CN112521756B - High-mechanical-strength ceramizable organic silicon material and preparation method thereof - Google Patents
High-mechanical-strength ceramizable organic silicon material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a high-mechanical-strength ceramizable organic silicon material and a preparation method thereof. The method is characterized in that: the modified silicon rubber is prepared from novel modified wollastonite, organic silicon rubber, a vulcanizing agent, an auxiliary agent white carbon black, hydroxyl silicone oil and zinc borate. The modification method comprises the following steps: firstly, modifying wollastonite by using a surface modifier 2,4, 6-trihydroxybenzoic acid. And secondly, repeatedly mixing the modified wollastonite, the silicon rubber and the auxiliary agent by using an internal mixer and an open mill, and then vulcanizing and molding to obtain the high-mechanical-strength ceramizable organic silicon material. The invention has the advantages that: the 2,4, 6-trihydroxybenzoic acid has high reactive hydroxyl and carboxyl, and can respectively react with hydroxyl on the surface of wollastonite and an organic silicon substrate to improve the interface bonding force and the mechanical strength of the material. The modified wollastonite has high thermal stability, a ceramic body formed at high temperature has better mechanical strength, and the ceramic body has simple preparation process, low equipment requirement, green and environmental protection and can be widely used in the field of fireproof and high-temperature-resistant materials.
Description
Technical Field
The invention relates to a ceramizable organic silicon material and a preparation method thereof, belonging to the field of high polymer materials. .
Background
The silicon rubber is a high molecular elastomer with organic and inorganic characteristics, the main chain of the silicon rubber is a repeated-Si-O-unit, and the side group connected with a silicon atom has organic groups such as methyl, vinyl, phenyl and the like, so that the silicon rubber becomes a typical semi-organic semi-inorganic polymer and has a plurality of excellent properties such as high temperature resistance, low temperature resistance, electric insulation, weather resistance, chemical corrosion resistance and the like.
The ceramizable organic silicon material is a novel fireproof high-temperature-resistant material, and is prepared by taking an organic silicon material as a matrix and adding a porcelain filler, an auxiliary agent and other functional fillers. Is flexible at room temperatureThe ceramic material has good tensile property in a rubber state, and can be converted into a ceramic body with compactness and hardness from the rubber state under a high-temperature condition. The mechanism of forming porcelain of the ceramization organosilicon material mainly comprises two processes: a) at a lower temperature, the inorganic ceramic filler is uniformly dispersed in the silicon rubber matrix; b) when exposed to high temperature, the organosilicon is decomposed into SiO2The fluxing agent in the porcelain-forming filler begins to melt, and a liquid-phase eutectic body is formed at the edge of the filler, so that SiO2Eutectic reaction with the ceramic filler, and SiO is generated along with the rise of the ablation temperature and the prolongation of the ablation time2The particles form "bridges" with the filler, thereby forming an inorganic ceramic body.
The ceramizable silicon rubber composite material needs to meet the actual use requirements, not only needs to meet the mechanical strength requirements of excellent tensile property, elongation at break, tearing strength and the like at room temperature, but also needs to meet the characteristic of high strength in the state of a ceramic body. In order to meet various requirements at the same time, a great deal of research is carried out at home and abroad.
Due to simple preparation process and simple and convenient equipment, the existing ceramic organic silicon rubber can be widely used for fireproof and high-temperature-resistant materials, thermal insulation layers, fireproof thermal insulation materials and cable protection circuits, and ceramic organic silicon rubber with different structural sizes can be designed according to requirements. For example, U.S. patent No. 4269757 discloses a silicone material capable of forming a ceramic body at high temperatures, comprising a silicone polymer, a ceramic-forming filler and a peroxide curing agent, which when heated to a temperature of 500 ℃ or higher, can be converted to a ceramic material, which is a lightweight ceramic material having excellent dimensional stability, strength, electrical insulating ability, and which can be used as an insulating coating for an electrically conductive substance; chinese patent CN 109467936A discloses porcelainized fireproof heat-insulating foamed silicone rubber and a preparation method thereof, wherein the porcelainized fireproof heat-insulating foamed silicone rubber comprises base rubber, porcelainizing filler, a platinum catalyst, a foaming agent, silicone oil and a vulcanizing agent, wherein the base rubber is a rubber compound prepared from methyl vinyl silicone rubber, the foamed silicone rubber has a good ceramic effect after ablation, has no surface cracks and is hard in texture, a complete foam structure is kept, the volume retention rate is ensured to be 85% or higher, and the foamed silicone rubber has excellent fireproof performance; chinese patent CN 109423202A discloses a chemical-process organosilicon heat-resistant coating and a preparation method thereof, wherein organosilicon resin is used as a film-forming material, and a silicon dioxide material, a special ceramic material, zinc phosphate and a fiber material are used as fillers to prepare a heat-insulating, anti-corrosion and heat-resistant paint, and the heat-resistant paint has the characteristics of heat resistance, oil resistance, moisture resistance, insulation, strong adhesive force, good mechanical property and the like after being cured, has a good heat-insulating effect, and can form a compact ceramic layer at high temperature; US patent US 20060155039 discloses a fire resistant silicone composite comprising a silicone polymer, mica, fluxing agents, which is suitable for use in fire wall linings, fire barriers, screens, ceilings or linings, structural fire protection, fire door inserts, door and window seals, intumescent seals, products formed in electrical distribution cabinets or cables; chinese patent CN 102850805A discloses a preparation method of a fire-resistant ceramic silicon rubber and an application of the fire-resistant ceramic silicon rubber in electric wires and cables, wherein the rubber comprises 100 parts of methyl vinyl silicone rubber, 30-80 parts of white carbon black, 9-40 parts of alumina, 1.5-8 parts of a structure control agent, 3-5 parts of a sintering additive, 0.25-1.5 parts of a surface treatment agent and 0.5-2 parts of a cross-linking agent, and the formed fire-resistant ceramic silicon rubber has the characteristics of compact ceramic body, stable structure, stable fire resistance, good insulating property and the like; the patent WO 2017070893 of the world intellectual property organization discloses a ceramic silicon rubber and a preparation method thereof, the ceramic silicon rubber is added with a high-efficiency flame-retardant catalyst, inorganic mineral powder, nano metal oxide and/or metal hydroxide, lamellar nano powder and other fillers in a silicon rubber system, the flame retardance of the obtained ceramic silicon rubber meets the UL94V-0 requirement, the ceramic can be formed at 400 ℃, and the power is not cut off after the cable is formed for 180 min at 950 ℃.
The ceramifiable organic silicon is often required to be filled with a large amount of ceramic forming filler, wherein wollastonite is widely applied due to the characteristics of the wollastonite. Wollastonite is a triclinic, fine plate-like crystal, a radially or fibrous aggregate of silicates having the formula Ca3[Si3O9]Theoretical chemical composition: CaO48.25%, SiO251.75 percent. The wollastonite is used as a ceramic forming filler, so that the ceramic can be reducedThe shrinkage rate of the ceramic can also make the ceramic have higher mechanical strength. The higher filling amount easily causes agglomeration of the powder and simultaneously causes poor compatibility with a matrix, so that the wollastonite powder needs to be subjected to surface modification before use. The wollastonite is prepared from basic oxide CaO and acidic oxide SiO2Chemical combination composition and surface chemical structure are relatively complex, and the needle-shaped structure is also easily damaged in the modification process, so that the organic surface modification is relatively difficult.
At present, the modification of wollastonite powder is mostly surface chemical modification, and common modifiers mainly comprise coupling agents, ionic surfactants, organic acids (esters) and the like.
The coupling agents mainly comprise silane coupling agents, titanate coupling agents, aluminate coupling agents and the like, have organic and inorganic commonality, and can combine two materials with different properties into a composite material. Such as: CN111303487A is prepared by mixing titanate coupling agent, stearic acid and aliphatic polyoxyethylene ester to modify the surface of wollastonite powder, replacing hydroxyl on the surface of wollastonite with coupling agent to form a coupling agent layer on the surface, and then reacting with stearic acid and adding into polymer matrix. CN101235194A discloses a polylactic acid-modified wollastonite composite material and a preparation method thereof, wherein the wollastonite modifier is one or more selected from sodium oleate, stearic acid, silane coupling agents and titanate coupling agents, and modified wollastonite is obtained through wet modification.
The ionic surfactants can be classified into anionic surfactants and cationic surfactants, wherein the anionic surfactants mainly include sodium stearate, sodium lauryl sulfate, etc., and the cationic surfactants mainly include nitrogen-containing organic amine derivatives, such as quaternary ammonium salts, primary amine salts, etc. The modifiers cover the particle surface through the action of polar groups and the particle surface, so that the lipophilicity of the wollastonite filler can be greatly improved. Such as: CN105544206A discloses a method for modifying flexible wollastonite fibers, which comprises the steps of coating a cationic surfactant on the surface of wollastonite, and then copolymerizing and grafting polyethyleneimine and polymaleic acid in a wollastonite structure to obtain modified wollastonite. Hou et al use sodium stearateThe wollastonite is modified, the influence of modification time, modifier dosage and modification temperature on the modification effect is explored, and the mechanism in the modification process is analyzed. The results show that the modifier is used in an amount of 1.5%, the best effect can be obtained by reacting for 30min at 50 ℃, and meanwhile, the hydroxyl on the surface of the powder is unstable, and Ca is easily formed2+And reacted with a modifier. CN111892747A provides a surface modification method, which increases the compatibility of wollastonite and organic polymer when mixing by adding polyethylene glycol monostearate, 3- (methacryloyloxy) propyl trimethoxy silane, sodium dodecyl sulfate and other auxiliary agents, so that the wollastonite is uniformly dispersed in the organic polymer, and the mechanical property of the product is improved.
The organic acids (esters) include stearic acid, methacrylic acid and esters thereof, and sorbitan monooleate. The surface of wollastonite often has more hydroxyl groups, which is easy to generate chemical reaction with some organic acids (esters), and the modifier is successfully grafted on the surface of powder through the reaction. Such as: yuhaida et al prepared wollastonite/high density polyethylene/natural rubber composite material by grafting wollastonite with acrylic acid. The tensile strength and the elongation at break of the composite material are reduced by adding the wollastonite, and the treated composite material has better tensile property than an untreated composite material. Meanwhile, the treated wollastonite and the matrix show good compatibility. The chengchun clouds make methacrylic acid MAA and calcium silicate into slurry, and then stir at a certain temperature and dry to obtain the modified powder material. The results show that after MAA treatment, the morphology and microstructure of calcium silicate powder are changed, the main decomposition temperature of the silicon rubber is increased by 76.6 ℃, and the initial decomposition temperature and the final decomposition temperature are respectively increased by 33.6 ℃ and 108.6 ℃. The tensile strength, the elongation and the crosslinking density of the silicon rubber are all increased by adding the modified powder. CN104212089A discloses a high-temperature-resistant cable sheath material, wherein wollastonite is subjected to surface modification by utilizing poly epsilon-caprolactone, sorbitan monooleate and the like so as to improve the compatibility with a matrix and improve the filling effect. CN109181105A modification of wollastonite with EVA emulsion, alpha-sulfo fatty acid methyl ester and other materialAfter the EVA emulsion and wollastonite are mixed, the EVA emulsion is COO-And wollastonite surface equivalent to Ca2+The positive and negative ionic bonding occurs and the emulsion breaks and aggregates around the wollastonite particles to form primary particles. After modification, wollastonite can be better applied to olefin polymers. CN10774693A discloses a high temperature flame retardant cable, wherein modified wollastonite is used as a filler, the wollastonite is added into polyethylene glycol and stearic acid, and then tetrabutyl titanate is added to obtain the modified wollastonite after high temperature stirring. The Liangyu researches the reaction conditions for preparing the stearic acid/wollastonite composite particles, and the experimental result shows that: when the stearic acid content is 2 percent of wollastonite, the stirring speed reaches 800 r/min, the reaction time is 20 min, and the reaction temperature is 90 ℃, the activation index and the water contact angle reach maximum values, namely 90.2 percent and 140 degrees respectively. CN111875987A provides a method for modifying wollastonite, which comprises adding wollastonite powder into stearic acid ethanol solution, mixing and stirring. In Wuwei end, wollastonite and stearic acid are simultaneously placed in an airflow grinding cavity, and are chemically modified by supersonic airflow mechanical force, so that the wollastonite and the stearic acid undergo a mechanochemical reaction or mechanochemical adsorption, and two phase components at the interface are mutually permeated.
At present, a plurality of documents report the fireproof and high-temperature resistant materials of ceramizable organic silicon, including research on the use of different matrixes and different ceramic-forming fillers and the improvement of strength, but the prepared materials cannot meet the requirements of high mechanical property in a rubber state and a high-strength ceramic state at the same time, so that the ceramizable organic silicon materials still need to be further researched.
The patent provides a preparation method of a high-strength ceramizable organic silicon material, which is characterized in that 2,4, 6-trihydroxybenzoic acid is utilized to carry out surface modification on wollastonite as a ceramic filler, and the modified wollastonite, a vulcanizing agent and other additives are added into organic silicon rubber to prepare the organic silicon rubber with high mechanical strength.
Disclosure of Invention
The purpose of the invention is: the wollastonite is subjected to surface modification by using 2,4, 6-trihydroxybenzoic acid, and the modified wollastonite, a vulcanizing agent and other additives are uniformly dispersed in the organic silicon rubber to prepare the high-mechanical-strength ceramizable organic silicon material. By modifying the surface of the wollastonite, on one hand, the interface effect of the wollastonite and an organosilicon matrix can be improved, the powder agglomeration is reduced, and the compatibility of a filler and the matrix is improved, on the other hand, a group containing a benzene ring structure is introduced, so that the heat resistance of the material can be improved, and the performance of a ceramic body formed by the organosilicon material at high temperature is greatly improved.
The principle of the invention is as follows: the surface modifier 2,4, 6-trihydroxybenzoic acid has 1 carboxyl and 3 hydroxyls, wherein the carboxyl is easy to carry out chemical reaction with the hydroxyls on the surface of the wollastonite to form ester, so that the surface of the wollastonite is effectively coated; the 3 meta-phenolic hydroxyl groups have high activity and can participate in the chemical crosslinking reaction of the organic silicon, so that the interface bonding force of wollastonite and the organic silicon is obviously improved, and the mechanical strength of the organic silicon composite material is improved. Meanwhile, the surface modifier 2,4, 6-trihydroxybenzoic acid has high content of benzene rings in the structure, the thermal stability is relatively high, the modifier is connected in an organic silicon macromolecular network in a chemical bond mode, the thermal stability is further improved, the modifier starts to decompose at a high temperature, and a large amount of gas is not released, so that the produced ceramic body has high density and high strength.
The wollastonite powder modified by the surface modifier 2,4, 6-trihydroxybenzoic acid not only obviously improves the interface action so as to improve the mechanical strength of the organosilicon material, but also can improve the heat resistance and the thermal stability of the material, so that the mechanical strength of a ceramic body formed by the organosilicon material under a high-temperature condition is further improved, and the like.
The content of the invention is as follows: a high-mechanical-strength ceramizable organic silicon material. The curing agent is characterized by being prepared from modified wollastonite, organic silicon rubber, a curing agent, white carbon black, hydroxyl silicone oil, zinc borate and other auxiliaries; the dosage of each raw material is as follows: 100g of organic silicon rubber, 150g of modified wollastonite, 30g of white carbon black, 5g of hydroxyl silicone oil, 10g of zinc borate and 1g of vulcanizing agent. The organic silicon rubber is methyl vinyl silicon rubber, the modified wollastonite is 2,4, 6-trihydroxybenzoic acid modified wollastonite, the white carbon black is fumed silica, and the vulcanizing agent is 2, 5-dimethyl-2, 5-di-tert-butyl peroxy hexane (DBPMH).
The second content of the invention is: a preparation method of a high-mechanical-strength ceramizable organosilicon material. The method is characterized by comprising the following steps:
(1) preparation of modified wollastonite: 100g of wollastonite and 200g of distilled water are prepared into suspension, and 5-15g of 2,4, 6-trihydroxybenzoic acid is dissolved in 100g of distilled water and added into the wollastonite suspension to prepare modified wollastonite slurry. Carrying out modification reaction on the modified wollastonite slurry under the conditions of heating and stirring, wherein the reaction temperature is 30-90 ℃, and the reaction time is 1-4 h; filtering and washing the modified wollastonite slurry, and drying in a 120 ℃ oven to prepare modified wollastonite;
(2) weighing 150g of modified wollastonite prepared in the step (1), 100g of organic silicon rubber, 30g of auxiliary white carbon black, 5g of hydroxyl silicone oil and 10g of zinc borate according to the proportion, sequentially adding the materials into an internal mixer, and carrying out internal mixing at 100 ℃ for 30min to fully and uniformly mix the filler and the organic silicon matrix; placing the banburying adhesive on an open mill, adding 1g of vulcanizing agent, uniformly mixing, and vulcanizing and molding to obtain the high-mechanical-strength ceramizable organic silicon material.
The invention has the advantages that:
the surface modifier 2,4, 6-trihydroxybenzoic acid has 1 carboxyl and 3 hydroxyls, and the carboxyl is easy to carry out chemical reaction with the hydroxyls on the surface of the wollastonite to form ester so as to effectively coat the surface of the wollastonite; the 3 meta-phenolic hydroxyl groups have high activity and can participate in the chemical crosslinking reaction of the organic silicon, so that the interface bonding force of wollastonite and the organic silicon is obviously improved, and the mechanical strength of the organic silicon composite material is improved. Meanwhile, the surface modifier 2,4, 6-trihydroxy benzoic acid has high content of benzene rings in the structure, the thermal stability is relatively high, the modifier is connected in an organic silicon macromolecular network in a chemical bond mode, the thermal stability is further improved, the modifier starts to decompose at a high temperature, and a large amount of gas is not released, so that the produced ceramic body is high in air tightness and high in strength.
The wollastonite powder modified by the surface modifier 2,4, 6-trihydroxybenzoic acid can improve the interface action of the wollastonite and the organosilicon matrix, reduce powder agglomeration and improve the compatibility of the filler and the matrix; on the other hand, the introduction of the group containing a benzene ring structure can improve the heat resistance of the material, so that the performance of a ceramic body formed by the organic silicon material at high temperature is greatly improved. And the preparation process is simple, the equipment requirement is low, the environment is protected, and the preparation method can be widely applied to the field of fireproof and high-temperature-resistant materials.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
The present invention is further illustrated by the following specific examples, which are provided only for the purpose of facilitating understanding of the present invention, and are not to be construed as further limiting the scope of the present invention.
To illustrate the effect of the embodiment, the high-strength ceramifiable silicone rubber material prepared in the embodiment is hot-pressed and molded at 175 ℃ and 10MPa for vulcanization for 10 min, and the vulcanized rubber is placed into a 180 ℃ oven for secondary vulcanization for 2 h. The mechanical properties (tensile strength Rm, elongation at break A and tear strength Ts) of the rubber are respectively determined according to GB/T528-; volume resistivity (p)v) Testing according to GB/T1410-2006; breakdown strength (E)b) Testing according to GB/T1408.1-2016; the sample forms a ceramic body at 1000 ℃ for 30min, and the density (rho), the bending strength (sigma) and the water absorption (omega) of the ceramic body are respectively tested according to GB/T1033.1-2008, GB/T9341-; fire resistance test according to GB/T19216.21-2003, the material was cabled and tested at 1000 ℃ for 90min on electrical power.
Detailed description of the preferred embodiment 1
(1) Preparing 100g of wollastonite and 200g of distilled water into suspension, dissolving 5g of 2,4, 6-trihydroxybenzoic acid in 100g of distilled water, adding the mixture into the wollastonite suspension, placing the mixture into a flask, stirring the mixture for 1 hour at 30 ℃, filtering and washing the mixture after the reaction is finished, and drying the mixture in an oven at 120 ℃ to prepare modified wollastonite;
(2) adding 100g of methyl vinyl silicone rubber into an internal mixer, then sequentially adding 30g of white carbon black, 150g of modified wollastonite, 10g of zinc borate and 5g of hydroxyl silicone oil, and carrying out internal mixing at 100 ℃ for 30min to uniformly mix the filler and the colloid to obtain a rubber compound; and (3) placing the prepared banburying rubber on an open mill, adding 1g of vulcanizing agent DBPMH to obtain a rubber compound, and vulcanizing and molding. The obtained sample number is 1, and the specific properties are shown in table 1.
Specific example 2
(1) Preparing 100g of wollastonite and 200g of distilled water into suspension, dissolving 10g of 2,4, 6-trihydroxybenzoic acid in 100g of distilled water, adding the solution into the wollastonite suspension, placing the mixture into a flask, stirring the mixture for 1 hour at 30 ℃, filtering and washing the mixture after the reaction is finished, and drying the mixture in an oven at 120 ℃ to prepare modified wollastonite;
(2) adding 100g of methyl vinyl silicone rubber into an internal mixer, then sequentially adding 30g of white carbon black, 150g of modified wollastonite, 10g of zinc borate and 5g of hydroxyl silicone oil, and carrying out internal mixing at 100 ℃ for 30min to uniformly mix the filler and the colloid to obtain a rubber compound; and (3) placing the prepared banburying rubber on an open mill, adding 1g of vulcanizing agent DBPMH to obtain a rubber compound, and vulcanizing and molding. The sample number obtained is 2, and the specific properties are shown in Table 1.
Specific example 3
(1) Preparing 100g of wollastonite and 200g of distilled water into suspension, dissolving 15g of 2,4, 6-trihydroxybenzoic acid in 100g of distilled water, adding the solution into the wollastonite suspension, placing the mixture into a flask, stirring the mixture for 1 hour at 30 ℃, filtering and washing the mixture after the reaction is finished, and drying the mixture in an oven at 120 ℃ to prepare modified wollastonite;
(2) adding 100g of methyl vinyl silicone rubber into an internal mixer, then sequentially adding 30g of white carbon black, 150g of modified wollastonite, 10g of zinc borate and 5g of hydroxyl silicone oil, and carrying out internal mixing at 100 ℃ for 30min to uniformly mix the filler and the colloid to obtain a rubber compound; and (3) placing the prepared banburying rubber on an open mill, adding 1g of vulcanizing agent DBPMH to obtain a rubber compound, and vulcanizing and molding. The sample number was 3, and the specific properties are shown in Table 1.
TABLE 1 influence of different modifier contents on the mechanical Properties of organosilicon composites
Specific examples 1, 2 and 3 reflect the influence of different modifier contents on the mechanical properties of the composite material in the modification process of the wollastonite powder. When the ratio of the modifier to the wollastonite is 10:100, the mechanical property is high, when the ratio of the modifier to the wollastonite is 5:100, the wollastonite surface is less grafted, but when the content of the modifier reaches 15:100, the wollastonite surface may be saturated, and excessive modifier cannot react with the powder, is dispersed in the matrix or washed away, cannot play a role in improving the interface, and reduces the mechanical strength.
Specific example 4
(1) Preparing 100g of wollastonite and 200g of distilled water into suspension, dissolving 10g of 2,4, 6-trihydroxybenzoic acid in 100g of distilled water, adding the mixture into the wollastonite suspension, placing the mixture into a flask, stirring the mixture for 1 hour at 60 ℃, filtering and washing the mixture after the reaction is finished, and drying the mixture in an oven at 120 ℃ to prepare modified wollastonite;
(2) adding 100g of methyl vinyl silicone rubber into an internal mixer, then sequentially adding 30g of white carbon black, 150g of modified wollastonite, 10g of zinc borate and 5g of hydroxyl silicone oil, and carrying out internal mixing at 100 ℃ for 30min to uniformly mix the filler and the colloid to obtain a rubber compound; and (3) placing the prepared banburying rubber on an open mill, adding 1g of vulcanizing agent DBPMH to obtain a rubber compound, and vulcanizing and molding. The sample obtained was numbered 4 and the specific properties are shown in Table 2.
Specific example 5
(1) Preparing 100g of wollastonite and 200g of distilled water into suspension, dissolving 10g of 2,4, 6-trihydroxybenzoic acid in 100g of distilled water, adding the mixture into the wollastonite suspension, placing the mixture into a flask, stirring the mixture for 1 hour at 90 ℃, filtering and washing the mixture after the reaction is finished, and drying the mixture in an oven at 120 ℃ to prepare modified wollastonite;
(2) adding 100g of methyl vinyl silicone rubber into an internal mixer, then sequentially adding 30g of white carbon black, 150g of modified wollastonite, 10g of zinc borate and 5g of hydroxyl silicone oil, and carrying out internal mixing at 100 ℃ for 30min to uniformly mix the filler and the colloid to obtain a rubber compound; and (3) placing the prepared banburying rubber on an open mill, adding 1g of vulcanizing agent DBPMH to obtain a rubber compound, and vulcanizing and molding. The sample obtained was numbered 5 and the specific properties are shown in Table 2.
TABLE 2 influence of different modification temperatures on the mechanical Properties of organosilicon composites
Specific examples 2,4 and 5 reflect the influence of different temperatures of 30 ℃, 60 ℃ and 90 ℃ on the mechanical properties of the composite material in the modification process of the wollastonite powder. The result shows that when the modification temperature is 60 ℃, the mechanical property effect of the composite material is good, the reactivity among groups is reduced due to too low temperature, the hydroxyl on benzene rings is oxidized into jade due to too high temperature, the activity of the hydroxyl is reduced, and the modification effect is reduced.
Specific example 6
(1) Preparing 100g of wollastonite and 200g of distilled water into suspension, dissolving 10g of 2,4, 6-trihydroxybenzoic acid in 100g of distilled water, adding the solution into the wollastonite suspension, placing the mixture into a flask, stirring the mixture for 2 hours at 60 ℃, filtering and washing the mixture after the reaction is finished, and drying the mixture in an oven at 120 ℃ to prepare modified wollastonite;
(2) adding 100g of methyl vinyl silicone rubber into an internal mixer, then sequentially adding 30g of white carbon black, 150g of modified wollastonite, 10g of zinc borate and 5g of hydroxyl silicone oil, and carrying out internal mixing at 100 ℃ for 30min to uniformly mix the filler and the colloid to obtain a rubber compound; and (3) placing the prepared banburying rubber on an open mill, adding 1g of vulcanizing agent DBPMH to obtain a rubber compound, and vulcanizing and molding. The sample number obtained is 6, and the specific properties are shown in Table 3.
Specific example 7
(1) Preparing 100g of wollastonite and 200g of distilled water into suspension, dissolving 10g of 2,4, 6-trihydroxybenzoic acid in 100g of distilled water, adding the solution into the wollastonite suspension, placing the mixture into a flask, stirring the mixture for 4 hours at 60 ℃, filtering and washing the mixture after the reaction is finished, and drying the mixture in an oven at 120 ℃ to prepare modified wollastonite;
(2) adding 100g of methyl vinyl silicone rubber into an internal mixer, then sequentially adding 30g of white carbon black, 150g of modified wollastonite, 10g of zinc borate and 5g of hydroxyl silicone oil, and carrying out internal mixing at 100 ℃ for 30min to uniformly mix the filler and the colloid to obtain a rubber compound; and (3) placing the prepared banburying rubber on an open mill, adding 1g of vulcanizing agent DBPMH to obtain a rubber compound, and vulcanizing and molding. The sample number obtained is 7, and the specific properties are shown in Table 3.
TABLE 3 influence of different stirring times on the mechanical properties of the organosilicon composites
Specific examples 2, 6 and 7 discuss the influence of different stirring times of 1h, 2h and 4h on the mechanical properties of the material in the modification process, when the stirring time is 2h, the mechanical properties of the material are the most excellent, the stirring time is too short, the modifier and the powder can not react for a long time, but the modification time is too long, the needle-shaped structure of part of wollastonite is easily destroyed, and the strength in the matrix can not be improved.
In order to illustrate the advantages of the present invention, the present invention will be illustrated herein by way of comparative examples.
Comparative example 1
Adding 100g of methyl vinyl silicone rubber into an internal mixer, then sequentially adding 30g of white carbon black, 150g of wollastonite, 10g of zinc borate and 5g of hydroxyl silicone oil, and carrying out internal mixing at 100 ℃ for 30min to uniformly mix the filler and the colloid to obtain a dense rubber; and (3) placing the prepared banburying rubber on an open mill, adding 1g of vulcanizing agent DBPMH to obtain a rubber compound, and vulcanizing and molding. The sample obtained was numbered 8 and the specific properties are shown in Table 4.
Comparative example 2
(1) Preparing 100g of wollastonite and 300g of distilled water into a suspension, heating to 60 ℃, adding 10g of stearic acid, stirring for 2 hours, filtering and washing after the reaction is finished, and drying in a 120 ℃ oven to prepare modified wollastonite;
(2) adding 100g of methyl vinyl silicone rubber into an internal mixer, then sequentially adding 30g of white carbon black, 150g of modified wollastonite, 10g of zinc borate and 5g of hydroxyl silicone oil, and carrying out internal mixing at 100 ℃ for 30min to uniformly mix the filler and the colloid to obtain a rubber compound; and (3) placing the prepared banburying rubber on an open mill, adding 1g of vulcanizing agent DBPMH to obtain a rubber compound, and vulcanizing and molding. The sample obtained was numbered 9 and the specific properties are shown in Table 4.
Comparative example 3
(1) Preparing suspension from 100g of wollastonite and 200g of distilled water, dissolving 10g of sodium stearate in 100g of distilled water, adding the suspension into the wollastonite suspension, placing the mixture into a flask, stirring the mixture for 2 hours at 60 ℃, filtering and washing the mixture after the reaction is finished, and drying the mixture in an oven at 120 ℃ to prepare modified wollastonite;
(2) adding 100g of methyl vinyl silicone rubber into an internal mixer, then sequentially adding 30g of white carbon black, 150g of modified wollastonite, 10g of zinc borate and 5g of hydroxyl silicone oil, and carrying out internal mixing at 100 ℃ for 30min to uniformly mix the filler and the colloid to obtain a rubber compound; and (3) placing the prepared banburying rubber on an open mill, adding 1g of vulcanizing agent DBPMH to obtain a rubber compound, and vulcanizing and molding. The sample number obtained is 10, and the specific properties are shown in Table 4.
Comparative example 4
(1) Preparing 100g of wollastonite and 200g of distilled water into suspension, dissolving 10g of hexadecyl ammonium bromide in 100g of distilled water, adding the solution into the wollastonite suspension, placing the mixture into a flask, stirring the mixture for 2 hours at 60 ℃, filtering and washing the mixture after the reaction is finished, and drying the mixture in an oven at 120 ℃ to prepare modified wollastonite;
(2) adding 100g of methyl vinyl silicone rubber into an internal mixer, then sequentially adding 30g of white carbon black, 150g of modified wollastonite, 10g of zinc borate and 5g of hydroxyl silicone oil, and carrying out internal mixing at 100 ℃ for 30min to uniformly mix the filler and the colloid to obtain a rubber compound; and (3) placing the prepared banburying rubber on an open mill, adding 1g of vulcanizing agent DBPMH to obtain a rubber compound, and vulcanizing and molding. The sample obtained was numbered 11 and the specific properties are shown in Table 4.
Comparative example 5
(1) Preparing 100g of wollastonite and 200g of distilled water into suspension, dissolving 10g of KH-550 in 100g of distilled water, adding the solution into the wollastonite suspension, placing the mixture into a flask, stirring the mixture for 2 hours at 60 ℃, filtering and washing the mixture after the reaction is finished, and drying the mixture in an oven at 120 ℃ to prepare modified wollastonite;
(2) adding 100g of methyl vinyl silicone rubber into an internal mixer, then sequentially adding 30g of white carbon black, 150g of modified wollastonite, 10g of zinc borate and 5g of hydroxyl silicone oil, and carrying out internal mixing at 100 ℃ for 30min to uniformly mix the filler and the colloid to obtain a rubber compound; and (3) placing the prepared banburying rubber on an open mill, adding 1g of vulcanizing agent DBPMH to obtain a rubber compound, and vulcanizing and molding. The sample obtained was numbered 12 and the specific properties are shown in Table 4.
Comparative example 6
(1) Preparing 100g of wollastonite and 200g of distilled water into suspension, dissolving 10g of KH-560 in 100g of distilled water, adding the suspension into the wollastonite suspension, placing the mixture into a flask, stirring the mixture for 2 hours at 60 ℃, filtering and washing the mixture after the reaction is finished, and drying the mixture in an oven at 120 ℃ to prepare modified wollastonite;
(2) adding 100g of methyl vinyl silicone rubber into an internal mixer, then sequentially adding 30g of white carbon black, 150g of modified wollastonite, 10g of zinc borate and 5g of hydroxyl silicone oil, and carrying out internal mixing at 100 ℃ for 30min to uniformly mix the filler and the colloid to obtain a rubber compound; and (3) placing the prepared banburying rubber on an open mill, adding 1g of vulcanizing agent DBPMH to obtain a rubber compound, and vulcanizing and molding. The sample number obtained is 13, and the specific properties are shown in Table 4.
Comparative example 7
(1) Preparing 100g of wollastonite and 200g of distilled water into suspension, dissolving 10g of KH-570 in 100g of distilled water, adding the solution into the wollastonite suspension, placing the mixture into a flask, stirring the mixture for 2 hours at 60 ℃, filtering and washing the mixture after the reaction is finished, and drying the mixture in an oven at 120 ℃ to prepare modified wollastonite;
(2) adding 100g of methyl vinyl silicone rubber into an internal mixer, then sequentially adding 30g of white carbon black, 150g of modified wollastonite, 10g of zinc borate and 5g of hydroxyl silicone oil, and carrying out internal mixing at 100 ℃ for 30min to uniformly mix the filler and the colloid to obtain a rubber compound; and (3) placing the prepared banburying rubber on an open mill, adding 1g of vulcanizing agent DBPMH to obtain a rubber compound, and vulcanizing and molding. The sample obtained was numbered 14 and the specific properties are shown in Table 4.
TABLE 4 Effect of different types of modifiers on the mechanical Properties of the composites
The effect of different types of modifiers on the mechanical properties of the composite material can be reflected by analyzing specific example 6 and comparative examples 1 to 7, and specific results are shown in Table 4. The wollastonite powder is prepared by using stearic acid, sodium stearate, hexadecyl ammonium bromide, KH-550, KH-560 and KH-570 respectively, and the modified powder has different influences on the composite material. Compared with an unmodified formula, the mechanical property of the composite material modified by the coupling agents KH-550, KH-560 and KH-570 and the organic acid (ester) 2,4, 6-trihydroxybenzoic acid and stearic acid is improved, and the mechanical property of the composite material cannot be improved by the surfactant sodium stearate and hexadecyl ammonium bromide. This is because the surface active agent may modify the wollastonite powder, but the groups grafted thereon after modification do not react with the silicone matrix.
Comparative example 8
(1) Preparing 100g of wollastonite and 200g of distilled water into suspension, dissolving 10g of p-hydroxybenzoic acid in 100g of distilled water, adding the dissolved p-hydroxybenzoic acid into the wollastonite suspension, placing the mixture into a flask, stirring for 2 hours at 60 ℃, filtering and washing after the reaction is finished, and drying in an oven at 120 ℃ to prepare modified wollastonite;
(2) adding 100g of methyl vinyl silicone rubber into an internal mixer, then sequentially adding 30g of white carbon black, 150g of modified wollastonite, 10g of zinc borate and 5g of hydroxyl silicone oil, and carrying out internal mixing at 100 ℃ for 30min to uniformly mix the filler and the colloid to obtain a rubber compound; and (3) placing the prepared banburying rubber on an open mill, adding 1g of vulcanizing agent DBPMH to obtain a rubber compound, and vulcanizing and molding. The sample obtained was numbered 15 and the specific properties are shown in Table 5.
Comparative example 9
(1) Preparing 100g of wollastonite and 200g of distilled water into suspension, dissolving 10g of 3, 5-dihydroxybenzoic acid in 100g of distilled water, adding the mixture into the wollastonite suspension, placing the mixture into a flask, stirring the mixture for 2 hours at 60 ℃, filtering and washing the mixture after the reaction is finished, and drying the mixture in an oven at 120 ℃ to prepare modified wollastonite;
(2) adding 100g of methyl vinyl silicone rubber into an internal mixer, then sequentially adding 30g of white carbon black, 150g of modified wollastonite, 10g of zinc borate and 5g of hydroxyl silicone oil, and carrying out internal mixing at 100 ℃ for 30min to uniformly mix the filler and the colloid to obtain a rubber compound; and (3) placing the prepared banburying rubber on an open mill, adding 1g of vulcanizing agent DBPMH to obtain a rubber compound, and vulcanizing and molding. The sample obtained was numbered 16 and the specific properties are shown in Table 5.
Comparative example 10
(1) Preparing 100g of wollastonite and 200g of distilled water into suspension, dissolving 10g of 3,4, 5-trihydroxybenzoic acid in 100g of distilled water, adding the mixture into the wollastonite suspension, placing the mixture into a flask, stirring the mixture for 2 hours at 60 ℃, filtering and washing the mixture after the reaction is finished, and drying the mixture in an oven at 120 ℃ to prepare modified wollastonite;
(2) adding 100g of methyl vinyl silicone rubber into an internal mixer, then sequentially adding 30g of white carbon black, 150g of modified wollastonite, 10g of zinc borate and 5g of hydroxyl silicone oil, and carrying out internal mixing at 100 ℃ for 30min to uniformly mix the filler and the colloid to obtain a rubber compound; and (3) placing the prepared banburying rubber on an open mill, adding 1g of vulcanizing agent DBPMH to obtain a rubber compound, and vulcanizing and molding. The sample number obtained was 17, and the specific properties are shown in Table 5.
TABLE 5 influence of different kinds of hydroxybenzoic acids on mechanical properties of organosilicon composites
Specific example 6 and comparative examples 8-10 reflect the effect of modifiers of different hydroxyl content on the composite, with specific properties as shown in table 5. The number of hydroxyl groups contained in the modifier has great influence on the modification result, and the mechanical property of the composite material is obviously improved along with the increase of the number of the hydroxyl groups in the modifier, because the organic groups grafted on the surface of the wollastonite can improve the dispersion of the wollastonite and reduce agglomeration on the one hand, and on the other hand, the hydroxyl groups can participate in the addition reaction of the organosilicon and improve the interface action of the powder and the matrix. Meanwhile, the relative position of the hydroxyl has a larger influence, and three meta-hydroxyl has higher steric hindrance effect than three ortho-hydroxyl, so that the performance of the final material is slightly inferior.
The organic silicon composite material prepared in the specific example 6 is also tested for volume resistivity, breakdown strength, tensile strength after thermal aging of the material, elongation, fire resistance test and density of ceramic body obtained by high temperature calcination, and specific parameters are shown in table 6.
Table 6 specific examples 6 various properties of silicone composites
The patent provides a preparation method of a high-strength ceramizable organic silicon material, which utilizes 2,4, 6-trihydroxybenzoic acid to carry out surface modification on wollastonite as a ceramic filler, and the modified wollastonite, a vulcanizing agent and other additives are added into organic silicon rubber to prepare the organic silicon rubber with high mechanical strength, and meanwhile, a ceramic body formed at high temperature also has better mechanical strength, and the preparation method is simple, low in equipment requirement, green and environment-friendly, and can be widely applied to the field of fireproof high-temperature-resistant materials.
The upper and lower limits and interval values of the raw materials and the upper and lower limits and interval values of the process parameters can all realize the invention, and examples are not listed here.
Claims (3)
1. A high mechanical strength ceramizable organic silicon material is characterized in that the material is prepared from 2,4, 6-trihydroxybenzoic acid modified wollastonite, organic silicon rubber, a vulcanizing agent, white carbon black, hydroxyl silicone oil, zinc borate and other auxiliary agents; the dosage of each raw material is as follows: 100g of organic silicon rubber, 150g of modified wollastonite, 30g of white carbon black, 5g of hydroxyl silicone oil, 10g of zinc borate and 1g of vulcanizing agent.
2. A high mechanical strength ceramifiable silicone material as claimed in claim 1, wherein said silicone rubber is methyl vinyl silicone rubber, said silica is fumed silica, and said vulcanizing agent is 2, 5-dimethyl-2, 5-di-tert-butyl-peroxy-hexane (DBPMH).
3. The method of claim 1, wherein the method comprises the following steps:
(1) preparation of modified wollastonite: preparing 100g of wollastonite and 200g of distilled water into suspension, dissolving 5-15g of 2,4, 6-trihydroxybenzoic acid in 100g of distilled water, and adding the solution into the wollastonite suspension to prepare modified wollastonite slurry; carrying out modification reaction on the modified wollastonite slurry under the conditions of heating and stirring, wherein the reaction temperature is 30-90 ℃, and the reaction time is 1-4 h; filtering and washing the modified wollastonite slurry, and drying in a 120 ℃ oven to prepare modified wollastonite;
(2) weighing 150g of modified wollastonite prepared in the step (1), 100g of organic silicon rubber, 30g of auxiliary white carbon black, 5g of hydroxyl silicone oil and 10g of zinc borate according to the proportion, sequentially adding the materials into an internal mixer, and carrying out internal mixing at 100 ℃ for 30min to fully and uniformly mix the filler and the organic silicon matrix; placing the banburying adhesive on an open mill, adding 1g of vulcanizing agent, uniformly mixing, and vulcanizing and molding to obtain the high-mechanical-strength ceramizable organic silicon material.
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