CN113321935A - High-corrosion-resistance silicone rubber material and preparation method thereof - Google Patents
High-corrosion-resistance silicone rubber material and preparation method thereof Download PDFInfo
- Publication number
- CN113321935A CN113321935A CN202110751535.2A CN202110751535A CN113321935A CN 113321935 A CN113321935 A CN 113321935A CN 202110751535 A CN202110751535 A CN 202110751535A CN 113321935 A CN113321935 A CN 113321935A
- Authority
- CN
- China
- Prior art keywords
- silicone rubber
- stirring
- rubber material
- mixing
- corrosion resistance
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of 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; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
- C08L83/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/04—Thermoplastic elastomer
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Silicon Polymers (AREA)
Abstract
The invention discloses a high corrosion-resistant silicone rubber material and a preparation method thereof, and relates to the field of rubber materials.A modified silicone rubber and a thermoplastic polyurethane elastomer are added into an open mill for open milling, then a hydrolysis inhibitor and white carbon black are sequentially added for mixing, blanking is carried out, the rubber material is placed at room temperature, then secondary mixing is carried out, and then the mixed rubber material is placed into a vulcanizing machine for completing vulcanization, so that the high corrosion-resistant silicone rubber material is obtained; according to the preparation method, the modified silicone rubber is prepared, so that the hydrophobic property and stability of the silicone rubber are improved, the hydrolysis of the thermoplastic polyurethane elastomer is inhibited by the ring-opening addition reaction of the prepared hydrolysis inhibitor and the carboxyl, hydroxyl, amino and the like containing protons generated in the hydrolysis process of the thermoplastic polyurethane elastomer, and under the synergistic effect of the modified silicone rubber and the hydrolysis inhibitor, the silicone rubber and polyurethane composite material has excellent mechanical properties and excellent corrosion resistance.
Description
Technical Field
The invention relates to the field of rubber materials, in particular to a high-corrosion-resistance silicone rubber material and a preparation method thereof.
Background
The silicon rubber is straight-chain polysiloxane with high relative molecular mass, a molecular main chain consists of silicon atoms and oxygen atoms which are alternately arranged (-Si-O-Si-), the bond energy (422KJ/mol) between silicon oxygen bonds is more than the bond energy (240KJ/mol) between carbon bonds, and the silicon rubber is nontoxic and tasteless, has electric insulating property, light aging resistance, good high and low temperature resistance (the original strength and elasticity are not lost at 300 ℃ and 90 ℃ below zero), mildew resistance, oxygen aging resistance and chemical stability, and is widely applied to the fields of aerospace, chemical engineering, agriculture, medical sanitation, electronic and electrical appliance industry and the like;
the thermoplastic polyurethane is a high polymer material integrating high hardness, high strength and wear resistance, tear resistance, bending resistance, tensile strength, high elongation at break and oil resistance, and can be used for toughening and modifying the silicon rubber by utilizing the high elasticity of the thermoplastic polyurethane, so that various properties of the silicon rubber are further improved, the application range of the silicon rubber is expanded, and the development of the silicon rubber is promoted.
However, the existing silicone rubber and polyurethane composite materials have excellent mechanical properties, but the existing silicone rubber and polyurethane composite materials have poor hydrolysis resistance and corrosion resistance, and are easy to generate hydrolysis reaction, so that the mechanical properties of products are rapidly reduced. Therefore, how to improve the corrosion resistance of the silicon rubber and polyurethane composite material is the key point of the invention.
Disclosure of Invention
In order to overcome the technical problems, the invention aims to provide a high-corrosion-resistance silicone rubber material and a preparation method thereof, wherein the preparation method comprises the following steps: the high-corrosion-resistance silicone rubber material is obtained by adding modified silicone rubber and a thermoplastic polyurethane elastomer into an open mill for open milling, then adding a hydrolysis inhibitor for mixing, then adding white carbon black for continuous mixing, blanking, placing the rubber material at room temperature, then carrying out secondary mixing, and then placing the mixed rubber material into a vulcanizing machine for vulcanizing, so that the problem that the mechanical properties of the product are sharply reduced due to the fact that the existing silicone rubber and polyurethane composite material is excellent in mechanical properties, but poor in hydrolysis resistance and corrosion resistance and easy to generate hydrolysis reaction is solved.
The purpose of the invention can be realized by the following technical scheme:
a high corrosion-resistant silicone rubber material comprises the following components in parts by weight:
100-150 parts of modified silicon rubber, 50-70 parts of thermoplastic polyurethane elastomer, 1-10 parts of hydrolysis inhibitor and 15-25 parts of white carbon black;
the high-corrosion-resistance silicone rubber material is prepared by the following steps:
the method comprises the following steps: preparing modified silicon rubber;
step two: preparing a hydrolysis inhibitor;
step three: adding the modified silicone rubber and the thermoplastic polyurethane elastomer into an open mill for open milling, then adding a hydrolysis inhibitor for mixing for 10-20min, then adding white carbon black for continuously mixing for 30-60min, blanking, placing the rubber material at room temperature for 2-3h, then carrying out secondary mixing, then placing the mixed rubber material into a vulcanizing machine, and completing vulcanization under the condition of 10-12MPa to obtain the high corrosion-resistant 1-corrosion-resistant silicone rubber material.
As a further scheme of the invention: the preparation process of the modified silicone rubber is as follows:
a1: adding p-bromophenol, cesium carbonate and dimethyl sulfoxide into a three-neck flask provided with a stirrer, a gas-guide tube and a constant-pressure dropping funnel, introducing argon for protection, stirring at room temperature and at a stirring rate of 800r/min for 10-12h, then dropwise adding p-bromobenzotrifluoride while stirring, controlling the dropwise adding rate to be 1-5mL/min, heating to 50-55 ℃ after dropwise adding, continuing to stir for 20-30h, controlling the heating rate to be 1 ℃/min, after the reaction is finished, removing insoluble substances by vacuum filtration, extracting the filtrate for 2-3 times by using ethyl acetate, combining the extracts, washing 2-3 times by using a saturated sodium chloride solution, standing for layering, drying the organic layer by using anhydrous sodium sulfate, concentrating the organic layer, and purifying by using normal hexane as a mobile phase through silica gel column chromatography, then, removing the solvent and the extractant by rotary evaporation to obtain an intermediate 1;
the reaction principle is as follows:
a2: adding magnesium powder, methyltrimethoxysilane and tetrahydrofuran into a three-neck flask provided with a stirrer, a gas-guide tube and a constant-pressure dropping funnel, introducing argon gas for protection, stirring and dropwise adding the intermediate 1 solution while stirring at the room temperature and the stirring rate of 300-400r/min, controlling the dropwise adding rate to be 1-2 drops/s, continuously stirring and reacting for 20-30h after the dropwise adding is finished, heating to boiling after the reaction is finished, cooling to the room temperature by using an ice water bath, adding toluene into the reaction product, stirring and mixing for 3-5min, carrying out vacuum filtration, and distilling the filtrate under reduced pressure to obtain an intermediate 2;
the reaction principle is as follows:
a3: adding a hydrochloric acid solution and half of toluene into a three-neck flask provided with a stirrer and a constant pressure dropping funnel, uniformly mixing an intermediate 2, the other half of toluene and dimethyl dimethoxysilane, then adding into the constant pressure dropping funnel, stirring and dropwise adding into the three-neck flask under the condition that the stirring speed is 500-600r/min, controlling the dropwise adding speed to be 0.5-1mL/min, then heating to 50-55 ℃, stirring and reacting for 6-8h, after the reaction is finished, washing a reaction product to be neutral by using distilled water, then drying by using anhydrous sodium sulfate, filtering, and distilling the filtrate under reduced pressure to obtain an intermediate 3;
the reaction principle is as follows:
a4: adding the intermediate 3 and octamethylcyclotetrasiloxane into a reaction kettle, heating to 35-40 ℃, performing reduced pressure dehydration for 30-50min, introducing argon for protection, then adding a catalyst and N, N-dimethylformamide, heating to 80-110 ℃, and reacting at constant temperature for 30-40min to obtain the modified silicone rubber.
The reaction principle is as follows:
as a further scheme of the invention: the dosage ratio of the p-bromophenol, the cesium carbonate, the dimethyl sulfoxide and the p-bromotrifluorotoluene in the step A1 is 0.10 mol: 0.15 mol: 150-200 mL: 0.20 mol.
As a further scheme of the invention: the using ratio of the magnesium powder, the methyltrimethoxysilane, the tetrahydrofuran, the intermediate 1 solution and the toluene in the step A2 is 0.8 mol: 66.44 g: 150-200 mL: 20mL of: 100-150mL, wherein the solution of the intermediate 1 is the mixture of the intermediate 1 and tetrahydrofuran according to the mol ratio of 0.08 mol: 10mL of the resulting solution after mixing.
As a further scheme of the invention: the dosage ratio of the hydrochloric acid solution, the toluene, the intermediate 2 and the dimethyl dimethoxy silane in the step A3 is 30 mL: 30mL of: 9 mmol: 27 mmol.
As a further scheme of the invention: the dosage ratio of the intermediate 3, the octamethylcyclotetrasiloxane, the catalyst and the N, N-dimethylformamide in the step A4 is 0.5-1.0 g: 50 g: 1.0 g: 100 and 200 mL.
As a further scheme of the invention: the catalyst in step a4 was prepared as follows:
adding potassium hydroxide into a three-neck flask provided with a stirrer and a constant-pressure dropping funnel, heating to 60-70 ℃, performing reduced-pressure dehydration for 2-3h, introducing argon for protection, then adding an intermediate 3, heating to 120-130 ℃, stirring and reacting for 4-5h under the condition that the stirring rate is 500-800r/min, and cooling a reaction product to room temperature after the reaction is finished to obtain the catalyst.
As a further scheme of the invention: the mass ratio of the potassium hydroxide to the intermediate 3 is 1: 50-100.
As a further scheme of the invention: the preparation process of the hydrolysis inhibitor comprises the following steps:
adding bisphenol A, epichlorohydrin, deionized water and isopropanol into a four-neck flask provided with a stirrer, a reflux condenser tube and a constant pressure dropping funnel, stirring at the stirring rate of 500-800r/min until the bisphenol A is completely dissolved, heating to 70-80 ℃, dropwise adding a sodium hydroxide solution while stirring, controlling the dropwise adding rate to be 2-5 seconds/drop, stirring at constant temperature for 2-3 hours after dropwise adding, cooling to room temperature after the reaction is finished, adding trichloromethane into a reaction product, continuously stirring for 5-10min, washing with distilled water for 3-5 times, standing for layering, collecting an organic phase, drying with anhydrous magnesium sulfate, filtering, rotatably evaporating the filtrate to remove the solvent, purifying the evaporation product by a silica gel column chromatography with dichloromethane as an eluent, and then placing the mixture in a vacuum drying oven to be dried until dichloromethane is completely volatilized, so as to obtain the hydrolysis inhibitor.
The reaction principle is as follows:
as a further scheme of the invention: the dosage ratio of the bisphenol A, the epichlorohydrin, the deionized water, the isopropanol, the sodium hydroxide solution and the trichloromethane is 2.47 g: 9.0 mL: 1.0 mL: 7.0 mL: 12mL, and the mass fraction of the sodium hydroxide solution is 10%.
As a further scheme of the invention: a preparation method of a high corrosion-resistant silicone rubber material comprises the following steps:
the method comprises the following steps: preparing modified silicon rubber;
step two: preparing a hydrolysis inhibitor;
step three: weighing 100 parts of modified silicone rubber, 150 parts of thermoplastic polyurethane elastomer, 50-70 parts of hydrolysis inhibitor and 15-25 parts of white carbon black according to parts by weight;
step four: adding the modified silicone rubber and the thermoplastic polyurethane elastomer into an open mill for open milling, then adding a hydrolysis inhibitor for mixing for 10-20min, then adding white carbon black for continuously mixing for 30-60min, blanking, placing the rubber material at room temperature for 2-3h, then carrying out secondary mixing, then placing the mixed rubber material into a vulcanizing machine, and completing vulcanization under the condition of 10-12MPa to obtain the silicone rubber material with high corrosion resistance.
The invention has the beneficial effects that:
the high corrosion-resistant silicone rubber material and the preparation method thereof are characterized in that modified silicone rubber and a thermoplastic polyurethane elastomer are added into an open mill for open milling, then a hydrolysis inhibitor is added for mixing, then white carbon black is added for continuous mixing, blanking is carried out, the rubber material is placed at room temperature and then is subjected to secondary mixing, and then the mixed rubber material is placed into a vulcanizing machine for completing vulcanization, so that the high corrosion-resistant silicone rubber material is obtained; according to the preparation method, the modified silicone rubber is prepared firstly, so that the hydrophobic property and the stability of the silicone rubber are improved, the contact between the interior of a molecule and water is reduced, the corrosion resistance of the molecule is improved, ester groups, urethane groups and urea groups in the molecules of the thermoplastic polyurethane elastomer are easy to hydrolyze and break, carboxyl groups are generated, the existence of the carboxyl groups promotes the hydrolysis of the thermoplastic polyurethane elastomer, the epoxy groups in the hydrolysis inhibitor and the carboxyl, hydroxyl, amino and the like containing protons generated in the hydrolysis process of the thermoplastic polyurethane elastomer are subjected to ring-opening addition reaction through preparing the hydrolysis inhibitor, the hydrolysis of the thermoplastic polyurethane elastomer is inhibited, the hydrolysis resistance and the corrosion resistance of the thermoplastic polyurethane elastomer are improved, and under the synergistic effect of the modified silicone rubber and the hydrolysis inhibitor, the silicone rubber and polyurethane composite material are excellent in mechanical properties and excellent.
The modified silicone rubber is prepared in the process of preparing the high corrosion-resistant silicone rubber material, p-bromophenol is used as a raw material, cesium carbonate is used as an acid-binding agent, the p-bromobenzotrifluoride reacts with the cesium carbonate to generate an intermediate 1, the intermediate 1 and methyltrimethoxysilane undergo a Grignard reaction to generate an intermediate 2, the intermediate 2 is hydrolyzed under the catalysis of strong acid to form an intermediate 3 containing siloxane, finally the intermediate 3 and octamethylcyclotetrasiloxane undergo an anion ring-opening polymerization reaction by using potassium hydroxide as a catalyst to prepare the modified silicone rubber, a large number of benzene rings and C-F bonds are introduced into the molecular chain of the modified silicone rubber, the benzene rings are good in stability and high in rigidity, the electronegativity of fluorine atoms is high, the polarizability is low, the bond length of the C-F bonds is short, the carbon chains are easy to be tightly surrounded by the fluorine atoms to form a negative charge shielding layer, and the attack of nucleophilic reagents is blocked, the surface energy of the material is reduced, and in addition, the bond energy of the C-F bond is higher than that of the C-H bond and the C-C bond, and the thermal stability is higher, so that the modified silicone rubber not only keeps a series of excellent performances of good high and low temperature resistance, electrical insulation, weather resistance, rebound resilience and the like of the silicone rubber, but also increases the corrosion resistance, the high temperature resistance, the oil resistance and the chemical solvent resistance.
The hydrolysis inhibitor is prepared in the process of preparing the high-corrosion-resistance silicon rubber material, bisphenol A and epoxy chloropropane are used as raw materials, phenolic hydroxyl of the bisphenol A reacts with epoxy groups of the epoxy chloropropane to form chlorohydroxy ether, HCl is removed under the action of alkali to generate the hydrolysis inhibitor, two ends of a molecular chain of the hydrolysis inhibitor are respectively provided with an epoxy functional group, the epoxy functional groups can perform ring-opening addition reaction with carboxyl, hydroxyl, amino and the like containing protons, the epoxy functional groups are eliminated, and the irrational influence of the existence of the functional groups on the silicon rubber material is avoided.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
the embodiment is a preparation method of modified silicone rubber, comprising the following steps:
a1: adding p-bromophenol, cesium carbonate and dimethyl sulfoxide into a three-neck flask provided with a stirrer, a gas guide tube and a constant-pressure dropping funnel, introducing argon for protection, stirring for 10 hours at room temperature and at a stirring speed of 500r/min, then dropwise adding p-bromotrifluorotoluene while stirring, controlling the dropwise adding speed to be 5mL/min, heating to 50 ℃ after dropwise adding, continuing stirring for reaction for 20 hours, controlling the heating speed to be 1 ℃/min, after the reaction is finished, carrying out vacuum filtration, extracting the filtrate for 2 times by using ethyl acetate, combining the extract solutions, washing for 2 times by using a saturated sodium chloride solution, standing for layering, drying the organic layer by using anhydrous sodium sulfate, concentrating the organic layer, purifying by using a silica gel column chromatography, and then carrying out rotary evaporation to obtain an intermediate 1; controlling the dosage ratio of p-bromophenol, cesium carbonate, dimethyl sulfoxide and p-bromotrifluorotoluene to be 0.10 mol: 0.15 mol: 200mL of: 0.20 mol;
a2: adding magnesium powder, methyltrimethoxysilane and tetrahydrofuran into a three-neck flask provided with a stirrer, a gas guide tube and a constant-pressure dropping funnel, introducing argon gas for protection, dropwise adding the intermediate 1 solution while stirring at the room temperature and the stirring speed of 300r/min, controlling the dropwise adding speed to be 2 drops/s, continuously stirring and reacting for 20 hours after the dropwise adding is finished, heating to boil after the reaction is finished, cooling to the room temperature by using an ice water bath, adding toluene into the reaction product, stirring and mixing for 3min, then carrying out vacuum filtration, and distilling the filtrate under reduced pressure to obtain an intermediate 2; controlling the dosage ratio of magnesium powder, methyltrimethoxysilane, tetrahydrofuran, the intermediate 1 solution and toluene to be 0.8 mol: 66.44 g: 200mL of: 20mL of: 150mL, intermediate 1 solution is intermediate 1 and tetrahydrofuran according to 0.08 mol: 10mL of the solution formed after mixing;
a3: adding a hydrochloric acid solution and half of toluene into a three-neck flask provided with a stirrer and a constant pressure dropping funnel, uniformly mixing an intermediate 2, the other half of toluene and dimethyl dimethoxy silane, adding into the constant pressure dropping funnel, stirring while dropwise adding into the three-neck flask under the condition that the stirring speed is 500r/min, controlling the dropwise adding speed to be 1mL/min, heating to 50 ℃, stirring for reacting for 6 hours, after the reaction is finished, washing the reaction product with distilled water to be neutral, drying with anhydrous sodium sulfate, filtering, and distilling the filtrate under reduced pressure to obtain an intermediate 3; controlling the dosage ratio of the hydrochloric acid solution, the toluene, the intermediate 2 and the dimethyl dimethoxy silane to be 30 mL: 30mL of: 9 mmol: 27mmol of the total weight of the mixture;
a4: adding potassium hydroxide into a three-neck flask provided with a stirrer and a constant-pressure dropping funnel, heating to 60 ℃, performing reduced-pressure dehydration for 2 hours, introducing argon for protection, then adding an intermediate 3, heating to 120 ℃, stirring and reacting for 4 hours at a stirring speed of 500r/min, and cooling a reaction product to room temperature after the reaction is finished to obtain a catalyst; adding the intermediate 3 and octamethylcyclotetrasiloxane into a reaction kettle, heating to 35 ℃, performing reduced pressure dehydration for 30min, introducing argon for protection, then adding a catalyst and N, N-dimethylformamide, heating to 80 ℃, and performing constant temperature reaction for 30min to obtain modified silicone rubber; controlling the dosage ratio of the intermediate 3, the octamethylcyclotetrasiloxane, the catalyst and the N, N-dimethylformamide to be 0.5 g: 50 g: 1.0 g: 200 mL; the mass ratio of the potassium hydroxide to the intermediate 3 is 1: 100.
example 2:
the embodiment is a preparation method of modified silicone rubber, comprising the following steps:
a1: adding p-bromophenol, cesium carbonate and dimethyl sulfoxide into a three-neck flask provided with a stirrer, a gas guide tube and a constant-pressure dropping funnel, introducing argon for protection, stirring for 12 hours at room temperature and at a stirring speed of 800r/min, then dropwise adding p-bromotrifluorotoluene while stirring, controlling the dropwise adding speed to be 1mL/min, heating to 55 ℃ after dropwise adding, continuing stirring for reaction for 30 hours, controlling the heating speed to be 1 ℃/min, after the reaction is finished, carrying out vacuum filtration, extracting the filtrate for 3 times by using ethyl acetate, combining the extract solutions, washing for 3 times by using a saturated sodium chloride solution, standing for layering, drying an organic layer by using anhydrous sodium sulfate, concentrating the organic layer, purifying by using a silica gel column chromatography, and then carrying out rotary evaporation to obtain an intermediate 1; controlling the dosage ratio of p-bromophenol, cesium carbonate, dimethyl sulfoxide and p-bromotrifluorotoluene to be 0.10 mol: 0.15 mol: 150: 0.20 mol;
a2: adding magnesium powder, methyltrimethoxysilane and tetrahydrofuran into a three-neck flask provided with a stirrer, a gas guide tube and a constant-pressure dropping funnel, introducing argon gas for protection, dropwise adding the intermediate 1 solution while stirring at the room temperature and the stirring speed of 400r/min, controlling the dropwise adding speed to be 1 drop/s, continuously stirring and reacting for 30 hours after the dropwise adding is finished, heating to boil after the reaction is finished, cooling to the room temperature by using an ice water bath, adding toluene into the reaction product, stirring and mixing for 5min, then carrying out vacuum filtration, and distilling the filtrate under reduced pressure to obtain an intermediate 2; controlling the dosage ratio of magnesium powder, methyltrimethoxysilane, tetrahydrofuran, the intermediate 1 solution and toluene to be 0.8 mol: 66.44 g: 150mL of: 20mL of: 100mL, intermediate 1 solution is intermediate 1 and tetrahydrofuran according to 0.08 mol: 10mL of the solution formed after mixing;
a3: adding a hydrochloric acid solution and half of toluene into a three-neck flask provided with a stirrer and a constant pressure dropping funnel, uniformly mixing an intermediate 2, the other half of toluene and dimethyl dimethoxy silane, adding into the constant pressure dropping funnel, stirring and dropwise adding into the three-neck flask under the condition that the stirring speed is 600r/min, controlling the dropwise adding speed to be 0.5mL/min, heating to 55 ℃, stirring and reacting for 8 hours, after the reaction is finished, washing the reaction product to be neutral by using distilled water, drying by using anhydrous sodium sulfate, filtering, and distilling the filtrate under reduced pressure to obtain an intermediate 3; controlling the dosage ratio of the hydrochloric acid solution, the toluene, the intermediate 2 and the dimethyl dimethoxy silane to be 30 mL: 30mL of: 9 mmol: 27mmol of the total weight of the mixture;
a4: adding potassium hydroxide into a three-neck flask provided with a stirrer and a constant-pressure dropping funnel, heating to 70 ℃, performing reduced-pressure dehydration for 3 hours, introducing argon for protection, then adding an intermediate 3, heating to 130 ℃, stirring and reacting for 5 hours at a stirring speed of 800r/min, and cooling a reaction product to room temperature after the reaction is finished to obtain a catalyst; adding the intermediate 3 and octamethylcyclotetrasiloxane into a reaction kettle, heating to 40 ℃, decompressing and dehydrating for 50min, introducing argon for protection, then adding a catalyst and N, N-dimethylformamide, heating to 110 ℃, and reacting at constant temperature for 40min to obtain modified silicone rubber; controlling the dosage ratio of the intermediate 3, the octamethylcyclotetrasiloxane, the catalyst and the N, N-dimethylformamide to be 0.5-1.0 g: 50 g: 1.0 g: 100 mL; the mass ratio of the potassium hydroxide to the intermediate 3 is 1: 50.
example 3:
this embodiment is a method for preparing a hydrolysis inhibitor, comprising the steps of:
adding bisphenol A, epichlorohydrin, deionized water and isopropanol into a four-neck flask provided with a stirrer, a reflux condenser tube and a constant-pressure dropping funnel, stirring at a stirring rate of 500r/min until the bisphenol A is completely dissolved, heating to 70 ℃, dropwise adding a sodium hydroxide solution while stirring, controlling the dropwise adding rate to be 2 seconds/drop, stirring at constant temperature for reaction for 2 hours after the dropwise adding is finished, cooling to room temperature after the reaction is finished, adding trichloromethane into a reaction product, continuously stirring for 5min, washing with distilled water for 3 times, standing for layering, collecting an organic phase, drying with anhydrous magnesium sulfate, filtering, rotatably evaporating the filtrate, purifying the evaporation product by silica gel column chromatography, and then placing in a vacuum drying oven for drying to obtain a hydrolysis inhibitor; controlling the dosage ratio of bisphenol A, epichlorohydrin, deionized water, isopropanol, sodium hydroxide solution and chloroform to be 2.47 g: 9.0 mL: 1.0 mL: 7.0 mL: 12mL, and the mass fraction of the sodium hydroxide solution is 10%.
Example 4:
this embodiment is a method for preparing a hydrolysis inhibitor, comprising the steps of:
adding bisphenol A, epichlorohydrin, deionized water and isopropanol into a four-neck flask provided with a stirrer, a reflux condenser tube and a constant-pressure dropping funnel, stirring at a stirring speed of 800r/min until the bisphenol A is completely dissolved, heating to 80 ℃, dropwise adding a sodium hydroxide solution while stirring, controlling the dropwise adding speed to be 5 seconds/drop, stirring at constant temperature for reaction for 3 hours after the dropwise adding is finished, cooling to room temperature after the reaction is finished, adding trichloromethane into a reaction product, continuously stirring for 10min, washing with distilled water for 5 times, standing for layering, collecting an organic phase, drying with anhydrous magnesium sulfate, filtering, rotatably evaporating the filtrate, purifying the evaporation product by silica gel column chromatography, and then placing in a vacuum drying oven for drying to obtain a hydrolysis inhibitor; controlling the dosage ratio of bisphenol A, epichlorohydrin, deionized water, isopropanol, sodium hydroxide solution and chloroform to be 2.47 g: 9.0 mL: 1.0 mL: 7.0 mL: 12mL, and the mass fraction of the sodium hydroxide solution is 10%.
Example 5:
the embodiment is a preparation method of a high corrosion-resistant silicone rubber material, which comprises the following steps:
the method comprises the following steps: weighing 100 parts of modified silicone rubber from example 1, 50 parts of thermoplastic polyurethane elastomer, 1 part of hydrolysis inhibitor from example 3 and 15 parts of white carbon black according to parts by weight;
step two: adding the modified silicone rubber and the thermoplastic polyurethane elastomer into an open mill for open milling, then adding a hydrolysis inhibitor for mixing for 10min, then adding white carbon black for continuously mixing for 30min, blanking, placing the rubber material at room temperature for 2h, then carrying out secondary mixing, then placing the mixed rubber material into a vulcanizing machine, and completing vulcanization under the condition of 10MPa to obtain the silicone rubber material with high corrosion resistance.
Example 6:
the embodiment is a preparation method of a high corrosion-resistant silicone rubber material, which comprises the following steps:
the method comprises the following steps: weighing 150 parts of modified silicone rubber from example 2, 70 parts of thermoplastic polyurethane elastomer, 10 parts of hydrolysis inhibitor from example 4 and 25 parts of white carbon black according to parts by weight;
step two: adding the modified silicone rubber and the thermoplastic polyurethane elastomer into an open mill for open milling, then adding a hydrolysis inhibitor for mixing for 20min, then adding white carbon black for continuously mixing for 60min, blanking, placing the rubber material at room temperature for 3h, then carrying out secondary mixing, then placing the mixed rubber material into a vulcanizing machine, and completing vulcanization under the condition of 12MPa to obtain the silicone rubber material with high corrosion resistance.
Comparative example 1:
comparative example 1 differs from example 6 in that methyl silicone rubber is used instead of modified silicone rubber.
Comparative example 2:
comparative example 2 differs from example 6 in that no hydrolysis inhibitor was added.
Comparative example 3:
comparative example 3 is a corrosion-resistant silicone rubber material for a cable of application No. CN 201610714998.0.
The silicone rubber materials of examples 5-6 and comparative examples 1-3 were tested and the tensile strength, elongation at break and tear strength tests of the samples were tested according to GB/T528-. Corrosion resistance experiment: the rubber sheet is cut into a circle with the diameter of 30mm, placed in a salt fog environment specified by GJB 150.11A-2009 national military standard, continuously sprayed for 24h, dried for 24h under the conditions of 15-35 ℃ and relative humidity of 50%, 48h is a period, and the experiment is carried out for 3 periods (144 h).
The results are shown in the following table:
referring to the data in the table, according to the comparison between the example and the comparative example 1, it can be known that the modified silicone rubber has better corrosion resistance, according to the comparison between the example and the comparative example 2, the hydrolysis inhibitor can obviously improve the corrosion resistance of the rubber material, and the hydrolysis inhibition effect is good, and according to the comparison between the example and the comparative example 3, the silicone rubber material in the invention has better corrosion resistance than the corrosion-resistant silicone rubber material in the prior art.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications, additions, and substitutions may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the claims.
Claims (10)
1. The high-corrosion-resistance silicone rubber material is characterized by comprising the following components in parts by weight:
100-150 parts of modified silicon rubber, 50-70 parts of thermoplastic polyurethane elastomer, 1-10 parts of hydrolysis inhibitor and 15-25 parts of white carbon black;
the high-corrosion-resistance silicone rubber material is prepared by the following steps:
the method comprises the following steps: preparing modified silicon rubber;
step two: preparing a hydrolysis inhibitor;
step three: adding the modified silicone rubber and the thermoplastic polyurethane elastomer into an open mill for open milling, then adding a hydrolysis inhibitor for mixing for 10-20min, then adding white carbon black for continuously mixing for 30-60min, blanking, placing the rubber material at room temperature for 2-3h, then carrying out secondary mixing, then placing the mixed rubber material into a vulcanizing machine, and completing vulcanization under the condition of 10-12MPa to obtain the silicone rubber material with high corrosion resistance.
2. The silicone rubber material with high corrosion resistance according to claim 1, wherein the modified silicone rubber is prepared by the following steps:
a1: adding p-bromophenol, cesium carbonate and dimethyl sulfoxide into a three-neck flask provided with a stirrer, an air guide pipe and a constant-pressure dropping funnel, introducing argon for protection, stirring for 10-12h at room temperature and at a stirring rate of 500-800r/min, then dropwise adding para-bromobenzotrifluoride while stirring, controlling the dropping rate to be 1-5mL/min, heating to 50-55 ℃ after the dropping is finished, continuing stirring and reacting for 20-30h, controlling the heating rate to be 1 ℃/min, after the reaction is finished, vacuum filtering, extracting the filtrate with ethyl acetate for 2-3 times, mixing the extractive solutions, washing with saturated sodium chloride solution for 2-3 times, standing for layering, drying the organic layer with anhydrous sodium sulfate, concentrating the organic layer, purifying by silica gel column chromatography, and rotary evaporating to obtain intermediate 1;
a2: adding magnesium powder, methyltrimethoxysilane and tetrahydrofuran into a three-neck flask provided with a stirrer, a gas-guide tube and a constant-pressure dropping funnel, introducing argon gas for protection, stirring and dropwise adding the intermediate 1 solution while stirring at the room temperature and the stirring rate of 300-400r/min, controlling the dropwise adding rate to be 1-2 drops/s, continuously stirring and reacting for 20-30h after the dropwise adding is finished, heating to boiling after the reaction is finished, cooling to the room temperature by using an ice water bath, adding toluene into the reaction product, stirring and mixing for 3-5min, carrying out vacuum filtration, and distilling the filtrate under reduced pressure to obtain an intermediate 2;
a3: adding a hydrochloric acid solution and half of toluene into a three-neck flask provided with a stirrer and a constant pressure dropping funnel, uniformly mixing an intermediate 2, the other half of toluene and dimethyl dimethoxysilane, then adding into the constant pressure dropping funnel, stirring and dropwise adding into the three-neck flask under the condition that the stirring speed is 500-600r/min, controlling the dropwise adding speed to be 0.5-1mL/min, then heating to 50-55 ℃, stirring and reacting for 6-8h, after the reaction is finished, washing a reaction product to be neutral by using distilled water, then drying by using anhydrous sodium sulfate, filtering, and distilling the filtrate under reduced pressure to obtain an intermediate 3;
a4: adding the intermediate 3 and octamethylcyclotetrasiloxane into a reaction kettle, heating to 35-40 ℃, performing reduced pressure dehydration for 30-50min, introducing argon for protection, then adding a catalyst and N, N-dimethylformamide, heating to 80-110 ℃, and reacting at constant temperature for 30-40min to obtain the modified silicone rubber.
3. The silicone rubber material with high corrosion resistance according to claim 2, wherein the p-bromophenol, cesium carbonate, dimethyl sulfoxide, and p-bromotrifluorotoluene in step a1 are used in a ratio of 0.10 mol: 0.15 mol: 150-200 mL: 0.20 mol.
4. The silicone rubber material with high corrosion resistance according to claim 2, wherein the amount ratio of magnesium powder, methyltrimethoxysilane, tetrahydrofuran, intermediate 1 solution, and toluene in step a2 is 0.8 mol: 66.44 g: 150-200 mL: 20mL of: 100-150mL, wherein the solution of the intermediate 1 is the mixture of the intermediate 1 and tetrahydrofuran according to the mol ratio of 0.08 mol: 10mL of the resulting solution after mixing.
5. The silicone rubber material with high corrosion resistance according to claim 2, wherein the amount ratio of the hydrochloric acid solution, toluene, intermediate 2, and dimethyldimethoxysilane in step a3 is 30 mL: 30mL of: 9 mmol: 27 mmol.
6. The silicone rubber material with high corrosion resistance according to claim 2, wherein the intermediate 3, octamethylcyclotetrasiloxane, catalyst, and N, N-dimethylformamide in step a4 are used in a ratio of 0.5 to 1.0 g: 50 g: 1.0 g: 100 and 200 mL.
7. The silicone rubber material with high corrosion resistance according to claim 2, wherein the catalyst in step a4 is prepared by the following steps:
adding potassium hydroxide into a three-neck flask provided with a stirrer and a constant-pressure dropping funnel, heating to 60-70 ℃, performing reduced-pressure dehydration for 2-3h, introducing argon for protection, then adding an intermediate 3, heating to 120-; the mass ratio of the potassium hydroxide to the intermediate 3 is 1: 50-100.
8. The silicone rubber material with high corrosion resistance according to claim 1, wherein the hydrolysis inhibitor is prepared by the following steps:
adding bisphenol A, epichlorohydrin, deionized water and isopropanol into a four-neck flask provided with a stirrer, a reflux condenser tube and a constant-pressure dropping funnel, stirring at the stirring rate of 500-800r/min until the bisphenol A is completely dissolved, heating to 70-80 ℃, dropwise adding a sodium hydroxide solution while stirring, controlling the dropwise adding rate to be 2-5 seconds/drop, stirring at constant temperature for 2-3 hours after dropwise adding, cooling to room temperature after the reaction is finished, adding trichloromethane into a reaction product, continuously stirring for 5-10min, washing with distilled water for 3-5 times, standing for layering, collecting an organic phase, drying with anhydrous magnesium sulfate, filtering, rotationally evaporating the filtrate, purifying the evaporation product by a silica gel column chromatography, then placing in a vacuum drying oven for drying, obtaining the hydrolysis inhibitor.
9. The silicone rubber material with high corrosion resistance according to claim 8, wherein the usage ratio of the bisphenol A, the epichlorohydrin, the deionized water, the isopropanol, the sodium hydroxide solution and the chloroform is 2.47 g: 9.0 mL: 1.0 mL: 7.0 mL: 12mL, and the mass fraction of the sodium hydroxide solution is 10%.
10. The method for preparing the silicone rubber material with high corrosion resistance according to claim 1, comprising the steps of:
the method comprises the following steps: preparing modified silicon rubber;
step two: preparing a hydrolysis inhibitor;
step three: weighing 100 parts of modified silicone rubber, 150 parts of thermoplastic polyurethane elastomer, 50-70 parts of hydrolysis inhibitor and 15-25 parts of white carbon black according to parts by weight;
step four: adding the modified silicone rubber and the thermoplastic polyurethane elastomer into an open mill for open milling, then adding a hydrolysis inhibitor for mixing for 10-20min, then adding white carbon black for continuously mixing for 30-60min, blanking, placing the rubber material at room temperature for 2-3h, then carrying out secondary mixing, then placing the mixed rubber material into a vulcanizing machine, and completing vulcanization under the condition of 10-12MPa to obtain the silicone rubber material with high corrosion resistance.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110751535.2A CN113321935A (en) | 2021-07-02 | 2021-07-02 | High-corrosion-resistance silicone rubber material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110751535.2A CN113321935A (en) | 2021-07-02 | 2021-07-02 | High-corrosion-resistance silicone rubber material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113321935A true CN113321935A (en) | 2021-08-31 |
Family
ID=77425603
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110751535.2A Pending CN113321935A (en) | 2021-07-02 | 2021-07-02 | High-corrosion-resistance silicone rubber material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113321935A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115074026A (en) * | 2022-06-30 | 2022-09-20 | 马鞍山欧凯新材料科技有限公司 | Carbon fiber corona roller for lithium battery aluminum foil |
| CN115140872A (en) * | 2022-09-07 | 2022-10-04 | 中山市中环环保废液回收有限公司 | Low-energy-consumption treatment method for high-salt high-COD wastewater |
| CN115216073A (en) * | 2022-08-24 | 2022-10-21 | 广东安拓普聚合物科技有限公司 | Oil-resistant corrosion-resistant shore power cable sheath material and preparation method thereof |
| CN115478268A (en) * | 2022-08-04 | 2022-12-16 | 江阴市华昌不锈钢管有限公司 | Production process of large-caliber stainless steel seamless steel pipe |
| CN116640450A (en) * | 2023-06-15 | 2023-08-25 | 安徽工业大学 | Rubber based on sulfur-containing industrial solid waste and preparation method thereof |
| CN117264316A (en) * | 2023-08-24 | 2023-12-22 | 江苏海聚新材料科技有限公司 | Antistatic polyolefin composition and preparation method thereof |
| CN117986663A (en) * | 2023-12-26 | 2024-05-07 | 上海焦能新材料有限公司 | High-temperature-resistant corrosion-resistant alloy rubber and preparation method thereof |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1280995A (en) * | 1999-07-16 | 2001-01-24 | 中国科学院化学研究所 | Trapezoidal polysiloxane containing organic bridge radical and its preparing process |
| US20090039313A1 (en) * | 2007-07-27 | 2009-02-12 | Rohm And Haas Company | (Thio)phenoxy phenyl silane compostion and method for making same |
| CN102153855A (en) * | 2011-02-25 | 2011-08-17 | 深圳职业技术学院 | Hydrolysis-resistant thermoplastic polyurethane elastomer and manufacture method thereof |
| CN103408944A (en) * | 2013-07-01 | 2013-11-27 | 芜湖市银鸿液压件有限公司 | Silicon rubber/polyurethane rubber composite hydraulic sealing gasket and preparation method thereof |
| CN103992654A (en) * | 2014-04-22 | 2014-08-20 | 天长市富信电子有限公司 | Cold-resistant power line sheath material and preparing method thereof |
| CN104231598A (en) * | 2014-09-18 | 2014-12-24 | 苏州市雄林新材料科技有限公司 | TPU (thermoplastic polyurethane) film with high hydrolytic stability and preparation method of TPU film |
| CN104448289A (en) * | 2014-11-27 | 2015-03-25 | 山东一诺威新材料有限公司 | Polyether polyol capable of improving damping capacity of polyurethane, preparation method of polyether polyol and preparation method of damping material prepared from polyether polyol |
| CN104650591A (en) * | 2013-11-19 | 2015-05-27 | 青岛欧美亚橡胶工业有限公司 | Preparation method of polyurethane rubber / silicone gross rubber |
| CN109384958A (en) * | 2018-10-19 | 2019-02-26 | 山东大学 | A kind of room temperature vulcanized silicone rubber crosslinking agent preparation method and applications |
| CN112143231A (en) * | 2020-08-21 | 2020-12-29 | 北京化工大学 | Silicone rubber/polyurethane thermoplastic vulcanized rubber and preparation method and application thereof |
| CN112210219A (en) * | 2020-10-12 | 2021-01-12 | 东莞市润银实业有限公司 | Silicon rubber with wide temperature range and long storage life and preparation method thereof |
-
2021
- 2021-07-02 CN CN202110751535.2A patent/CN113321935A/en active Pending
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1280995A (en) * | 1999-07-16 | 2001-01-24 | 中国科学院化学研究所 | Trapezoidal polysiloxane containing organic bridge radical and its preparing process |
| US20090039313A1 (en) * | 2007-07-27 | 2009-02-12 | Rohm And Haas Company | (Thio)phenoxy phenyl silane compostion and method for making same |
| CN102153855A (en) * | 2011-02-25 | 2011-08-17 | 深圳职业技术学院 | Hydrolysis-resistant thermoplastic polyurethane elastomer and manufacture method thereof |
| CN103408944A (en) * | 2013-07-01 | 2013-11-27 | 芜湖市银鸿液压件有限公司 | Silicon rubber/polyurethane rubber composite hydraulic sealing gasket and preparation method thereof |
| CN104650591A (en) * | 2013-11-19 | 2015-05-27 | 青岛欧美亚橡胶工业有限公司 | Preparation method of polyurethane rubber / silicone gross rubber |
| CN103992654A (en) * | 2014-04-22 | 2014-08-20 | 天长市富信电子有限公司 | Cold-resistant power line sheath material and preparing method thereof |
| CN104231598A (en) * | 2014-09-18 | 2014-12-24 | 苏州市雄林新材料科技有限公司 | TPU (thermoplastic polyurethane) film with high hydrolytic stability and preparation method of TPU film |
| CN104448289A (en) * | 2014-11-27 | 2015-03-25 | 山东一诺威新材料有限公司 | Polyether polyol capable of improving damping capacity of polyurethane, preparation method of polyether polyol and preparation method of damping material prepared from polyether polyol |
| CN109384958A (en) * | 2018-10-19 | 2019-02-26 | 山东大学 | A kind of room temperature vulcanized silicone rubber crosslinking agent preparation method and applications |
| CN112143231A (en) * | 2020-08-21 | 2020-12-29 | 北京化工大学 | Silicone rubber/polyurethane thermoplastic vulcanized rubber and preparation method and application thereof |
| CN112210219A (en) * | 2020-10-12 | 2021-01-12 | 东莞市润银实业有限公司 | Silicon rubber with wide temperature range and long storage life and preparation method thereof |
Non-Patent Citations (8)
| Title |
|---|
| RUI HUANG 等: "Study on the Synthesis and Thermal Stability of Silicone Resin Containing Trifluorovinyl Ether Groups", 《POLYMERS》 * |
| 刘勇军 等: "二(4-苯氧基苯基)二甲基硅烷的合成与表征", 《江西师范大学学报(自然科学版)》 * |
| 岩仓义男 等著: "《缩聚与聚加成反应》", 30 April 1965, 上海科学技术出版社 * |
| 李子东 编著: "《实用粘接手册》", 30 April 1987, 上海科学技术出版社 * |
| 李恒德 主编: "《现代材料科学与工程辞典》", 31 August 2001, 山东科学技术出版社 * |
| 王文广 主编: "《聚合物改性原理》", 31 March 2018, 中国轻工业出版社 * |
| 王昌尧 等: "3,5-双(三氟甲基)苯基硅油的合成及性能研究", 《有机硅材料》 * |
| 赵洪池 等: "双酚A二缩水甘油醚的合成", 《合成树脂及塑料》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115074026A (en) * | 2022-06-30 | 2022-09-20 | 马鞍山欧凯新材料科技有限公司 | Carbon fiber corona roller for lithium battery aluminum foil |
| CN115478268A (en) * | 2022-08-04 | 2022-12-16 | 江阴市华昌不锈钢管有限公司 | Production process of large-caliber stainless steel seamless steel pipe |
| CN115478268B (en) * | 2022-08-04 | 2024-01-05 | 江阴市华昌不锈钢管有限公司 | Production process of large-caliber stainless steel seamless steel pipe |
| CN115216073A (en) * | 2022-08-24 | 2022-10-21 | 广东安拓普聚合物科技有限公司 | Oil-resistant corrosion-resistant shore power cable sheath material and preparation method thereof |
| CN115140872A (en) * | 2022-09-07 | 2022-10-04 | 中山市中环环保废液回收有限公司 | Low-energy-consumption treatment method for high-salt high-COD wastewater |
| CN116640450A (en) * | 2023-06-15 | 2023-08-25 | 安徽工业大学 | Rubber based on sulfur-containing industrial solid waste and preparation method thereof |
| CN117264316A (en) * | 2023-08-24 | 2023-12-22 | 江苏海聚新材料科技有限公司 | Antistatic polyolefin composition and preparation method thereof |
| CN117264316B (en) * | 2023-08-24 | 2024-05-14 | 江苏海聚新材料科技有限公司 | Antistatic polyolefin composition and preparation method thereof |
| CN117986663A (en) * | 2023-12-26 | 2024-05-07 | 上海焦能新材料有限公司 | High-temperature-resistant corrosion-resistant alloy rubber and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113321935A (en) | High-corrosion-resistance silicone rubber material and preparation method thereof | |
| CN114605838B (en) | High-water-resistance electronic silica gel and preparation method thereof | |
| CN1974633A (en) | Fluoric alkoxyl propyl methyl silicone oil and its prepn process | |
| CN112552482B (en) | Bio-based phosphaphenanthrene biphenyl type epoxy resin as well as preparation method and application thereof | |
| CN109734684B (en) | Bio-based flame-retardant epoxy resin precursor based on natural phenolic monomers, and preparation method and application thereof | |
| CN112409298B (en) | Epoxy resin monomer based on p-hydroxy cinnamic acid and preparation method and application thereof | |
| CN111363158A (en) | Epoxy group-containing polysiloxane borane hyperbranched polymer and preparation method thereof | |
| CN111253575A (en) | Preparation method and application of high-refractive-index phenyl methyl amino silicone resin | |
| CN107226909A (en) | A kind of fabric softener epoxy modified polysiloxane preparation method processed | |
| CN111117162A (en) | Resveratrol-based bio-based carbon fiber composite material and preparation method thereof | |
| CN102675645A (en) | Alpha, omega-hydroxyl-terminated diphenyl siloxane and dimethhyl siloxane copolymer and preparation method thereof | |
| CN102898567B (en) | Fluorine-containing epoxy resin, and preparation method and application thereof | |
| CN104371108B (en) | A kind of non-halogen non-phosphate Silicone-containing Flame Retardant and preparation method thereof | |
| CN113957721B (en) | Anti-wrinkle elastic silicone oil and preparation method thereof | |
| CN109593204A (en) | A kind of application method reducing the secondary addition by-product of hydrogen silicon | |
| CN115785759A (en) | High-strength, corrosion-resistant and high-temperature-resistant exhaust pipe flange for vehicle | |
| CN114752337A (en) | Waterproof MS sealant and preparation method thereof | |
| CN107915819A (en) | A kind of thermosetting resin with propargyl ether and preparation method thereof | |
| CN101215363A (en) | Method for synthesizing organic silicon di-block copolymers | |
| CN103539924A (en) | Low-electrical impedance epoxy resin and preparation method thereof | |
| CN112920160B (en) | Degradable monomer based on cyclic acetal structure, and synthesis method and application thereof | |
| CN113881392A (en) | Preparation method of deacidification type organic silicon adhesive | |
| CN113603879A (en) | Novel fluorine-containing hyperbranched polyglycidyl glycerin and preparation method thereof | |
| CN106631751B (en) | More two fluorine monomers of methyl chains of anti-oxidative and preparation method thereof | |
| CN110172024A (en) | A method of anhydrous ethylenediamine is produced from diamine base silane by-product ethylenediamine-hydrochloride |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210831 |