CN110698613A - Preparation method of high-crosslinking organic silicon rubber - Google Patents
Preparation method of high-crosslinking organic silicon rubber Download PDFInfo
- Publication number
- CN110698613A CN110698613A CN201911062288.4A CN201911062288A CN110698613A CN 110698613 A CN110698613 A CN 110698613A CN 201911062288 A CN201911062288 A CN 201911062288A CN 110698613 A CN110698613 A CN 110698613A
- Authority
- CN
- China
- Prior art keywords
- parts
- rubber
- nano
- silicon rubber
- weight
- 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
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
- C08K5/57—Organo-tin compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The invention relates to a preparation method of high-crosslinking organic silicon rubber, belonging to the technical field of rubber materials. The invention prepares a high cross-linking organic silicon rubber by adding methacrylic acid and nano zinc oxide, the nano zinc oxide can form strong interaction with the silicon rubber, the high cross-linking organic silicon rubber has excellent reinforcing effect on the silicon rubber, the methacrylic acid and the nano zinc oxide can generate in-situ polymerization reaction in a silicon rubber matrix to form nano particles, the silicon rubber is reinforced, the zinc methacrylate generated by the reaction of the methacrylic acid and the nano zinc oxide is a multifunctional rubber active auxiliary agent, the zinc methacrylate is easy to generate graft polymerization with rubber molecules to form a multi-element cross-linking network, the rubber is reinforced, the zinc methacrylate is polymerized in the silicon rubber and generates graft reaction with a matrix material in the initiating cross-linking process of benzoyl peroxide, and the nano zinc polymethacrylate formed by polymerization is uniformly dispersed in the rubber, and the high cross-linking organic silicon rubber has excellent reinforcing effect.
Description
Technical Field
The invention relates to a preparation method of high-crosslinking organic silicon rubber, belonging to the technical field of rubber materials.
Background
The main chain skeleton of the silicon rubber base rubber is silicon-oxygen-silicon bond, which is the same as the inorganic matter structure unit forming silicic acid and silicate, and at the same time, the silicon rubber base rubber also contains silicon-carbon bond, so that the silicon rubber has the property of partial organic matter, therefore, the silicon rubber is a polymer between organic and inorganic polymers, therefore, the working temperature range of the vulcanized silicon rubber is very wide and is in the range of-100 ~ 350 ℃, meanwhile, the silicon rubber has excellent high and low temperature resistance, excellent heat dissipation performance, excellent adhesion, fluidity and demoulding performance, and some special silicon rubbers also have excellent oil resistance, solvent resistance and other characteristics, and are widely applied to electronics and electricity, national defense and military industry, buildings, chemical engineering, control production and people life.
High temperature vulcanized silicone rubber (HTV rubber) having a molecular weight of 50 ~ 80 (80). times.104The straight-chain polysiloxane is used as base rubber, cross-linking agent, reinforcing filler, catalyst, etc. are compounded in a mixer to obtain homogeneous rubber material, and the rubber material is vulcanized at high temperature (150 ~ 200 deg.c) and then produced into silicone rubber product through mold pressing, extrusion and other technological process.
The room temperature vulcanized silicone rubber, RTV rubber for short, has the same rubber composition as HTV, and also comprises base rubber, reinforcing filler, cross-linking agent, catalyst and the like, but the base rubber is generally (1 ~ 8) x 10 in molar mass4g/mol of the active end group polyorganosiloxane, the mixed glue is viscous liquid with fluidity. The mixed rubber can be vulcanized into rubber elastomer under the condition of room temperature.
According to different packaging and storage forms, the room temperature vulcanized silicone rubber can be divided into single-component room temperature vulcanized silicone rubber (single-component RTV rubber) and double-component room temperature vulcanized silicone rubber (double-component RTV rubber); according to different curing reaction mechanisms, the method can be divided into condensation type and addition type. The single-component RTV glue is only one of condensation type, and the double-component RTV glue comprises two types of condensation type and addition type.
The unreinforced silicon rubber vulcanized rubber has very low mechanical property strength, the tensile strength is only 0.35MPa, the elongation is 50 percent ~ 80 percent, and almost no practical use value.
The following requirements are generally placed on the fillers of rubber products:
(1) the particle surface of the reinforcing filler has stronger chemical activity and can be well combined with a rubber product, so that the mechanical property, the aging resistance and the adhesive property of vulcanized rubber are improved. While the non-reinforcing filler particles are chemically inert at the surface and do not chemically bond to the rubber product. Therefore, the mechanical property, weather resistance, acid and alkali resistance, water resistance and other properties of the vulcanized rubber are not influenced.
High chemical purity, uniform particle fineness, and high wettability and dispersibility to rubber.
Is not easy to volatilize, odorless, tasteless and nontoxic. Has better storage stability.
The filler for white or light-colored rubber products is also required to have the characteristics of no pollution and no discoloration.
The reinforcing filler of silicone rubber has different reinforcing effect and is divided into strong reinforcing filler and weak reinforcing filler, the particle size of the strong reinforcing filler is 10 ~ 50nm, the specific surface area is 70 ~ 400m2The reinforcing effect is better, the particle size of the latter is between 300 ~ 1000nm and 1000nm, the particle size is larger, and the specific surface area is less than 30m2The reinforcing effect is poor.
The main reinforcing filler of silicone rubber is synthetic silica, i.e. silica micropowder, also known as white carbon black. The white carbon black can improve the strength of the rubber material, can also improve the processability of the rubber material, endows the silicone rubber finished product with excellent performances of wear resistance, tear resistance, heat resistance, cold resistance, oil resistance and the like, and can prolong the service life of the product.
White carbon black can be divided into three types: precipitated silica, fumed silica, and surface-treated silica (silica prepared by treating the surface with an organic silicon compound or an organic alcohol, or by adding an organic silicon compound or an organic alcohol during the manufacturing process).
Polyhedral oligomeric or polyhedral oligomeric silsesquioxanes, abbreviated as POSS, of the general formula (RSiO)3/2) n is the same as the formula (I). In recent years, cage-like polysilsesquioxanes have been implicatedThe reports of siloxanes have increased substantially, and cage Polysilsesquioxanes (POSS) additives are now increasingly being used as reinforcing fillers in the synthesis of hybrid nanocomposites because of their chemical versatility compared to silica, organic fillers, and nanomaterials such as carbon nanotubes and nanoclays. Depending on the number of pendant groups in the POSS, they can serve as a polymer backbone, or can serve as a crosslinker. POSS nanocubes can be dispersed as building blocks of controlled shape into polymers such as epoxies, acrylates, norbornenes, styrenes, acetoxystyrenes, and polyurethanes to improve miscibility and elasticity of the hybrid materials.
POSS falls into three basic types, depending on the pendant cage polysilsesquioxane group: from RSiX in which all substituents are identical3A prepared POSS; POSS prepared by type hydrosilation reactions; POSS obtained from the reaction of a part of the clathrate containing silanol groups.
According to the different crosslinking and curing reaction mechanism, silicone rubber is divided into several categories, namely, condensation reaction type (room temperature vulcanization type for short), free radical crosslinking vulcanization type (heating vulcanization type for short) and platinum-catalyzed hydrosilylation reaction type.
Disclosure of Invention
The technical problems to be solved by the invention are as follows: aiming at the problem of poor mechanical property of the existing silicone rubber, a preparation method of high-crosslinking organic silicone rubber is provided.
In order to solve the technical problems, the invention adopts the technical scheme that:
(1) putting hydroxyl silicone oil, modified nano silicon dioxide and nano zinc oxide into a double-roller rubber mixing mill, and carrying out mixed heat treatment for 2-4 h at the rotating speed of 100-120 r/min at the temperature of 100-120 ℃ to obtain a mixture;
(2) adding hydroxyl silicone oil, benzoyl peroxide and dibutyltin dilaurate into the mixture, and placing the mixture in a cold press for mould pressing for 2-4 min at normal temperature to obtain a silicone rubber precursor;
(3) and slowly injecting methacrylic acid into the silicon rubber precursor, and crosslinking for 8-10 days at normal temperature to obtain the high-crosslinking organic silicon rubber.
The hydroxyl silicone oil, the high hydrogen-containing silicone oil, the modified nano silicon dioxide, the nano zinc oxide, the methacrylic acid, the benzoyl peroxide, the antioxidant 1010 and the dibutyltin dilaurate are prepared from 100-120 parts by weight of the hydroxyl silicone oil, 10-12 parts by weight of the high hydrogen-containing silicone oil, 5-6 parts by weight of the modified nano silicon dioxide, 10-12 parts by weight of the nano zinc oxide, 20-24 parts by weight of the methacrylic acid, 0.10-0.12 part by weight of the benzoyl peroxide, 0.5-0.6 part by weight of the antioxidant 1010 and 0.10-0.12 part by weight of the dibutyltin dilaurate.
And (3) the pressure of the die pressing in the step (2) is 10-12 MPa.
The flow rate of the methacrylic acid in the step (3) is 10-20 mL/min.
The specific preparation steps of the modified nano silicon dioxide in the step (1) are as follows:
(1) adding vinyl silane, methyl trichlorosilane and absolute ethyl alcohol into deionized water, stirring for 10-15 min at a rotating speed of 200-240 r/min under a water bath condition of 40-50 ℃, and preserving heat to obtain a modified solution;
(2) adding nano silicon dioxide into the modified solution, stirring for 12-16 min at the rotating speed of 800-850 r/min under the water bath condition of 40-50 ℃, and then placing the mixture into an ultrasonic dispersion machine for ultrasonic dispersion for 20-30 min to obtain dispersion liquid;
(3) and (3) placing the dispersion liquid in a centrifuge, centrifuging and separating at the normal temperature at the rotating speed of 3500-4000 r/min for 10-12 min, taking out the lower-layer solid, and placing in an oven at the temperature of 50-60 ℃ for drying for 1-2 h to obtain the modified nano silicon dioxide.
The weight parts of the nano silicon dioxide, the methylvinylsilane, the methyltrichlorosilane, the absolute ethyl alcohol and the deionized water are 20-30 parts of the nano silicon dioxide, 4-6 parts of the methylvinylsilane, 2-3 parts of the methyltrichlorosilane, 20-30 parts of the absolute ethyl alcohol and 40-60 parts of the deionized water.
And (3) the power of the ultrasonic dispersion in the step (2) is 300-400W.
The specific preparation steps of the hydroxyl silicone oil in the step (1) are as follows:
(1) adding N, N-dimethylformamide, ionized water and magnesium hydroxide into octamethylcyclotetrasiloxane, and stirring at the rotation speed of 180-200 r/min at the temperature of 120-140 ℃ for reacting for 2-4 hours to obtain a reactant;
(2) and (3) placing the reactant in a reduced pressure distillation device for reduced pressure distillation for 30-40 min, and cooling at normal temperature to obtain the hydroxyl silicone oil.
The weight parts of the octamethylcyclotetrasiloxane, the N, N-dimethylformamide, the deionized water and the magnesium hydroxide are 100-120 parts of the octamethylcyclotetrasiloxane, 10-12 parts of the N, N-dimethylformamide, 0.10-0.12 part of the deionized water and 0.010-0.012 part of the magnesium hydroxide.
The reduced pressure distillation in the step (2) is carried out under the conditions of-0.2 to-0.1 MPa of pressure and 120 to 140 ℃.
Compared with other methods, the method has the beneficial technical effects that:
(1) the invention takes nano silicon dioxide as reinforcing filler, and adopts methylvinylsilane, methyltrichlorosilane and ultrasonic oscillation to modify the reinforcing filler, so as to prepare the high-crosslinking organic silicon rubber, the nano silicon dioxide has the physicochemical characteristics of small particle, large specific surface area, good dispersibility, looseness, porosity, good fluidity and the like, therefore, the high-crosslinking organic silicon rubber has good affinity with rubber and easy dispersion, can effectively improve the process performance and physical performance of the organic silicon rubber, the nano silicon dioxide has small particle size, large specific surface area, strong interaction with rubber molecules, high surface activity and high bonding degree with the rubber, can form 'bonding glue' with the rubber molecules, has large constraint effect on the rubber, can effectively improve the mechanical property and durability of the silicon rubber, the methylvinylsilane and the methyltrichlorosilane are substances with an amphoteric structure, part of functional groups of molecules of the silicon rubber can react with active groups on the surface of the nano silicon dioxide to form strong chemical bonding, and the other part of functional groups can physically wind with the organic silicon to enable the nano silicon dioxide and the organic silicon to generate molecular bridges with special functions, so that the comprehensive performance of the organic silicon rubber is improved;
(2) the invention prepares a high cross-linking organic silicon rubber by adding methacrylic acid and nano zinc oxide, the nano zinc oxide surface contains hydroxyl group, which can form strong interaction with silicon rubber, and has excellent reinforcement function to silicon rubber, after adding methacrylic acid, methacrylic acid and nano zinc oxide can generate 'in situ polymerization' reaction in silicon rubber matrix to form nano particles, and reinforce silicon rubber, the zinc methacrylate generated by the reaction of methacrylic acid and nano zinc oxide is a multifunctional rubber active auxiliary agent, the reactive functional group on the molecular structure has high activity in the presence of free radical, and is easy to generate graft polymerization with rubber molecules to form multi-element cross-linking network, reinforce rubber, in the initiation cross-linking process of benzoyl peroxide, the zinc methacrylate is polymerized in silicon rubber and generates graft reaction with matrix material, meanwhile, the nano zinc polymethacrylate formed by polymerization is uniformly dispersed in rubber, and has excellent reinforcing effect.
Detailed Description
Respectively weighing 100-120 parts by weight of octamethylcyclotetrasiloxane, 10-12 parts by weight of N, N-dimethylformamide, 0.10-0.12 part by weight of deionized water and 0.010-0.012 part by weight of magnesium hydroxide, adding N, N-dimethylformamide, ionized water and magnesium hydroxide into octamethylcyclotetrasiloxane, stirring and reacting for 2-4 h at the temperature of 120-140 ℃ at the rotating speed of 180-200 r/min to obtain a reactant, placing the reactant into a reduced pressure distillation device, carrying out reduced pressure distillation for 30-40 min at the pressure of-0.2-0.1 MPa and the temperature of 120-140 ℃, cooling at normal temperature to obtain hydroxyl silicone oil, respectively weighing 20-30 parts by weight of nano silicon dioxide, 4-6 parts by weight of methylvinylsilane, 2-3 parts by weight of methyltrichlorosilane, 20-30 parts by weight of absolute ethyl alcohol and 40-60 parts by weight of deionized water, and respectively weighing 20-30 parts by weight of methyltrichlorosilane, methyltrichlorosilane and magnesium hydroxide, Adding absolute ethyl alcohol into deionized water, stirring at a rotating speed of 200-240 r/min for 10-15 min under a water bath condition of 40-50 ℃, preserving heat to obtain a modified solution, adding nano-silica into the modified solution, stirring at a rotating speed of 800-850 r/min for 12-16 min under a water bath condition of 40-50 ℃, then placing the modified solution into an ultrasonic dispersion machine to ultrasonically disperse for 20-30 min at a power of 300-400W to obtain a dispersion solution, placing the dispersion solution into a centrifugal machine, centrifugally separating at a rotating speed of 3500-4000 r/min for 10-12 min at normal temperature, taking a lower-layer solid, placing the lower-layer solid in an oven of 50-60 ℃ to dry for 1-2 h to obtain modified nano-silica, and respectively weighing 100-120 parts by weight of hydroxyl silicone oil, 10-12 parts by weight of high-hydrogen-containing silicone oil, 5-6 parts by weight of modified nano-silica, 10-12 parts by weight of nano-zinc oxide, 20-24 parts by weight of methacrylic acid, 0.10-0.12 part, 0.5-0.6 part of antioxidant 1010 and 0.10-0.12 part of dibutyltin dilaurate, placing hydroxyl silicone oil, modified nano-silica and nano-zinc oxide in a double-roller rubber mixing mill, mixing and performing heat treatment for 2-4 h at the temperature of 100-120 ℃ at the rotating speed of 100-120 r/min to obtain a mixture, adding the hydroxyl silicone oil, benzoyl peroxide and dibutyltin dilaurate into the mixture, placing the mixture in a cold press, performing mould pressing for 2-4 min at the pressure of 10-12 MPa at normal temperature to obtain a silicon rubber precursor, slowly injecting methacrylic acid into the silicon rubber precursor at the flow speed of 10-20 mL/min, and performing crosslinking at the normal temperature for 8-10 days to obtain the high-crosslinking organic silicon rubber.
Example 1
Respectively weighing 100 parts by weight of octamethylcyclotetrasiloxane, 10 parts by weight of N, N-dimethylformamide, 0.10 part by weight of deionized water and 0.010 part by weight of magnesium hydroxide, adding the N, N-dimethylformamide, ionized water and the magnesium hydroxide into the octamethylcyclotetrasiloxane, stirring and reacting for 2 hours at the temperature of 120 ℃ at the rotating speed of 180r/min to obtain a reactant, putting the reactant into a reduced pressure distillation device, carrying out reduced pressure distillation at the pressure of-0.2 MPa and the temperature of 120 ℃ for 30 minutes, cooling at normal temperature to obtain hydroxyl silicone oil, respectively weighing 20 parts by weight of nano silicon dioxide, 4 parts by weight of methylvinylsilane, 2 parts by weight of methyltrichlorosilane, 20 parts by weight of anhydrous ethanol and 40 parts by weight of deionized water, adding the vinylsilane, the methyltrichlorosilane and the anhydrous ethanol into the deionized water, stirring for 10 minutes at the rotating speed of 200r/min under the water bath condition of 40 ℃, keeping the temperature to obtain a modified solution, adding nano-silicon dioxide into the modified solution, stirring for 12min at the rotating speed of 800r/min under the condition of water bath at 40 ℃, then placing the modified solution into an ultrasonic dispersion machine to ultrasonically disperse for 20min at the power of 300W to obtain a dispersion solution, placing the dispersion solution into a centrifugal machine, centrifugally separating for 10min at the rotating speed of 3500r/min at normal temperature, taking the solid of the lower layer, placing the solid in an oven at 50 ℃ for drying for 1h to obtain the modified nano-silicon dioxide, respectively weighing 100 parts by weight of hydroxy silicone oil, 10 parts by weight of high hydrogen silicone oil, 5 parts by weight of modified nano-silicon dioxide, 10 parts by weight of nano-zinc oxide, 20 parts by weight of methacrylic acid, 0.10 parts by weight of benzoyl peroxide, 0.5 parts by weight of antioxidant 1010 and 0.10 parts by weight of dibutyltin dilaurate, placing the hydroxy silicone oil, the modified nano-silicon dioxide and the nano-zinc oxide into a double-roll rubber mixing and heat treating, and (3) adding hydroxyl silicone oil, benzoyl peroxide and dibutyltin dilaurate into the mixture, placing the mixture in a cold press, performing mould pressing for 2min at the normal temperature under the pressure of 10MPa to obtain a silicon rubber precursor, slowly injecting methacrylic acid into the silicon rubber precursor at the flow rate of 10mL/min, and performing crosslinking for 8 days at the normal temperature to obtain the high-crosslinking organic silicon rubber.
Example 2
Respectively weighing 110 parts by weight of octamethylcyclotetrasiloxane, 11 parts by weight of N, N-dimethylformamide, 0.11 part by weight of deionized water and 0.011 part by weight of magnesium hydroxide, adding the N, N-dimethylformamide, ionized water and the magnesium hydroxide into the octamethylcyclotetrasiloxane, stirring and reacting for 3 hours at the temperature of 130 ℃ at the rotating speed of 190r/min to obtain a reactant, putting the reactant into a reduced pressure distillation device, carrying out reduced pressure distillation at the pressure of-0.2 MPa and the temperature of 130 ℃ for 35 minutes, cooling at normal temperature to obtain hydroxyl silicone oil, respectively weighing 25 parts by weight of nano silicon dioxide, 5 parts by weight of methylvinylsilane, 2 parts by weight of methyltrichlorosilane, 25 parts by weight of absolute ethyl alcohol and 50 parts by weight of deionized water, adding the vinylsilane, the methyltrichlorosilane and the absolute ethyl alcohol into the deionized water, stirring for 12 minutes at the rotating speed of 220r/min under the water bath condition of 45 ℃, keeping the temperature to obtain a modified solution, adding nano-silicon dioxide into the modified solution, stirring for 14min at the rotational speed of 825r/min under the water bath condition of 45 ℃, then placing the solution into an ultrasonic dispersion machine for ultrasonic dispersion for 25min at the power of 350W to obtain a dispersion solution, placing the dispersion solution into a centrifugal machine, centrifugally separating for 11min at the rotational speed of 3750r/min at normal temperature, taking the lower-layer solid, placing the lower-layer solid into a drying oven at 55 ℃ for drying for 1h to obtain the modified nano-silicon dioxide, respectively weighing 110 parts by weight of hydroxy silicone oil, 11 parts by weight of high hydrogen silicone oil, 5 parts by weight of modified nano-silicon dioxide, 11 parts by weight of nano-zinc oxide, 22 parts by weight of methacrylic acid, 0.11 part by weight of benzoyl peroxide, 0.5 parts by weight of antioxidant 1010 and 0.11 part by weight of dibutyltin dilaurate, placing the hydroxy silicone oil, the modified nano-silicon dioxide and the nano-zinc oxide into a double-roll glue mixing machine, carrying, and (3) obtaining a mixture, adding hydroxyl silicone oil, benzoyl peroxide and dibutyltin dilaurate into the mixture, placing the mixture in a cold press, performing mould pressing for 3min at the normal temperature under the pressure of 11MPa to obtain a silicon rubber precursor, slowly injecting methacrylic acid into the silicon rubber precursor at the flow rate of 15mL/min, and performing crosslinking for 9 days at the normal temperature to obtain the high-crosslinking organic silicon rubber.
Example 3
Respectively weighing 120 parts by weight of octamethylcyclotetrasiloxane, 12 parts by weight of N, N-dimethylformamide, 0.12 part by weight of deionized water and 0.012 part by weight of magnesium hydroxide, adding the N, N-dimethylformamide, the ionized water and the magnesium hydroxide into the octamethylcyclotetrasiloxane, stirring and reacting for 4 hours at 140 ℃ at a rotating speed of 200r/min to obtain a reactant, putting the reactant into a reduced pressure distillation device, carrying out reduced pressure distillation at a pressure of-0.1 MPa and a temperature of 140 ℃ for 40 minutes, cooling at normal temperature to obtain hydroxyl silicone oil, respectively weighing 30 parts by weight of nano silicon dioxide, 6 parts by weight of methylvinylsilane, 3 parts by weight of methyltrichlorosilane, 30 parts by weight of absolute ethyl alcohol and 60 parts by weight of deionized water, adding the vinylsilane, the methyltrichlorosilane and the absolute ethyl alcohol into the deionized water, stirring for 15 minutes at a water bath condition of 50 ℃ at a rotating speed of 240r/min, keeping the temperature to obtain a modified solution, adding nano-silicon dioxide into the modified solution, stirring for 16min at the rotating speed of 850r/min under the condition of a water bath at 50 ℃, then placing the modified solution into an ultrasonic dispersion machine to carry out ultrasonic dispersion for 30min at the power of 400W to obtain a dispersion solution, placing the dispersion solution into a centrifugal machine, carrying out centrifugal separation for 12min at the rotating speed of 4000r/min at normal temperature, taking out lower-layer solid, placing the lower-layer solid in a drying oven at 60 ℃ to dry for 2h to obtain modified nano-silicon dioxide, respectively weighing 120 parts by weight of hydroxyl silicone oil, 12 parts by weight of high hydrogen-containing silicone oil, 6 parts by weight of modified nano-silicon dioxide, 12 parts by weight of nano-zinc oxide, 24 parts by weight of methacrylic acid, 0.12 part by weight of benzoyl peroxide, 0.6 part by weight of antioxidant 1010 and 0.12 part by weight of dibutyltin dilaurate, placing the hydroxyl silicone oil, the modified nano-silicon dioxide and the nano-zinc oxide, and (3) adding hydroxyl silicone oil, benzoyl peroxide and dibutyltin dilaurate into the mixture, placing the mixture in a cold press, performing mould pressing for 4min at the normal temperature under the pressure of 12MPa to obtain a silicon rubber precursor, slowly injecting methacrylic acid into the silicon rubber precursor at the flow rate of 20mL/min, and performing crosslinking for 10 days at the normal temperature to obtain the high-crosslinking organic silicon rubber.
Comparative example: silicone rubber manufactured by Dongguan company.
The silicone rubbers prepared in the examples and the comparative examples were tested, specifically as follows:
tensile property: the thickness and the Shore hardness are measured according to the GB/T531-99 standard, the tensile strength and the elongation at break are measured at the speed of 50mm/min in a WDW-10 type micro-control electronic tensile testing machine according to the GB/T528-1998 standard, and the experimental temperature is 25 ℃.
Hydrophobic property: the surface contact angle was measured at room temperature using a Rame-hartNRL contact angle measuring instrument.
Swelling property: taking a small piece of dry sample, accurately weighing the sample, soaking the sample in toluene, taking out the sample after soaking for 72 hours, quickly wiping off toluene on the surface, accurately weighing the sample, and calculating the mass change rate of the sample.
The specific test results are shown in table 1.
Table 1 comparative table of property characterization
| Detecting items | Example 1 | Example 2 | Example 3 | Comparative example |
| Tensile strength/MPa | 7.82 | 7.25 | 7.33 | 3.69 |
| Elongation at break/% | 547.12 | 568.74 | 576.63 | 355.32 |
| Contact Angle/° | 110.40 | 110.32 | 109.93 | 75.56 |
| Rate of change of mass/%) | 97 | 99 | 95 | 215 |
As can be seen from Table 1, the silicone rubber prepared by the present invention has good tensile properties, hydrophobicity and swelling properties.
Claims (10)
1. The preparation method of the high-crosslinking organic silicon rubber is characterized by comprising the following specific preparation steps:
(1) putting hydroxyl silicone oil, modified nano silicon dioxide and nano zinc oxide into a double-roller rubber mixing mill, and carrying out mixed heat treatment for 2-4 h at the rotating speed of 100-120 r/min at the temperature of 100-120 ℃ to obtain a mixture;
(2) adding hydroxyl silicone oil, benzoyl peroxide and dibutyltin dilaurate into the mixture, and placing the mixture in a cold press for mould pressing for 2-4 min at normal temperature to obtain a silicone rubber precursor;
(3) and slowly injecting methacrylic acid into the silicon rubber precursor, and crosslinking for 8-10 days at normal temperature to obtain the high-crosslinking organic silicon rubber.
2. The method for preparing highly crosslinked silicone rubber according to claim 1, wherein the weight parts of the hydroxyl silicone oil, the highly hydrogen-containing silicone oil, the modified nano-silica, the nano-zinc oxide, the methacrylic acid, the benzoyl peroxide, the antioxidant 1010 and the dibutyltin dilaurate are 100-120 parts of the hydroxyl silicone oil, 10-12 parts of the highly hydrogen-containing silicone oil, 5-6 parts of the modified nano-silica, 10-12 parts of the nano-zinc oxide, 20-24 parts of the methacrylic acid, 0.10-0.12 part of the benzoyl peroxide, 0.5-0.6 part of the antioxidant 1010 and 0.10-0.12 part of the dibutyltin dilaurate.
3. The method for preparing highly crosslinked silicone rubber according to claim 1, wherein the pressure of the molding in step (2) is 10 to 12 MPa.
4. The method for preparing a highly crosslinked silicone rubber according to claim 1, wherein the flow rate of the methacrylic acid in step (3) is 10 to 20 mL/min.
5. The method for preparing highly crosslinked silicone rubber according to claim 1, wherein the specific preparation steps of the modified nanosilica described in step (1) are:
(1) adding vinyl silane, methyl trichlorosilane and absolute ethyl alcohol into deionized water, stirring for 10-15 min at a rotating speed of 200-240 r/min under a water bath condition of 40-50 ℃, and preserving heat to obtain a modified solution;
(2) adding nano silicon dioxide into the modified solution, stirring for 12-16 min at the rotating speed of 800-850 r/min under the water bath condition of 40-50 ℃, and then placing the mixture into an ultrasonic dispersion machine for ultrasonic dispersion for 20-30 min to obtain dispersion liquid;
(3) and (3) placing the dispersion liquid in a centrifuge, centrifuging and separating at the normal temperature at the rotating speed of 3500-4000 r/min for 10-12 min, taking out the lower-layer solid, and placing in an oven at the temperature of 50-60 ℃ for drying for 1-2 h to obtain the modified nano silicon dioxide.
6. The method for preparing highly crosslinked silicone rubber according to claim 5, wherein the weight parts of the nano-silica, the methylvinylsilane, the methyltrichlorosilane, the absolute ethanol, and the deionized water are 20 to 30 parts of the nano-silica, 4 to 6 parts of the methylvinylsilane, 2 to 3 parts of the methyltrichlorosilane, 20 to 30 parts of the absolute ethanol, and 40 to 60 parts of the deionized water.
7. The method for preparing highly crosslinked silicone rubber according to claim 5, wherein the power of the ultrasonic dispersion in step (2) is 300-400W.
8. The method for preparing highly crosslinked silicone rubber according to claim 1, wherein the hydroxyl silicone oil of step (1) is prepared by the following steps:
(1) adding N, N-dimethylformamide, ionized water and magnesium hydroxide into octamethylcyclotetrasiloxane, and stirring at the rotation speed of 180-200 r/min at the temperature of 120-140 ℃ for reacting for 2-4 hours to obtain a reactant;
(2) and (3) placing the reactant in a reduced pressure distillation device for reduced pressure distillation for 30-40 min, and cooling at normal temperature to obtain the hydroxyl silicone oil.
9. The method for preparing highly crosslinked silicone rubber according to claim 8, wherein the weight parts of octamethylcyclotetrasiloxane, N-dimethylformamide, deionized water, and magnesium hydroxide are 100-120 parts of octamethylcyclotetrasiloxane, 10-12 parts of N, N-dimethylformamide, 0.10-0.12 part of deionized water, and 0.010-0.012 part of magnesium hydroxide.
10. The method for preparing a highly crosslinked silicone rubber according to claim 8, wherein the reduced pressure distillation in step (2) is performed at a pressure of-0.2 to-0.1 MPa and a temperature of 120 to 140 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911062288.4A CN110698613A (en) | 2019-11-02 | 2019-11-02 | Preparation method of high-crosslinking organic silicon rubber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911062288.4A CN110698613A (en) | 2019-11-02 | 2019-11-02 | Preparation method of high-crosslinking organic silicon rubber |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110698613A true CN110698613A (en) | 2020-01-17 |
Family
ID=69203348
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911062288.4A Pending CN110698613A (en) | 2019-11-02 | 2019-11-02 | Preparation method of high-crosslinking organic silicon rubber |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110698613A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111171321A (en) * | 2020-02-24 | 2020-05-19 | 华南理工大学 | Long-chain alkyl silicone oil type silicon paste and preparation method and application thereof |
| CN114163932A (en) * | 2020-09-11 | 2022-03-11 | 上海共城通信科技有限公司 | Preparation method of ionic resin packaging adhesive film |
-
2019
- 2019-11-02 CN CN201911062288.4A patent/CN110698613A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111171321A (en) * | 2020-02-24 | 2020-05-19 | 华南理工大学 | Long-chain alkyl silicone oil type silicon paste and preparation method and application thereof |
| CN111171321B (en) * | 2020-02-24 | 2021-05-14 | 华南理工大学 | Long-chain alkyl silicone oil type silicon paste and preparation method and application thereof |
| CN114163932A (en) * | 2020-09-11 | 2022-03-11 | 上海共城通信科技有限公司 | Preparation method of ionic resin packaging adhesive film |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Reuvekamp et al. | Effects of time and temperature on the reaction of TESPT silane coupling agent during mixing with silica filler and tire rubber | |
| CN103408948B (en) | A kind of rubber combination and application thereof | |
| CN110240746A (en) | A kind of anti-skidding heat-proof aging EVA, NR composite foam material and preparation method thereof | |
| KR101240602B1 (en) | Master batch elastomer containing organized silica and method of the same | |
| CN110698613A (en) | Preparation method of high-crosslinking organic silicon rubber | |
| KR20110085968A (en) | Use of polyorganosiloxanes in the processing and vulcanization of rubber | |
| Jincheng et al. | Application of modified calcium sulfate whisker in methyl vinyl silicone rubber composites | |
| CN112375262A (en) | Wear-resistant sole material and preparation method thereof | |
| CN110746647B (en) | Vulcanizing agent emulsion and preparation method and application thereof | |
| CN113999531A (en) | Mold glue and preparation method thereof | |
| CN114409980A (en) | Anti-wear low-rolling-resistance rubber composition, preparation process and tire | |
| Rajesh et al. | Liquid silicone rubber Vulcanizates: network structure-property relationship and cure kinetics | |
| CN112251165B (en) | Special prime coat-free platinum vulcanizing agent for combination of metal substrate and silica gel and preparation method thereof | |
| Dileep et al. | Functionalized nanosilica for vulcanization efficiency and mechanical properties of natural rubber composites | |
| CN111171271B (en) | Preparation method of heat-resistant polyurethane elastomer | |
| CN114874443B (en) | Silicon rubber with low curing shrinkage and preparation method thereof | |
| CN115960464B (en) | Liquid vinyl cage polysilsesquioxane modified addition type liquid silicone rubber and preparation method thereof | |
| Dong et al. | Aminopropyl-modified silica as cross-linkers of polysiloxane containing γ-chloropropyl groups for preparing heat-curable silicone rubber | |
| Katueangngan et al. | Interfacial interactions of silica and natural rubber enhanced by hydroxyl telechelic natural rubber as interfacial modifier | |
| CN106146788B (en) | Tire modified organic silicon material and preparation method thereof | |
| CN114874496B (en) | High-strength low-curing shrinkage silicone rubber and preparation method thereof | |
| CN112226068A (en) | Super-hydrophobic wear-resistant TPU film and preparation method thereof | |
| Poochai et al. | Polyisoprene-coated silica/natural rubber composite | |
| CN110437545A (en) | A kind of silicon rubber and ethylene propylene diene rubber Blend rubber and preparation method thereof | |
| Saleh et al. | Effect of vinyltrimethoxysilane as a coupling agent on the mechanical and electrical properties of acrylic rubber |
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 |