting a green chemical foaming method, the preparation process is simple and efficient, and no three wastes are discharged in the preparation process.
Drawings
FIG. 1 is a photograph of a cross-section of the fluorine-containing oil-resistant antiswelling silicone rubber foam (FSiRF) of example 1;
FIG. 2 is a photograph of a cross section of a fluorine-containing silicone rubber foam material of comparative example 2;
FIG. 3 is a photograph of a cross section of a fluorine-containing silicone rubber foam material of comparative example 3;
FIG. 4 is a photograph comparing the swelling performance of FSiRF of example 1 and dimethylsilicone foam (SiRF) of comparative example 4 in cyclohexane;
fig. 5 is a photograph comparing FSiRF of example 1 and SiRF of comparative example 4 before and after soaking in cyclohexane for 1 month.
Detailed Description
The invention is further described with reference to the following drawings and specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The following examples are conducted under conditions not specified, usually according to conventional conditions, or according to conditions recommended by the manufacturer.
Example 1
Preparation of fluorine-containing oil-resistant antiswelling silicone rubber foam (FSiRF):
taking 4.0g of hydrogen-containing fluorosilicone oil with the viscosity of 55mPa & s and the hydrogen content of 0.3 wt% and 16.0g of perfluoro silicone oil with the viscosity of 20Pa & s and the vinyl content of 0.15 wt%, adding 0.1g of [ (1, 1-dimethyl-2-propynyl) oxy ] trimethylsilane and 0.4g of ethylene glycol (mass ratio of 1:1) mixed by a fluorosilicone surfactant AC-805 (ark), and fully and uniformly mixing by mechanical stirring to prepare a component A; meanwhile, 20.0g of perfluorosilicone oil with the viscosity of 20 pas and the vinyl content of 0.15 wt% is taken, 0.47g of chloroplatinic acid catalyst with the Pt mass concentration of 3000ppm is added, and the component B is prepared after the components are fully and uniformly mixed through mechanical stirring. Then, the component A, B is mechanically stirred for 30s and mixed according to the mass ratio of 1:1, the mixture is reacted for 5min at room temperature after being uniformly mixed, and then the mixture is put into an oven to be treated for 15min at 120 ℃ to prepare the fluorine-containing oil-resistant swelling-resistant silicon rubber foam material, as shown in figure 1, the sample has uniform cells. The prepared foam is placed in oil for oil resistance and anti-swelling test, and the foam material is found not to have swelling phenomenon, even does not have obvious swelling phenomenon after being soaked for one month, and has excellent oil resistance and anti-swelling performance. As shown in figures 4 and 5, FSiRF can not generate obvious swelling phenomenon after being soaked in cyclohexane for 1 month, and has excellent oil resistance and swelling resistance.
Example 2
Preparing a fluorine-containing oil-resistant anti-swelling silicone rubber foam material:
taking 5.0g of hydrogen-containing fluorosilicone oil with the viscosity of 55mPa & s and the hydrogen content of 0.3 wt% and 15.0g of perfluoro silicone oil with the viscosity of 20Pa & s and the vinyl content of 0.15 wt%, adding 0.1g of 1-acetylene-1- (trimethylsiloxy) cyclohexane and 0.4g of glycerol (mass ratio of 1:1) mixed with a fluorosilicone surfactant BNK-4036 (Changhui chemical industry), and fully and uniformly mixing by mechanical stirring to prepare a component A; meanwhile, 20.0g of perfluorosilicone oil with the viscosity of 20 pas and the vinyl content of 0.15 wt% is taken, 0.47g of chloroplatinic acid catalyst with the Pt mass concentration of 3000ppm is added, and the component B is prepared after the components are fully and uniformly mixed through mechanical stirring. Then, the component A, B is mechanically stirred and mixed for 30s according to the mass ratio of 1:1, the mixture is uniformly mixed and then is reacted for 5min at room temperature, and then the mixture is put into an oven to be treated for 15min at 120 ℃ to prepare the fluorine-containing oil-resistant swelling-resistant silicon rubber foam material, and the sample cells are observed to be uniform visually. The prepared foam is placed in oil for oil resistance and anti-swelling test, and the foam material is found not to have swelling phenomenon, even does not have obvious swelling phenomenon after being soaked for one month, and has excellent oil resistance and anti-swelling performance.
Example 3
Preparing a fluorine-containing oil-resistant anti-swelling silicone rubber foam material:
taking 6.0g of hydrogen-containing fluorosilicone oil with the viscosity of 75mPa & s and the hydrogen content of 0.3 wt% and 14.0g of perfluoro silicone oil with the viscosity of 20Pa & s and the vinyl content of 0.35 wt%, adding 0.1g of [ (1, 1-dimethyl-2-propynyl) oxy ] triethylsilane and 0.4g of glycerol (the mass ratio is 1:1) mixed with a fluorosilicone surfactant BNK-4036 (long-glow chemical industry), and fully and uniformly mixing by mechanical stirring to obtain a component A; meanwhile, 20.0g of perfluorosilicone oil with the viscosity of 20 pas and the vinyl content of 0.35 wt% is taken, 0.67g of chloroplatinic acid catalyst with the Pt mass concentration of 3000ppm is added, and the component B is prepared after the components are fully and uniformly mixed through mechanical stirring. Then, the component A, B is mechanically stirred for 30s and mixed according to the mass ratio of 1:1, the mixture is reacted for 6min at room temperature after being uniformly mixed, and then the mixture is put into an oven to be treated for 30min at 120 ℃ to prepare the fluorine-containing oil-resistant swelling-resistant silicon rubber foam material, and the sample cells are observed to be uniform visually. The prepared foam is placed in oil for oil resistance and anti-swelling test, and the foam material is found not to have swelling phenomenon, even does not have obvious swelling phenomenon after being soaked for one month, and has excellent oil resistance and anti-swelling performance.
Example 4
Preparing a fluorine-containing oil-resistant anti-swelling silicone rubber foam material:
taking 7.0g of hydrogen-containing fluorosilicone oil with the viscosity of 75mPa & s and the hydrogen content of 0.3 wt% and 13.0g of perfluoro silicone oil with the viscosity of 20Pa & s and the vinyl content of 0.35 wt%, adding 0.1g of 1-acetylene-1- (triethylsiloxy) cyclohexane and 0.4g of polyethylene glycol (mass ratio of 1:1) mixed with a fluorosilicone surfactant BNK-4046 (Changhui chemical industry), and fully and uniformly mixing by mechanical stirring to obtain a component A; meanwhile, 20.0g of perfluorosilicone oil with the viscosity of 20 pas and the vinyl content of 0.35 wt% is taken, 0.67g of Kansted platinum catalyst with the Pt mass concentration of 3000ppm is added, and the components B are prepared after being fully and uniformly mixed through mechanical stirring. Then, the component A, B is mechanically stirred for 30s and mixed according to the mass ratio of 1:1, the mixture is reacted for 5min at room temperature after being uniformly mixed, and then the mixture is put into an oven to be treated for 30min at 120 ℃ to prepare the fluorine-containing oil-resistant swelling-resistant silicon rubber foam material, and the sample cells are observed to be uniform visually. The prepared foam is placed in oil for oil resistance and anti-swelling test, and the foam material is found not to have swelling phenomenon, even does not have obvious swelling phenomenon after being soaked for one month, and has excellent oil resistance and anti-swelling performance.
Example 5
Preparing a fluorine-containing oil-resistant anti-swelling silicone rubber foam material:
taking 8.0g of hydrogen-containing fluorosilicone oil with the viscosity of 80mPa & s and the hydrogen content of 0.3 wt% and 12.0g of perfluoro silicone oil with the viscosity of 20Pa & s and the vinyl content of 0.55 wt%, adding 0.1g of [ (1, 1-dimethyl-2-propynyl) oxy ] methylsilane and 0.4g of polyethylene glycol (mass ratio is 1:1) mixed with fluorosilicone surfactant 7250 type (Onwema chemical industry), and fully and uniformly mixing by mechanical stirring to prepare a component A; meanwhile, 20.0g of perfluorosilicone oil with the viscosity of 20 pas and the vinyl content of 0.55 wt% is taken, 1.0g of Kansted platinum catalyst with the Pt mass concentration of 3000ppm is added, and the components B are prepared after being fully and uniformly mixed through mechanical stirring. Then, the component A, B is mechanically stirred and mixed for 30s according to the mass ratio of 1:1, the mixture is uniformly mixed and then is reacted for 5min at room temperature, and then the mixture is put into an oven to be treated for 45min at 120 ℃ to prepare the fluorine-containing oil-resistant swelling-resistant silicon rubber foam material, and the sample cells are observed to be uniform visually. The prepared foam is placed in oil for oil resistance and anti-swelling test, and the foam material is found not to have swelling phenomenon, even does not have obvious swelling phenomenon after being soaked for one month, and has excellent oil resistance and anti-swelling performance.
Example 6
Preparing a fluorine-containing oil-resistant anti-swelling silicone rubber foam material:
taking 8.0g of hydrogen-containing fluorosilicone oil with the viscosity of 55mPa & s and the hydrogen content of 0.3 wt% and 12.0g of perfluoro-silicone oil with the viscosity of 20Pa & s and the vinyl content of 0.55 wt%, adding 0.1g of 1-acetylene-1- (ethyl-siloxane) cyclohexane and 0.4g of water (mass ratio of 1:1) mixed with fluorosilicone surfactant 7250 (Onwema chemical industry), and fully and uniformly mixing by mechanical stirring to obtain a component A; meanwhile, 20.0g of perfluorosilicone oil with the viscosity of 20 pas and the vinyl content of 0.55 wt% is taken, 0.67g of Kansted platinum catalyst with the Pt mass concentration of 3000ppm is added, and the components B are prepared after being fully and uniformly mixed through mechanical stirring. Then, the component A, B is mechanically stirred and mixed for 30s according to the mass ratio of 1:1, the mixture is uniformly mixed and then is reacted for 10min at room temperature, and then the mixture is put into an oven to be treated for 60min at 120 ℃ to prepare the fluorine-containing oil-resistant swelling-resistant silicon rubber foam material, and the sample is visually inspected to have uniform cells. The prepared foam is placed in oil for oil resistance and anti-swelling test, and the foam material is found not to have swelling phenomenon, even does not have obvious swelling phenomenon after being soaked for one month, and has excellent oil resistance and anti-swelling performance.
Comparative example 1
Taking 4.0g of hydrogen-containing fluorosilicone oil with the viscosity of 55mPa & s and the hydrogen content of 0.3 wt% and 16.0g of perfluoro silicone oil with the viscosity of 20Pa & s and the vinyl content of 0.15 wt%, adding 0.1g of propiolic alcohol and 0.4g of ethylene glycol into the mixture, and fully and uniformly mixing the mixture through mechanical stirring to obtain a component A; meanwhile, 20.0g of perfluorosilicone oil with the viscosity of 20 pas and the vinyl content of 0.15 wt% is taken, 0.47g of chloroplatinic acid catalyst with the Pt mass concentration of 3000ppm is added, and the component B is prepared after the components are fully and uniformly mixed through mechanical stirring. Component A, B was then mixed uniformly by mechanical stirring for 30s at a mass ratio of 1: 1. In the experimental process, the problem of the matching property of the fluorine-silicon foaming silica gel crosslinking and the foaming reaction activity is found due to the poor compatibility between the systems, and the cell structure is difficult to form effectively.
Comparative example 2
Taking 4.0g of hydrogen-containing fluorosilicone oil with the viscosity of 55mPa & s and the hydrogen content of 0.3 wt% and 16.0g of perfluorosilicone oil with the viscosity of 20Pa & s and the vinyl content of 0.15 wt%, adding 0.1g of propiolic alcohol and 0.4g of ethylene glycol (the mass ratio is 1:1) mixed with a fluorosilicone surfactant AC-805, and fully and uniformly mixing through mechanical stirring to prepare a component A; meanwhile, 20.0g of perfluorosilicone oil with the viscosity of 20 pas and the vinyl content of 0.15 wt% is taken, 0.47g of chloroplatinic acid catalyst with the Pt mass concentration of 3000ppm is added, and the component B is prepared after the components are fully and uniformly mixed through mechanical stirring. And then mechanically stirring the A, B components for 30s according to the mass ratio of 1:1, uniformly mixing, reacting at room temperature for 5min, then placing the mixture into an oven to treat at 120 ℃ for 15min to prepare the fluorine-containing silicon rubber foam material, wherein the finally prepared fluorine-silicon foam material has higher magnification, and the problem that the foam holes are generally large is found through section analysis. The reason is that the conventional inhibitor propargyl alcohol and fluorine-silicon system has poor dispersibility, so that the inhibition effect is poor and the cells are large.
Comparative example 3
Taking 4.0g of hydrogen-containing fluorosilicone oil with the viscosity of 55mPa & s and the hydrogen content of 0.3 wt% and 16.0g of perfluoro silicone oil with the viscosity of 20Pa & s and the vinyl content of 0.15 wt%, adding 0.1g of [ (1, 1-dimethyl-2-propynyl) oxy ] trimethylsilane and 0.4g of ethylene glycol, and fully and uniformly mixing through mechanical stirring to obtain a component A; meanwhile, 20.0g of perfluorosilicone oil with the viscosity of 20 pas and the vinyl content of 0.15 wt% is taken, 0.47g of chloroplatinic acid catalyst with the Pt mass concentration of 3000ppm is added, and the component B is prepared after the components are fully and uniformly mixed through mechanical stirring. Then, the component A, B is mixed by mechanical stirring for 30s according to the mass ratio of 1:1, the mixture is reacted for 5min at room temperature after being mixed evenly, and then the mixture is put into an oven to be processed for 15min at 120 ℃ to prepare the fluorine-containing silicon rubber foam material. Through profile analysis, the problem of uneven cells was found. The reason is that the direct addition of the hydroxyl-containing agent and the fluorine-silicon system has poor dispersibility, so that the foaming agent is not uniformly dispersed in the system, and the foam material prepared by the foaming agent has non-uniform cells.
From comparative examples 1 to 3, it can be seen that if the conventional method (comparative example 1) is used, the problem of activity matching between the cross-linking of the fluorosilicone foaming silica gel and the foaming reaction exists due to poor compatibility between systems, and the fluorine-containing silicone rubber foam with a complete pore structure cannot be formed; if only the fluorosilicone surfactant is used in combination with the hydroxyl containing agent (comparative example 2), there is a problem that the cells are generally large; the addition of only the specific inhibitor (comparative example 3) also results in the formation of foams having non-uniform cells.
Comparative example 4
Preparation of a dimethyl silicone rubber foam (SiRF):
taking 15g of hydroxyl silicone oil with the viscosity of 10 Pa.s and the hydroxyl content of 6 wt%, adding 5g of methyl high hydrogen silicone oil with the viscosity of 55 mPa.s and the hydrogen content of 1.5 wt%, adding 0.1g of propiolic alcohol and 0.4g of ethylene glycol, stirring by a dispersion stirrer, and fully and uniformly mixing to obtain a component A; adding 20g of terminal vinyl silicone oil with viscosity of 60 Pa.s and vinyl content of 0.15 wt% into 0.47g of chloroplatinic acid catalyst with Pt mass concentration of 3000ppm, stirring by a dispersion stirrer, and fully and uniformly mixing to obtain a component B; stirring and mixing the component A, B for 30s by using a dispersion mixer according to the mass ratio of 1:1, uniformly mixing, reacting for 5min at room temperature, and then placing in an oven for processing for 15min at 120 ℃ to obtain the dimethylsilicone rubber foam material. As shown in fig. 4 and 5, after soaking in cyclohexane, SiRF showed significant swelling in several minutes, and after 1 month, the swelling was more significant, indicating poor oil and swelling resistance.
Furthermore, it should be understood that various changes and modifications can be made by one skilled in the art after reading the above description of the present invention, and equivalents also fall within the scope of the invention as defined by the appended claims.
Claims (8)
1. A preparation method of a fluorine-containing oil-resistant anti-swelling silicone rubber foam material is characterized by comprising the following steps:
(1) uniformly mixing hydrogen-containing fluorosilicone oil, perfluorinated silicone oil, a foaming agent and an inhibitor in a mass ratio of 1-2: 3-4: 0.01-0.5: 0.01-0.2 to obtain a component A, and uniformly mixing perfluorinated silicone oil and a platinum catalyst to obtain a component B; respectively and independently preparing the component A and the component B by adopting perfluoro silicone oil with the viscosity of 10-30 pas and the vinyl content of 0.1-1.0 percent by mass;
in the component A, the foaming agent is a mixture of a fluorine-silicon surfactant and a hydroxyl-containing reagent, the inhibitor is a silalkyne compound, and the structural formula is as follows:
wherein R is1、R2、R3Each independently selected from H, methyl or ethyl, R is selected from cyclohexyl or isopropyl;
in the component B, the mass ratio of the perfluorinated silicone oil to Pt in the platinum catalyst is 100: 0.0001-0.01;
(2) and mixing the component A and the component B according to the mass ratio of 1:1, uniformly stirring, reacting at room temperature for 5-30 min, and crosslinking and curing the obtained product at 50-125 ℃ for 10-60 min to obtain the fluorine-containing oil-resistant anti-swelling silicone rubber foam material.
2. The preparation method of the fluorine-containing oil-resistant anti-swelling silicone rubber foam material according to claim 1, wherein the viscosity of the hydrogen-containing fluorosilicone oil is 50-100 mPa-s, and the active hydrogen mass fraction is 0.1-1.0%.
3. The method for preparing the fluorine-containing oil-resistant and swelling-resistant silicone rubber foam material according to claim 1, wherein the mass ratio of the fluorosilicone surfactant to the hydroxyl-containing agent in the foaming agent is 1: 1.
4. The method for preparing the fluorine-containing oil-resistant and swelling-resistant silicone rubber foam material according to claim 1 or 3, wherein the fluorosilicone surfactant is one or more selected from the types of AC-805, BNK-4036, BNK-4046 and 7250.
5. The method for producing a fluorine-containing oil-resistant and swelling-resistant silicone rubber foam material according to claim 1 or 3, wherein the hydroxyl group-containing agent is selected from water and/or a hydrophilic agent;
the hydrophilic agent is at least one selected from ethylene glycol, polyethylene glycol and glycerol.
6. The method for preparing the fluorine-containing oil-resistant and swelling-resistant silicone rubber foam material according to claim 1, wherein the platinum group catalyst is chloroplatinic acid and/or a Kansted platinum catalyst.
7. The method for preparing the fluorine-containing oil-resistant anti-swelling silicone rubber foam material according to claim 1, wherein in the step (2), the stirring time is 30-120 s.
8. The fluorine-containing oil-resistant anti-swelling silicone rubber foam material prepared by the preparation method according to any one of claims 1 to 7.
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