CN114891443A - Hot vulcanization primer for fluorosilicone rubber and preparation process thereof - Google Patents
Hot vulcanization primer for fluorosilicone rubber and preparation process thereof Download PDFInfo
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- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
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Abstract
The invention discloses a heat-vulcanization primer for fluorosilicone rubber, which is characterized by comprising, by weight, 60-80 parts of an alkane solvent, 10-15 parts of an aromatic hydrocarbon solvent, 2-10 parts of an alcohol solvent, 0.5-3 parts of fluorosilicone rubber cement, 2-10 parts of a film-forming agent, 3-5 parts of a cross-linking agent and 1-2 parts of a catalyst, wherein the film-forming agent comprises alkoxy, vinyl and fluoropropyl groups, and the heat-vulcanization primer for fluorosilicone rubber has good compatibility with fluorosilicone rubber, strong binding power and temperature and oil resistance. The invention also discloses a preparation method of the heat vulcanization primer for the fluorosilicone rubber.
Description
Technical Field
The invention relates to the field of fluorosilicone rubber additives, in particular to a heat-vulcanization primer for fluorosilicone rubber and a preparation process thereof.
Background
The fluorosilicone rubber has excellent heat resistance, oil resistance, cold resistance, dielectric property, ozone resistance, atmospheric aging resistance and other performances, and can be used for a long time at the temperature of minus 60 ℃ to plus 250 ℃. The molecular branch chain of the fluorosilicone rubber contains trifluoropropyl, so that the fluorosilicone rubber has lower surface energy and is less prone to adhesion compared with silicon rubber.
At present, no hot vulcanization primer specially used for fluorosilicone rubber exists on the market, a silicon rubber hot vulcanization primer is commonly used for bonding fluorosilicone rubber with metal and plastic, and is mainly a silane coupling agent or a mixture primer of organic silicon resin, a coupling agent and a catalyst, and the defects of poor compatibility with fluorosilicone rubber, low bonding force, no temperature resistance, no oil resistance and the like exist.
Disclosure of Invention
The invention aims to provide a heat-vulcanization primer for fluorosilicone rubber, which has the advantages of good compatibility with fluorosilicone rubber and strong adhesive force.
The technical purpose of the invention is realized by the following technical scheme:
a fluorosilicone rubber hot vulcanization primer coating comprises the following raw materials in parts by weight,
the structural formula of the film forming agent is as follows:
wherein R1 is methoxyl or ethoxyl, R2 is ethenyl, R3 is fluoropropyl, n, m, x are integers more than or equal to 1, and the structure must contain R1, R2 and R3.
By adopting the technical scheme, the film-forming agent contains unsaturated vinyl, so that the interface bonding strength of the fluorosilicone rubber and the polar organic material can be improved; the R1 group is alkoxy, and can form active Si-OH when contacting with trace moisture in the air, and Si-OH forms Si-O-Si bond through self condensation or reaction with terminal hydroxyl in the fluorosilicone rubber, and can form firm combination with the fluorosilicone rubber.
Further setting: the cross-linking agent is one or a mixture of more of methyl orthosilicate, ethyl orthosilicate hydrolysis polycondensate, bis-trimethoxy ethane and bis-triethoxy ethane.
By adopting the technical scheme, the film forming agent only contains two alkoxy groups and is also in a linear structure in the mutual combination process, and the crosslinking agent containing more than three alkoxy groups is selected and can be combined with the alkoxy groups on the film forming agent to form a network structure through crosslinking, and the network structure is solidified to form a film.
Further setting: the film forming agent is a product obtained by hydrolysis and condensation of fluorine-containing siloxane and a silane coupling agent under the condition of an acidic catalyst.
Further setting: the fluorine-containing siloxane contains two or more hydroxyl groups or alkoxy groups; the fluorine-containing siloxane is one or more of hydroxyl-terminated fluorosilicone oil, perfluorooctyl triethoxysilane and perfluorooctyl trimethoxysilane.
Further setting: the silane coupling agent has a C ═ C activated double bond; the silane coupling agent is one or more of methacryloxypropyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, methylvinyldiethoxysilane, methylvinyldimethoxysilane and vinyltris (methoxyethoxy) silane.
By adopting the technical scheme, the fluorine-containing siloxane is combined with the silane coupling agent, so that the fluorine-containing siloxane has good binding capacity with the fluorosilicone rubber, and the binding capacity of the fluorosilicone rubber is improved.
Further setting: the preparation method of the film forming agent comprises the following steps:
sp1, adding an alcohol solvent, an alkane solvent, fluorine-containing siloxane and a silane coupling agent into a three-port glass reaction kettle with a heating, condensing, refluxing, stirrer and temperature measuring device in sequence, starting stirring, starting condensed water, and heating to 40 ℃;
sp2, continuously dripping the mixture of the acid catalyst and the deionized water, gradually heating to 78-95 ℃ after the addition is finished for 30min, and keeping refluxing for 1.5-2.5 hr;
sp3, after cooling, a small amount of sodium bicarbonate was added to neutralize the acidic catalyst in solution and filtered to give the film former.
Wherein the fluorine-containing siloxane and the silane coupling agent: alcohol solvent: the weight ratio of the alkane solvent is 1:1:3, and the molar ratio of the fluorine-containing siloxane to the silane coupling agent is 1: 4-6.
Further setting: the alkane solvent is one or a mixture of n-heptane, n-hexane and n-octane; the aromatic hydrocarbon solvent is one or a mixture of toluene, xylene and trimethylbenzene; the alcohol solvent is one or more of methanol, ethanol and isopropanol.
Further setting: the preparation method of the fluorosilicone rubber cement comprises the following steps: placing the fluorosilicone rubber compound on an open rubber mixing mill, thinly passing the fluorosilicone rubber compound to form a rubber sheet with the thickness of not more than 5mm, cutting the rubber sheet into rubber blocks with the thickness of not more than 3cm multiplied by 3cm by using a cutter, weighing the rubber blocks, putting the rubber blocks into a basket type grinding machine charging barrel with a cooling water jacket, and simultaneously adding an aromatic hydrocarbon solvent to ensure that the weight ratio of the fluorosilicone rubber sheet to the solvent is 1: 15-25, starting a grinding machine, adjusting the rotating speed to be 4500 rpm at 3000, grinding for 45-60 minutes under the condition that the temperature of the mixture in the barrel is controlled not to exceed 40 ℃ by cooling water to obtain the fluorosilicone rubber cement with the solid content of 3-5%, the crude rubber molecular weight of the fluorosilicone rubber compound of 45-60 ten thousand, the vinyl content of 0.3-0.8% and the reinforcing agent of fumed silica.
By adopting the technical scheme, the fluorosilicone rubber cement is doped with the components similar to the matrix structure in the primer, so that the fluorosilicone rubber cement and the fluorosilicone rubber can be well combined during primer coating, and the combination effect of the primer and the fluorosilicone rubber is enhanced.
Further setting: the catalyst is one or a mixture of butyl titanate, titanium acetylacetonate, dibutyltin dilaurate, tin acetate and bismuth neodecanoate.
By adopting the technical scheme, the catalyst is used for catalyzing the occurrence of a crosslinking reaction and promoting the crosslinking of the film-forming agent to form the fluorosilicone rubber primer.
The invention also aims to provide a preparation process of the fluorosilicone rubber heat vulcanization primer.
The technical purpose of the invention is realized by the following technical scheme:
the preparation process of the fluorosilicone rubber hot vulcanization primer comprises the following steps
Step one, preparing fluorosilicone rubber cement:
placing the selected fluorosilicone rubber compound on an open rubber mixing mill, thinly passing for at least 10 times to obtain a rubber sheet with the thickness of not more than 5mm, cutting the rubber sheet into rubber blocks with the thickness of not more than 3cm multiplied by 3cm by using a cutter, weighing a certain weight of the rubber blocks, putting the rubber blocks into a basket type grinder charging barrel with a cooling water jacket, and simultaneously adding an aromatic hydrocarbon solvent to ensure that the weight ratio of the fluorosilicone rubber sheet to the solvent is 1: 15-25, starting the grinding machine, adjusting the rotating speed to 3000 and 4500 revolutions per minute, controlling the temperature of the mixture in the barrel to be not more than 40 ℃ by cooling water, grinding for 45 minutes, and pouring out the fluorosilicone glue paste for later use;
step two, preparation of a film forming agent:
sequentially adding an alcohol solvent, an alkane solvent, fluorine-containing siloxane and a silane coupling agent into a three-port glass reaction kettle with a heating, condensing and refluxing function, a stirrer and a temperature measuring device, starting stirring, starting condensed water, and heating to 40 ℃; continuously dropwise adding the mixture of the acidic catalyst and deionized water, gradually heating to 78-95 deg.C after adding for 30min, and refluxing for 1.5-2.5 hr; after cooling, a small amount of sodium bicarbonate was added to neutralize the acidic catalyst in the solution and filtered to give the film-forming agent.
Step three, preparation of a primer.
And (2) stirring and mixing the fluorosilicone rubber cement prepared in the step one, the film-forming agent prepared in the step two, the alkane solvent, the aromatic hydrocarbon solvent, the alcohol solvent, the cross-linking agent and the catalyst according to parts by weight, wherein the stirring temperature is 20-60 ℃, and the stirring time is 60-120 min.
Detailed Description
Example 1:
a fluorosilicone rubber heat vulcanization primer comprises the following raw materials by weight (unit g),
the alkane solvent is n-hexane, the aromatic hydrocarbon solvent is xylene, the alcohol solvent is methanol, the cross-linking agent is methyl orthosilicate, and the catalyst is titanium acetylacetonate.
The preparation method of the primer of the embodiment comprises the following steps
The method comprises the following steps: the preparation method of the fluorosilicone rubber cement comprises the following steps:
placing the fluorosilicone rubber compound on an open rubber mixing mill, thinly passing the fluorosilicone rubber compound to form a rubber sheet with the thickness of not more than 5mm, cutting the rubber sheet into rubber blocks with the thickness of not more than 3cm multiplied by 3cm by using a cutter, weighing the rubber blocks, putting the rubber blocks into a basket type grinding machine charging barrel with a cooling water jacket, and simultaneously adding an aromatic hydrocarbon solvent to ensure that the weight ratio of the fluorosilicone rubber sheet to the solvent is 1: 15-25, starting a grinding machine, adjusting the rotating speed to be 4500 rpm at 3000, grinding for 45-60 minutes under the condition that the temperature of the mixture in the barrel is controlled not to exceed 40 ℃ by cooling water to obtain the fluorosilicone rubber cement with the solid content of 3-5%, the crude rubber molecular weight of the fluorosilicone rubber compound of 45-60 ten thousand, the vinyl content of 0.3-0.8% and the reinforcing agent of fumed silica.
Step two, preparation of film forming agent
The preparation method comprises the following steps:
sp1, adding an alcohol solvent, an alkane solvent, fluorine-containing siloxane and a silane coupling agent into a three-port glass reaction kettle with a heating, condensing, refluxing, stirrer and temperature measuring device in sequence, starting stirring, starting condensed water, and heating to 40 ℃;
sp2, continuously dropwise adding concentrated hydrochloric acid as a mixture of catalyst and deionized water, gradually heating to 78 deg.C after adding for 30min, and refluxing for 1.5 hr;
sp3, adding a small amount of sodium bicarbonate after cooling to neutralize the acidic catalyst in the solution, and filtering to obtain a film-forming agent,
wherein the fluorine-containing siloxane and the silane coupling agent: alcohol solvent: the weight ratio of the alkane solvent is 1:1:3, and the molar ratio of the fluorine-containing siloxane to the silane coupling agent is 1: 4.5.
The alkane solvent is n-heptane, the alcohol solvent is ethanol, the fluorine-containing siloxane is hydroxyl-terminated fluorosilicone oil, and the silane coupling agent is vinyl triethoxysilane
Preparation of a primer:
and (3) stirring and mixing the fluorosilicone rubber cement prepared in the step one, the film-forming agent prepared in the step two, the alkane solvent, the aromatic hydrocarbon solvent, the alcohol solvent, the cross-linking agent and the catalyst according to parts by weight, wherein the stirring temperature is 60 ℃, and the stirring time is 60 min.
Example 2:
a fluorosilicone rubber heat vulcanization primer comprises the following raw materials by weight (unit g),
the alkane solvent is n-heptane, the aromatic hydrocarbon solvent is trimethylbenzene, the alcohol solvent is ethanol, the cross-linking agent is ethyl orthosilicate, and the catalyst is tetrabutyl titanate.
The preparation method of the primer of the embodiment comprises the following steps
The method comprises the following steps: the preparation method of the fluorosilicone rubber cement comprises the following steps:
placing the fluorosilicone rubber compound on an open rubber mixing mill, thinly passing the fluorosilicone rubber compound to form a rubber sheet with the thickness of not more than 5mm, cutting the rubber sheet into rubber blocks with the thickness of not more than 3cm multiplied by 3cm by using a cutter, weighing the rubber blocks, putting the rubber blocks into a basket type grinding machine charging barrel with a cooling water jacket, and simultaneously adding an aromatic hydrocarbon solvent to ensure that the weight ratio of the fluorosilicone rubber sheet to the solvent is 1: 15-25, starting a grinding machine, adjusting the rotating speed to be 4500 rpm at 3000, grinding for 45-60 minutes under the condition that the temperature of the mixture in the barrel is controlled not to exceed 40 ℃ by cooling water to obtain the fluorosilicone rubber cement with the solid content of 3-5%, the crude rubber molecular weight of the fluorosilicone rubber compound of 45-60 ten thousand, the vinyl content of 0.3-0.8% and the reinforcing agent of fumed silica.
Step two, preparation of film forming agent
The preparation method comprises the following steps:
sp1, adding an alcohol solvent, an alkane solvent, fluorine-containing siloxane and a silane coupling agent into a three-port glass reaction kettle with a heating, condensing, refluxing, stirrer and temperature measuring device in sequence, starting stirring, starting condensed water, and heating to 40 ℃;
sp2, continuously dropwise adding concentrated hydrochloric acid as a mixture of catalyst and deionized water, gradually heating to 85 deg.C after adding for 30min, and refluxing for 2 hr;
sp3, adding a small amount of sodium bicarbonate after cooling to neutralize the acidic catalyst in the solution, and filtering to obtain a film-forming agent,
wherein the fluorine-containing siloxane and the silane coupling agent: alcohol solvent: the weight ratio of the alkane solvent is 1:1:3, and the molar ratio of the fluorine-containing siloxane to the silane coupling agent is 1: 6.
The alkane solvent is n-hexane, the alcohol solvent is isopropanol, the fluorine-containing siloxane is perfluorooctyl triethoxysilane, and the silane coupling agent is methacryloxypropyl trimethoxysilane
Preparation of a primer:
and (3) stirring and mixing the fluorosilicone rubber cement prepared in the step one, the film-forming agent prepared in the step two, the alkane solvent, the aromatic hydrocarbon solvent, the alcohol solvent, the cross-linking agent and the catalyst according to parts by weight, wherein the stirring temperature is 50 ℃, and the stirring time is 90 min.
Example 3:
a fluorosilicone rubber heat vulcanization primer comprises the following raw materials by weight (unit g),
the alkane solvent is n-octane, the aromatic hydrocarbon solvent is toluene, the alcohol solvent is isopropanol, the cross-linking agent is bis-trimethoxy ethane, and the catalyst is bismuth neodecanoate.
The preparation method of the primer of the embodiment comprises the following steps
The method comprises the following steps: the preparation method of the fluorosilicone rubber cement comprises the following steps:
placing the fluorosilicone rubber compound on an open rubber mixing mill, thinly passing the fluorosilicone rubber compound to form a rubber sheet with the thickness of not more than 5mm, cutting the rubber sheet into rubber blocks with the thickness of not more than 3cm multiplied by 3cm by using a cutter, weighing the rubber blocks, putting the rubber blocks into a basket type grinding machine charging barrel with a cooling water jacket, and simultaneously adding an aromatic hydrocarbon solvent to ensure that the weight ratio of the fluorosilicone rubber sheet to the solvent is 1: 15-25, starting a grinding machine, adjusting the rotating speed to be 4500 rpm at 3000, grinding for 45-60 minutes under the condition that the temperature of the mixture in the barrel is controlled not to exceed 40 ℃ by cooling water to obtain the fluorosilicone rubber cement with the solid content of 3-5%, the crude rubber molecular weight of the fluorosilicone rubber compound of 45-60 ten thousand, the vinyl content of 0.3-0.8% and the reinforcing agent of fumed silica.
Step two, preparation of film forming agent
The preparation method comprises the following steps:
sp1, adding an alcohol solvent, an alkane solvent, fluorine-containing siloxane and a silane coupling agent into a three-port glass reaction kettle with a heating, condensing, refluxing, stirrer and temperature measuring device in sequence, starting stirring, starting condensed water, and heating to 40 ℃;
sp2, continuously dropwise adding concentrated hydrochloric acid as a mixture of catalyst and deionized water, gradually heating to 90 deg.C after adding for 30min, and refluxing for 2 hr;
sp3, adding a small amount of sodium bicarbonate after cooling to neutralize the acidic catalyst in the solution, and filtering to obtain a film-forming agent,
wherein the fluorine-containing siloxane and the silane coupling agent: alcohol solvent: the weight ratio of the alkane solvent is 1:1:3, and the molar ratio of the fluorine-containing siloxane to the silane coupling agent is 1:5.
The alkane solvent is n-octane, the alcohol solvent is isopropanol, the fluorine-containing siloxane is perfluorooctyl trimethoxysilane, and the silane coupling agent is methyl vinyl diethoxy silane.
Preparation of a primer:
and (3) stirring and mixing the fluorosilicone rubber cement prepared in the step one, the film-forming agent prepared in the step two, the alkane solvent, the aromatic hydrocarbon solvent, the alcohol solvent, the cross-linking agent and the catalyst according to parts by weight, wherein the stirring temperature is 40 ℃, and the stirring time is 90 min.
Example 4:
a fluorosilicone rubber heat vulcanization primer comprises the following raw materials by weight (unit g),
the alkane solvent is n-octane, the aromatic hydrocarbon solvent is toluene, the alcohol solvent is isopropanol, the cross-linking agent is bis-trimethoxy ethane, and the catalyst is bismuth neodecanoate.
The preparation method of the primer of the embodiment comprises the following steps
The method comprises the following steps: the preparation method of the fluorosilicone rubber cement comprises the following steps:
placing the fluorosilicone rubber compound on an open rubber mixing mill, thinly passing the fluorosilicone rubber compound to form a rubber sheet with the thickness of not more than 5mm, cutting the rubber sheet into rubber blocks with the thickness of not more than 3cm multiplied by 3cm by using a cutter, weighing the rubber blocks, putting the rubber blocks into a basket type grinding machine charging barrel with a cooling water jacket, and simultaneously adding an aromatic hydrocarbon solvent to ensure that the weight ratio of the fluorosilicone rubber sheet to the solvent is 1: 15-25, starting a grinding machine, adjusting the rotating speed to be 4500 rpm at 3000, grinding for 45-60 minutes under the condition that the temperature of the mixture in the barrel is controlled not to exceed 40 ℃ by cooling water to obtain the fluorosilicone rubber cement with the solid content of 3-5%, the crude rubber molecular weight of the fluorosilicone rubber compound of 45-60 ten thousand, the vinyl content of 0.3-0.8% and the reinforcing agent of fumed silica.
Step two, preparation of film forming agent
The preparation method comprises the following steps:
sp1, adding an alcohol solvent, an alkane solvent, fluorine-containing siloxane and a silane coupling agent into a three-port glass reaction kettle with a heating, condensing, refluxing, stirrer and temperature measuring device in sequence, starting stirring, starting condensed water, and heating to 40 ℃;
sp2, continuously dropwise adding concentrated hydrochloric acid as a mixture of a catalyst and deionized water, gradually heating to 82 ℃ after the addition is finished for 30min, and keeping refluxing for 2 hr;
sp3, adding a small amount of sodium bicarbonate after cooling to neutralize the acidic catalyst in the solution, and filtering to obtain a film-forming agent,
wherein the fluorine-containing siloxane and the silane coupling agent: alcohol solvent: the weight ratio of the alkane solvent is 1:1:3, and the molar ratio of the fluorine-containing siloxane to the silane coupling agent is 1: 5.5.
The alkane solvent is n-octane, the alcohol solvent is isopropanol, the fluorine-containing siloxane is perfluorooctyl trimethoxysilane, and the silane coupling agent is methyl vinyl diethoxy silane.
Preparation of a primer:
and (3) stirring and mixing the fluorosilicone rubber cement prepared in the step one, the film-forming agent prepared in the step two, the alkane solvent, the aromatic hydrocarbon solvent, the alcohol solvent, the cross-linking agent and the catalyst according to parts by weight, wherein the stirring temperature is 30 ℃, and the stirring time is 120 min.
Example 5:
a fluorosilicone rubber heat vulcanization primer comprises the following raw materials by weight (unit g),
the alkane solvent is n-octane, the aromatic hydrocarbon solvent is toluene, the alcohol solvent is isopropanol, the cross-linking agent is bis-trimethoxy ethane, and the catalyst is bismuth neodecanoate.
The preparation method of the primer of the embodiment comprises the following steps
The method comprises the following steps: the preparation method of the fluorosilicone rubber cement comprises the following steps:
placing the fluorosilicone rubber compound on an open rubber mixing mill, thinly passing the fluorosilicone rubber compound to form a rubber sheet with the thickness of not more than 5mm, cutting the rubber sheet into rubber blocks with the thickness of not more than 3cm multiplied by 3cm by using a cutter, weighing the rubber blocks, putting the rubber blocks into a basket type grinding machine charging barrel with a cooling water jacket, and simultaneously adding an aromatic hydrocarbon solvent to ensure that the weight ratio of the fluorosilicone rubber sheet to the solvent is 1: 15-25, starting a grinding machine, adjusting the rotating speed to be 4500 rpm at 3000, grinding for 45-60 minutes under the condition that the temperature of the mixture in the barrel is controlled not to exceed 40 ℃ by cooling water to obtain the fluorosilicone rubber cement with the solid content of 3-5%, the crude rubber molecular weight of the fluorosilicone rubber compound of 45-60 ten thousand, the vinyl content of 0.3-0.8% and the reinforcing agent of fumed silica.
Step two, preparation of film forming agent
The preparation method comprises the following steps:
sp1, adding an alcohol solvent, an alkane solvent, fluorine-containing siloxane and a silane coupling agent into a three-port glass reaction kettle with a heating, condensing, refluxing, stirrer and temperature measuring device in sequence, starting stirring, starting condensed water, and heating to 40 ℃;
sp2, continuously dropwise adding concentrated hydrochloric acid as a mixture of catalyst and deionized water, gradually heating to 95 deg.C after adding for 30min, and refluxing for 2 hr;
sp3, adding a small amount of sodium bicarbonate after cooling to neutralize the acidic catalyst in the solution, and filtering to obtain a film-forming agent,
wherein the fluorine-containing siloxane and the silane coupling agent: alcohol solvent: the weight ratio of the alkane solvent is 1:1:3, and the molar ratio of the fluorine-containing siloxane to the silane coupling agent is 1:4.
The alkane solvent is n-octane, the alcohol solvent is isopropanol, the fluorine-containing siloxane is perfluorooctyl trimethoxysilane, and the silane coupling agent is methyl vinyl diethoxy silane.
Preparation of a primer:
and (3) stirring and mixing the fluorosilicone rubber cement prepared in the step one, the film-forming agent prepared in the step two, the alkane solvent, the aromatic hydrocarbon solvent, the alcohol solvent, the cross-linking agent and the catalyst according to parts by weight, wherein the stirring temperature is 20 ℃, and the stirring time is 60 min.
Comparative example 1:
a fluorosilicone rubber heat vulcanization primer comprises the following raw materials by weight (unit g),
the alkane solvent is n-octane, the aromatic hydrocarbon solvent is toluene, the alcohol solvent is isopropanol, the cross-linking agent is bis-trimethoxy ethane, and the catalyst is bismuth neodecanoate.
The preparation method of the primer of the embodiment comprises the following steps
Step one, preparation of film forming agent
The preparation method comprises the following steps:
sp1, adding an alcohol solvent, an alkane solvent, fluorine-containing siloxane and a silane coupling agent into a three-port glass reaction kettle with a heating, condensing, refluxing, stirrer and a temperature measuring device in sequence, starting stirring, starting condensed water, and heating to 40 ℃;
sp2, continuously dropwise adding concentrated hydrochloric acid as a mixture of catalyst and deionized water, gradually heating to 90 deg.C after adding for 30min, and refluxing for 2 hr;
sp3, adding a small amount of sodium bicarbonate after cooling to neutralize the acidic catalyst in the solution, and filtering to obtain a film-forming agent,
wherein the fluorine-containing siloxane and silane coupling agent: alcohol solvent: the weight ratio of the alkane solvent is 1:1:3, and the molar ratio of the fluorine-containing siloxane to the silane coupling agent is 1:5.
The alkane solvent is n-octane, the alcohol solvent is isopropanol, the fluorine-containing siloxane is perfluorooctyl trimethoxysilane, and the silane coupling agent is methyl vinyl diethoxy silane.
Preparation of a primer:
and (3) stirring and mixing the fluorosilicone rubber, the film forming agent prepared in the step two, the alkane solvent, the aromatic hydrocarbon solvent, the alcohol solvent, the cross-linking agent and the catalyst according to parts by weight, wherein the stirring temperature is 40 ℃, and the stirring time is 90 min.
Comparative example 2: the commercial primer, conceivably 34T.
Comparative example 3: a commercially available primer, kellac CH 608.
Detecting the bonding strength test:
NFS9760 fluorosilicone rubber compound as raw material, 304 stainless steel sheet
Uniformly adding 0.75% of aksuo di-penta vulcanizing agent and 0.3% of Taike 1801 color master batch into NFS9760 fluorosilicone rubber compound by a two-roll open mill, then hot-vulcanizing molded rubber samples according to the size of GB/T7760-2003 at 175 ℃ for 10min, and treating the rubber samples with the primer in the examples and the comparative examples;
a test piece is made on a 304 stainless steel sheet according to GB/T7760-2003, the test piece is tested by a 90-degree stripping method, the coverage of the residual rubber on the surface is checked, the higher the coverage is, the better the adhesion of the primer is,
and (3) testing conditions are as follows: 1. after bonding, testing at normal temperature;
testing after hot air aging for 72 hours at the temperature of 2.150 ℃;
the test was carried out at 3.23 ℃ after 72 hours of oil immersion in IRM 903.
The test results are shown in table 1 below:
table 190 ° peel test results table
Comparative example 1, in comparison with examples 1 to 5, where no fluorosilicone rubber cement was prepared, the peeling property was reduced; comparative example 2 is a common primer for silicone rubber in the market, and has a certain difference in peeling performance from the examples at normal temperature, and after heat treatment and oil treatment, the difference in peeling performance is obviously increased, so that the primers used in the examples 1-5 have good temperature and oil resistance; example 3 has better performance compared with other examples, and the preparation process and the component composition of the primer in example 3 have better effects.
The above-described embodiments do not limit the scope of the present invention. Any modification, equivalent replacement, and improvement made within the spirit and principle of the above-mentioned embodiments should be included in the protection scope of the technical solution.
Claims (10)
1. A heat-vulcanization primer for fluorosilicone rubber is characterized by comprising the following raw materials in parts by weight,
the structural formula of the film forming agent is as follows:
wherein R1 is methoxyl or ethoxyl, R2 is ethenyl, R3 is fluoropropyl, n, m, x are integers more than or equal to 1, and the structure must contain R1, R2 and R3.
2. The heat-vulcanization primer for fluorosilicone rubber according to claim 1, wherein the crosslinking agent is a mixture of one or more of methyl orthosilicate, ethyl orthosilicate, a hydrolyzed polycondensate of ethyl orthosilicate, bistrimethoxyethane, and bistriethoxyethane; the fluoropropyl radical can.
3. The heat-vulcanization primer for fluorosilicone rubber according to claim 1, wherein the film-forming agent is a product of hydrolytic condensation of a fluorine-containing siloxane and a silane coupling agent under an acidic catalyst.
4. The heat-cure primer for fluorosilicone rubber according to claim 4, wherein the fluorine-containing silicone contains two or more hydroxyl groups or alkoxy groups; the fluorine-containing siloxane is one or more of hydroxyl-terminated fluorosilicone oil, perfluorooctyl triethoxysilane and perfluorooctyl trimethoxysilane.
5. The heat-vulcanization primer for fluorosilicone rubber according to claim 3, wherein the silane coupling agent has a C ═ C activated double bond; the silane coupling agent is one or more of methacryloxypropyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, methylvinyldiethoxysilane, methylvinyldimethoxysilane and vinyltris (methoxyethoxy) silane.
6. The heat-vulcanization primer for fluorosilicone rubber according to claim 1, wherein the preparation method of the film-forming agent comprises the steps of:
sp1, adding an alcohol solvent, an alkane solvent, fluorine-containing siloxane and a silane coupling agent into a three-port glass reaction kettle with a heating, condensing, refluxing, stirrer and temperature measuring device in sequence, starting stirring, starting condensed water, and heating to 40 ℃;
sp2, continuously dripping the mixture of the acid catalyst and the deionized water, gradually heating to 78-95 ℃ after the addition is finished for 30min, and keeping refluxing for 1.5-2.5 hr;
sp3, adding a small amount of sodium bicarbonate after cooling to neutralize the acidic catalyst in the solution, and filtering to obtain a film-forming agent,
wherein the fluorine-containing siloxane and the silane coupling agent: alcohol solvent: the weight ratio of the alkane solvent is 1:1:3, and the molar ratio of the fluorine-containing siloxane to the silane coupling agent is 1: 4-6.
7. The heat-cure primer for fluorosilicone rubber according to claim 1 or 6, wherein the alkane solvent is a mixture of one or more of n-heptane, n-hexane, and n-octane; the aromatic hydrocarbon solvent is one or a mixture of toluene, xylene and trimethylbenzene; the alcohol solvent is one or more of methanol, ethanol and isopropanol.
8. The heat-vulcanization primer for fluorosilicone rubber according to claim 1, wherein the preparation method of the fluorosilicone rubber paste comprises: placing the fluorosilicone rubber compound on an open rubber mixing mill, thinly passing the fluorosilicone rubber compound to form a rubber sheet with the thickness of not more than 5mm, cutting the rubber sheet into rubber blocks with the thickness of not more than 3cm multiplied by 3cm by using a cutter, weighing the rubber blocks, putting the rubber blocks into a basket type grinding machine charging barrel with a cooling water jacket, and simultaneously adding an aromatic hydrocarbon solvent to ensure that the weight ratio of the fluorosilicone rubber sheet to the solvent is 1: 15-25, starting a grinding machine, adjusting the rotating speed to be 4500 rpm at 3000, grinding for 45-60 minutes under the condition that the temperature of the mixture in the barrel is controlled not to exceed 40 ℃ by cooling water to obtain the fluorosilicone rubber cement with the solid content of 3-5%, the crude rubber molecular weight of the fluorosilicone rubber compound of 45-60 ten thousand, the vinyl content of 0.3-0.8% and the reinforcing agent of fumed silica.
9. The primer for hot vulcanization of fluorosilicone rubber according to claim 1, wherein the catalyst is one or a mixture of butyl titanate, titanium acetylacetonate, dibutyltin dilaurate, tin acetate, and bismuth neodecanoate.
10. A process for preparing a heat-curable primer for fluorosilicone rubber as set forth in any one of claims 1 to 9, which comprises: comprises the following steps
Step one, preparing fluorosilicone rubber cement:
placing the selected fluorosilicone rubber compound on an open rubber mixing mill, thinly passing for at least 10 times to obtain a rubber sheet with the thickness of not more than 5mm, cutting the rubber sheet into rubber blocks with the thickness of not more than 3cm multiplied by 3cm by using a cutter, weighing a certain weight of the rubber blocks, putting the rubber blocks into a basket type grinder charging barrel with a cooling water jacket, and simultaneously adding an aromatic hydrocarbon solvent to ensure that the weight ratio of the fluorosilicone rubber sheet to the solvent is 1: 15-25, starting the grinding machine, adjusting the rotating speed to 3000 and 4500 revolutions per minute, controlling the temperature of the mixture in the barrel to be not more than 40 ℃ by cooling water, grinding for 45 minutes, and pouring out the fluorosilicone glue paste for later use;
step two, preparation of a film forming agent:
sequentially adding an alcohol solvent, an alkane solvent, fluorine-containing siloxane and a silane coupling agent into a three-port glass reaction kettle with a heating, condensing and refluxing function, a stirrer and a temperature measuring device, starting stirring, starting condensed water, and heating to 40 ℃; continuously dropwise adding the mixture of the acidic catalyst and deionized water, gradually heating to 78-95 deg.C after adding for 30min, and refluxing for 1.5-2.5 hr; after cooling, adding a small amount of sodium bicarbonate to neutralize the acid catalyst in the solution, and filtering to obtain a film-forming agent;
step three, preparing a primer:
and (2) stirring and mixing the fluorosilicone rubber cement prepared in the step one, the film-forming agent prepared in the step two, the alkane solvent, the aromatic hydrocarbon solvent, the alcohol solvent, the cross-linking agent and the catalyst according to parts by weight, wherein the stirring temperature is 20-60 ℃, and the stirring time is 60-120 min.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109762346A (en) * | 2018-12-26 | 2019-05-17 | 福建拓烯新材料科技有限公司 | A kind of Fluorosilicone rubber composition and preparation method |
| CN110577747A (en) * | 2019-10-12 | 2019-12-17 | 广州道林合成材料有限公司 | room temperature vulcanized fluorosilicone rubber and preparation method thereof |
| CN112300579A (en) * | 2020-10-16 | 2021-02-02 | 浙江新安化工集团股份有限公司 | Fluorosilicone rubber with adhesion with silicone rubber and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109762346A (en) * | 2018-12-26 | 2019-05-17 | 福建拓烯新材料科技有限公司 | A kind of Fluorosilicone rubber composition and preparation method |
| CN110577747A (en) * | 2019-10-12 | 2019-12-17 | 广州道林合成材料有限公司 | room temperature vulcanized fluorosilicone rubber and preparation method thereof |
| CN112300579A (en) * | 2020-10-16 | 2021-02-02 | 浙江新安化工集团股份有限公司 | Fluorosilicone rubber with adhesion with silicone rubber and preparation method thereof |
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