CN115304931B - High-hydrophobicity and high-insulativity electrical grade magnesia and production method thereof - Google Patents
High-hydrophobicity and high-insulativity electrical grade magnesia and production method thereof Download PDFInfo
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Abstract
The invention discloses high-hydrophobicity and high-insulation electrical grade magnesia and a production method thereof, wherein magnesia particles are arranged inside the electrical grade magnesia, and a high-hydrophobicity organic silicon composite resin moistureproof additive is uniformly sprayed outside the electrical grade magnesia, and the electrical grade magnesia is cured for 1 hour at a high temperature of 120 ℃. The high-hydrophobicity organic silicon composite resin moisture-proof auxiliary agent is formed by crosslinking reaction of low-polymerization resin and siloxane polymer. The preparation method is simple to operate and low in energy consumption, the curing performance of the resin is utilized to promote the curing of the organosilicon on the surface of the high-purity magnesia, and the prepared magnesia has excellent hydrophobicity and insulativity, and can keep excellent insulativity even if immersed for a long time; and the high-hydrophobicity organic silicon composite resin moistureproof auxiliary agent has good high temperature resistance, and can be used as a middle-high temperature electrical grade magnesia moistureproof auxiliary agent.
Description
Technical Field
The invention belongs to the field of magnesia functional materials, and particularly relates to high-hydrophobicity and high-insulation electrical grade magnesia and a production method thereof.
Background
The electrical grade magnesia has excellent insulativity and heat conductivity and is mainly used for manufacturing various electric heating elements. After the electric fused crystalline magnesia is crushed, processed and mixed in granularity, the electric grade magnesia produced through a series of treatments is widely used for insulating fillers of various heating electrical elements. The main factors influencing the performance of the electrical grade magnesia are thermal conductivity, insulativity, moisture absorption rate and the like. Because the electrical grade magnesia is formed by crushing fused magnesia, most fused magnesia has low magnesia content and high moisture absorption rate, and the electrical performance of the electric heating element can be damaged after the fused magnesia is used, electric leakage and even tube explosion are easy, and great potential safety hazards exist.
At present, the problem of insulativity and hygroscopicity of the electrical grade magnesia is that low-grade fused magnesia is added with organic silicon materials for mixing, as disclosed in CN16967309A, an electrical grade magnesia powder production method for a water-boiling aluminum pipe is disclosed. The patent CN111899914A discloses an electrical grade magnesia powder for an electric heating tube of a water vapor generator and a production method thereof, and the method comprises the steps of firstly crushing and screening an electric smelting magnesium block, adding one or more inorganic auxiliary materials, then placing the crushed and screened electric smelting magnesium block in a kiln at 800-1100 ℃ for high-temperature heat treatment, adding an organosilicon material for mixing, and curing the mixed material at 200-280 ℃ again to finally obtain the electrical grade magnesia powder. In the method, most of the organic silicon has certain viscosity, so that the fluidity of magnesia is reduced after the organic silicon is added, and the production of various electric heating elements in the later period is affected, so that the organic silicon is often required to be cured at high temperature for many times; and when the organic silicon is cured, a certain amount of inorganic material is required to be added as an oil absorbent, so that the continuous fluidity is ensured in the subsequent tubing process, and then the product is ensured to be beneficial to manufacturing the electric heating element after multiple curing or high temperature is required. Not only is the operation complicated, but also the performance of magnesia can be affected to a certain extent by adding the inorganic oil absorbent, more energy is required for high-temperature curing, and the organic silicon can be damaged to a certain extent in the high-temperature curing process, so that the service life of the later-stage electrical device is affected. Therefore, it is particularly important to find a curing mode of organosilicon applied to electrical grade magnesium oxide.
Disclosure of Invention
The technical problem to be solved by the invention is to provide the high-hydrophobicity and high-insulativity electrical grade magnesia and the production method thereof, the method is to form the organic silicon composite resin moistureproof auxiliary agent by carrying out crosslinking reaction on resin and organic silicon, the curing performance of the resin is utilized to promote the curing of the organic silicon on the surface of the high-purity magnesia, and the obtained electrical grade magnesia has excellent insulativity and can still keep high insulativity after being immersed in water for 72 hours.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the high-hydrophobicity high-insulativity electrical grade magnesia, wherein magnesia particles are arranged inside the electrical grade magnesia, and a high-hydrophobicity organic silicon composite resin moistureproof auxiliary agent which is uniformly sprayed is arranged outside the electrical grade magnesia;
the preparation method of the high-hydrophobicity organic silicon composite resin moistureproof auxiliary agent comprises the following steps of:
1) Crushing and screening to obtain magnesia with 40-325 meshes;
2) Mixing and dissolving organic silane with an amino end group and other organic silane in solvent ethanol, wherein the other organic silane is at least one of methyltriethoxysilane, phenyltriethoxysilane, dimethyldichlorosilane, phenyltrichlorosilane, diphenyldichlorosilane and methylphenyldichlorosilane, adding ammonia water as an inducer, reacting for 30 minutes at 40 ℃, then heating to 55 ℃ for continuous reaction for 1 hour, and finally controlling the reaction temperature at 70 ℃ for continuous reaction for 45 minutes to synthesize an organic silicon prepolymer;
3) Mixing phenol and formaldehyde according to a molar ratio of 1:1.5, dispersing in ethanol solvent, adding ammonia water as a catalyst, reacting for 1 hour at 70 ℃, adding and mixing the organosilicon prepolymer in the step 2) according to a molar ratio of 1:1 of organosilane with amino groups as end groups in the organosilicon prepolymer, continuously reacting for 3 hours at 70 ℃, and removing ethanol and ammonia water through reduced pressure distillation to obtain the high-hydrophobicity organosilicon composite resin moistureproof auxiliary agent;
and atomizing and spraying the magnesia with the high-hydrophobicity organic silicon composite resin moistureproof auxiliary agent, and curing for 1 hour at a high temperature of 120 ℃ to obtain the high-hydrophobicity high-insulation electrical grade magnesia.
Further preferably, in step 2) the monomeric organosilicon is an amino-terminated organosilane 3-aminopropyl triethoxysilane.
Further preferably, the mass ratio of the organic silicon composite resin moisture-proof auxiliary agent to the magnesia is 200:1.
It is further preferred that the molar ratio of amino terminated organosilane to other organosilane is 1:1.
It is further preferred that in step 2) the molar volume ratio of the amino terminated organosilane to the aqueous ammonia is 0.05mol/mL.
It is further preferred that in step 3), the molar volume ratio of phenol to aqueous ammonia is 0.05mol/mL.
Further preferably, the mass concentration of the aqueous ammonia in step 2) and step 3) is 25%.
On the other hand, the production method of the high-hydrophobicity and high-insulativity electrical grade magnesia is characterized by comprising the following steps of:
the method comprises the following specific steps:
1) Crushing and screening to obtain magnesia with 40-325 meshes;
2) Mixing and dissolving organic silane with an amino end group and other organic silane in solvent ethanol, wherein the other organic silane is at least one of methyltriethoxysilane, phenyltriethoxysilane, dimethyldichlorosilane, phenyltrichlorosilane, diphenyldichlorosilane and methylphenyldichlorosilane, adding ammonia water as an inducer, reacting for 30 minutes at 40 ℃, then heating to 55 ℃ for continuous reaction for 1 hour, and finally controlling the reaction temperature at 70 ℃ for continuous reaction for 45 minutes to synthesize an organic silicon prepolymer;
3) Mixing phenol and formaldehyde according to a molar ratio of 1:1.5, dispersing in ethanol solvent, adding ammonia water as a catalyst, reacting for 1 hour at 70 ℃, adding and mixing the organosilicon prepolymer in the step 2) according to a molar ratio of 1:1 of organosilane with amino groups as end groups in the organosilicon prepolymer, continuously reacting for 3 hours at 70 ℃, and removing ethanol and ammonia water through reduced pressure distillation to obtain the organosilicon composite resin moistureproof auxiliary agent;
4) Spraying the organic silicon composite resin moisture-proof auxiliary agent and the magnesia of the step 1) in a mixer in a atomizing mode, stirring for 15 minutes at a stirring speed of 80r/min, and obtaining a material A;
5) And (3) curing the material A obtained in the step (4) at a high temperature of 120 ℃ for 1 hour, and screening the cured material to obtain the final high-hydrophobicity and high-insulation electrical grade magnesia.
Compared with the prior art, the invention has the following advantages:
(1) The resin and the organic silicon are subjected to a crosslinking reaction to form an organic silicon composite resin moistureproof auxiliary agent, the organic silicon composite resin moistureproof auxiliary agent has good high temperature resistance, can be used as a medium-high temperature electrical grade magnesia moistureproof auxiliary agent, and can promote the solidification of the organic silicon on the surface of high-purity magnesia by utilizing the solidification performance of the resin, so that the electrical grade magnesia has excellent hydrophobic performance, and still maintains excellent insulating performance after being soaked in water; in addition, the reaction temperature is the same in the process of crosslinking the organosilicon prepolymer and the resin, and no temperature difference exists in the reaction process, so that the crosslinking reaction is facilitated.
(2) The organosilicon monomer with amino groups and other organosilicon monomers without amino groups are adopted to synthesize the organosilicon prepolymer with amino groups, so that the organosilicon prepolymer can be crosslinked with carboxyl groups in resin to form novel organosilicon crosslinked resin on the premise of having good insulating effect, the adhesion of organosilicon on the surface of magnesium oxide is promoted, the organosilicon is cured to form a film at a lower temperature at 120 ℃ by utilizing the low-temperature curing characteristic of the resin, and the electrical grade magnesia after low-temperature curing still maintains excellent insulating performance after soaking for 72 hours, so that the soaking insulating property for a long time can be maintained.
(3) The electrical grade magnesia does not need to add any inorganic filler as an oil absorbent in the manufacturing process, and the magnesia modified by the organic silicon composite resin moisture-proof auxiliary agent still has excellent fluidity.
Detailed Description
The following further illustrates the invention in connection with specific examples, which are not intended to limit the scope of the invention.
Example 1
(1) Firstly, weighing 0.1mol of 3-aminopropyl triethoxysilane and 0.1mol of methyl triethoxysilane, mixing and stirring in an ethanol solution for 10 minutes, adding 2mL of ammonia water inducer with the mass concentration of 25%, reacting for 30 minutes at 40 ℃, then heating to 55 ℃ for continuous reaction for 1 hour, and finally controlling the reaction at 70 ℃ for 45 minutes to generate an organosilicon prepolymer No. 1;
(2) Mixing 0.1mol of phenol and 0.15mol of formaldehyde, dispersing in ethanol, adding 2mL of ammonia water with mass concentration of 25% as a catalyst, reacting for 1 hour at 70 ℃, mixing the organosilicon prepolymer No. 1 obtained in the step (1) with the mixture, continuously reacting for 3 hours at 70 ℃, and removing the ethanol and the ammonia water by reduced pressure distillation to obtain an organosilicon composite resin moistureproof auxiliary No. 1;
(3) Uniformly mixing the organic silicon composite resin moisture-proof auxiliary agent No. 1 and diluent dimethylbenzene according to the mass ratio of 7:3 to prepare organic silicon composite resin moisture-proof auxiliary agent solution No. 1;
(4) Crushing and screening to obtain 40-325 mesh magnesia powder, weighing 200g of magnesia particles, spraying and mixing 200g of the magnesia particles with 1.0g of the organic silicon composite resin moisture-proof auxiliary agent solution No. 1 prepared in the step (3) in a mixer, stirring for 15 minutes at the rotating speed of 80r/min, and uniformly coating the organic silicon composite resin moisture-proof auxiliary agent solution No. 1 on the surfaces of the magnesia particles, and marking the mixture as a material A;
(5) And (3) curing the material A obtained in the step (4) at a high temperature of 120 ℃ for 1 hour, and screening the cured material to obtain the final high-hydrophobicity and high-insulation electrical grade magnesia.
Example 2
In comparison with example 1, the methyltriethoxysilane in step (1) was replaced with phenyltriethoxysilane, and the final highly hydrophobic and highly insulating electrical grade magnesia, designated as 2-MgO, was obtained in the same manner as in example 1.
(1) Firstly, weighing 0.1mol of 3-aminopropyl triethoxysilane and 0.1mol of phenyl triethoxysilane, mixing and stirring in an ethanol solution for 10 minutes, adding 2mL of ammonia water inducer with the mass concentration of 25%, reacting for 30 minutes at 40 ℃, then heating to 55 ℃ for continuous reaction for 1 hour, and finally controlling the reaction at 70 ℃ for 45 minutes to generate an organosilicon prepolymer No. 2;
(2) Mixing 0.1mol of phenol and 0.15mol of formaldehyde, dispersing in ethanol, adding 2mL of ammonia water with mass concentration of 25% as a catalyst, reacting for 1 hour at 70 ℃, mixing the organosilicon prepolymer No. 2 obtained in the step (1) with the mixture, continuously reacting for 3 hours at 70 ℃, and removing the ethanol and the ammonia water by reduced pressure distillation to obtain an organosilicon composite resin dampproof auxiliary No. 2;
(3) Uniformly mixing the organic silicon composite resin moisture-proof auxiliary agent No. 2 with diluent dimethylbenzene according to the mass ratio of 7:3 to prepare organic silicon composite resin moisture-proof auxiliary agent solution No. 2;
(4) Crushing and screening to obtain 40-325 mesh magnesia powder, weighing 200g of magnesia particles, spraying and mixing 200g of the magnesia particles with 1.0g of the organic silicon composite resin moisture-proof auxiliary agent solution No. 2 prepared in the step (3) in a mixer, stirring for 15 minutes at the rotating speed of 80r/min, and uniformly coating the organic silicon composite resin moisture-proof auxiliary agent solution No. 2 on the surfaces of the magnesia particles, and marking the mixture as a material B;
(5) And (3) curing the material B obtained in the step (4) at a high temperature of 120 ℃ for 1 hour, and screening the cured material to obtain the final high-hydrophobicity and high-insulation electrical grade magnesia.
Example 3
In comparison with example 1, the difference is that the methyltriethoxysilane in step (1) is replaced with phenyltrichlorosilane, and the final high-hydrophobicity and high-insulation electrical grade magnesia, which is designated as 3-MgO, is obtained.
(1) Firstly, weighing 0.1mol of 3-aminopropyl triethoxysilane and 0.1mol of phenyl trichlorosilane, mixing and stirring in an ethanol solution for 10 minutes, adding 2mL of ammonia water inducer with the mass concentration of 25%, reacting for 30 minutes at 40 ℃, then heating to 55 ℃ for continuous reaction for 1 hour, and finally controlling the reaction at 70 ℃ for 45 minutes to generate an organosilicon prepolymer No. 3;
(2) Mixing 0.1mol of phenol and 0.15mol of formaldehyde, dispersing in ethanol, adding 2mL of ammonia water with mass concentration of 25% as a catalyst, reacting for 1 hour at 70 ℃, mixing the organosilicon prepolymer No. 3 obtained in the step (1) with the mixture, continuously reacting for 3 hours at 70 ℃, and removing the ethanol and the ammonia water by reduced pressure distillation to obtain an organosilicon composite resin dampproof auxiliary No. 3;
(3) Uniformly mixing the organic silicon composite resin moisture-proof auxiliary agent No. 3 and diluent dimethylbenzene according to the mass ratio of 7:3 to prepare organic silicon composite resin moisture-proof auxiliary agent solution No. 3;
(4) Crushing and screening to obtain 40-325 mesh magnesia powder, weighing 200g of magnesia particles, spraying and mixing 200g of magnesia particles with 1.0g of the organic silicon composite resin moisture-proof auxiliary agent solution No. 3 prepared in the step (3) in a mixer, stirring for 15 minutes at the rotating speed of 80r/min, uniformly coating the organic silicon composite resin moisture-proof auxiliary agent solution No. 3 on the surfaces of the magnesia particles, and marking as a material C;
(5) And (3) curing the material C obtained in the step (4) at a high temperature of 120 ℃ for 1 hour, and screening the cured material to obtain the final high-hydrophobicity and high-insulation electrical grade magnesia.
Example 4
In comparison with example 1, the methyltriethoxysilane in step (1) was replaced with diphenyldichlorosilane, and the final highly hydrophobic and highly insulating electrical grade magnesia, designated 4-MgO, was obtained in the same manner as in example 1.
(1) Firstly, weighing 0.1mol of 3-aminopropyl triethoxysilane and 0.1mol of diphenyl dichlorosilane, mixing and stirring in an ethanol solution for 10 minutes, adding 2mL of ammonia water inducer with the mass concentration of 25%, reacting for 30 minutes at 40 ℃, then heating to 55 ℃ for continuous reaction for 1 hour, and finally controlling the reaction at 70 ℃ for 45 minutes to generate an organosilicon prepolymer No. 4;
(2) Mixing 0.1mol of phenol and 0.15mol of formaldehyde, dispersing in ethanol, adding 2mL of ammonia water with mass concentration of 25% as a catalyst, reacting for 1 hour at 70 ℃, mixing the organosilicon prepolymer No. 4 obtained in the step (1) with the mixture, continuously reacting for 3 hours at 70 ℃, and removing the ethanol and the ammonia water by reduced pressure distillation to obtain an organosilicon composite resin moistureproof auxiliary No. 4;
(3) Uniformly mixing the organic silicon composite resin moisture-proof auxiliary agent No. 4 with diluent dimethylbenzene according to the mass ratio of 7:3 to prepare organic silicon composite resin moisture-proof auxiliary agent solution No. 4;
(4) Crushing and screening to obtain 40-325 mesh magnesia powder, weighing 200g of magnesia particles, spraying and mixing 200g of the magnesia particles with 1.0g of the organic silicon composite resin moisture-proof auxiliary agent solution No. 4 prepared in the step (3) in a mixer, stirring for 15 minutes at the rotating speed of 80r/min, uniformly coating the organic silicon composite resin moisture-proof auxiliary agent solution No. 4 on the surfaces of the magnesia particles, and marking as a material D;
(5) And (3) curing the material D obtained in the step (4) at a high temperature of 120 ℃ for 1 hour, and screening the cured material to obtain the final high-hydrophobicity and high-insulation electrical grade magnesia.
Example 5
In comparison with example 1, the methyltriethoxysilane in step (1) was replaced with methylphenyldichlorosilane, and the final highly hydrophobic and highly insulating electrical grade magnesia, designated 5-MgO, was obtained in the same manner as in example 1.
(1) Firstly, weighing 0.1mol of 3-aminopropyl triethoxysilane and 0.1mol of methyl phenyl dichlorosilane, mixing and stirring in an ethanol solution for 10 minutes, adding 2mL of ammonia water inducer with the mass concentration of 25%, reacting for 30 minutes at 40 ℃, then heating to 55 ℃ for continuous reaction for 1 hour, and finally controlling the reaction at 70 ℃ for 45 minutes to generate an organosilicon prepolymer No. 5;
(2) Mixing 0.1mol of phenol and 0.15mol of formaldehyde, dispersing in ethanol, adding 2mL of ammonia water with mass concentration of 25% as a catalyst, reacting for 1 hour at 70 ℃, mixing the organosilicon prepolymer No. 5 obtained in the step (1) with the mixture, continuously reacting for 3 hours at 70 ℃, and removing the ethanol and the ammonia water by reduced pressure distillation to obtain an organosilicon composite resin moistureproof auxiliary No. 5;
(3) Uniformly mixing the organic silicon composite resin moisture-proof auxiliary agent No. 5 with diluent dimethylbenzene according to the mass ratio of 7:3 to prepare organic silicon composite resin moisture-proof auxiliary agent solution No. 5;
(4) Crushing and screening to obtain 40-325 mesh magnesia powder, weighing 200g of magnesia particles, spraying and mixing 200g of the magnesia particles with 1.0g of the organic silicon composite resin moisture-proof auxiliary agent solution No. 5 prepared in the step (3) in a mixer, stirring for 15 minutes at the rotating speed of 80r/min, uniformly coating the organic silicon composite resin moisture-proof auxiliary agent solution No. 5 on the surfaces of the magnesia particles, and marking as a material E;
(5) And (3) curing the material E obtained in the step (4) at a high temperature of 120 ℃ for 1 hour, and screening the cured material to obtain the final high-hydrophobicity and high-insulation electrical grade magnesia.
The organic silicon composite resin moisture-proof auxiliary agent solutions 1-5 of the embodiment 1-5 can be used as high-temperature electrician magnesia moisture-proof agents.
Comparative example 1
(1) Uniformly mixing methyl hydrogen-containing silicone oil and diluent dimethylbenzene according to a mass ratio of 7:3 to prepare a uniform organosilicon auxiliary agent;
(2) 200g of magnesium oxide particles and 1.0g of the organic silicon dampproof auxiliary agent prepared in the step (1) are weighed, sprayed and mixed in a mixer for 15 minutes, and the rotating speed is 80r/min, so that the particles are fully coated on the surfaces of the magnesium oxide particles and marked as a material a;
(3) And (3) solidifying the material a obtained in the step (2) in a kiln at 150 ℃ for 2 hours, naturally cooling after solidifying at the temperature of 250 ℃ for 1 hour, sieving, and packaging to obtain the conventional process electrical grade magnesium oxide serving as a comparative example, which is denoted as comparative example 1.
Comparative example 2
In comparison with example 1, the organosilicon in step (1) was added with 3-aminopropyl triethoxysilane alone, and the electrical grade magnesite finally obtained was designated as comparative example 2, otherwise identical to example 1.
(1) Firstly, weighing 0.2mol of 3-aminopropyl triethoxysilane, mixing and stirring in ethanol solution for 10 minutes, adding 2mL of ammonia water inducer with mass concentration of 25%, reacting at 40 ℃ for 30 minutes, heating to 55 ℃ and continuing to react for 1 hour, and finally controlling the reaction at 70 ℃ to react for 45 minutes to generate organosilicon prepolymer comparative example No. 2;
(2) Mixing 0.1mol of phenol and 0.15mol of formaldehyde, dispersing in ethanol, adding 2mL of ammonia water with mass concentration of 25% as a catalyst, reacting for 1 hour at 70 ℃, mixing the organosilicon prepolymer obtained in the step (1) with the organosilicon prepolymer in comparative example No. 2, continuously reacting for 3 hours at 70 ℃, and removing ethanol and ammonia water by reduced pressure distillation to obtain organosilicon composite resin;
(3) Uniformly mixing the organic silicon composite resin and the diluent dimethylbenzene according to the mass ratio of 7:3 to prepare an organic silicon composite resin solution;
(4) Crushing and screening to obtain 40-325 mesh magnesia powder, weighing 200g of magnesia particles, spraying and mixing 200g of magnesia particles with 1.0g of the organic silicon composite resin solution prepared in the step (3) in a mixer, stirring for 15 minutes at the rotating speed of 80r/min, and uniformly coating the organic silicon composite resin solution on the surfaces of the magnesia particles, and marking as a material b;
(5) And (3) curing the material b obtained in the step (4) at a high temperature of 120 ℃ for 1 hour, and screening the cured material to obtain the electrical grade magnesia.
Comparative example 3
In comparison with example 1, the silicone in step (1) was added with methyltriethoxysilane alone, and the resulting electrical grade magnesite was designated as comparative example 3, otherwise identical to example 1.
(1) Firstly, weighing 0.1mol of methyltriethoxysilane, mixing and stirring in an ethanol solution for 10 minutes, adding 2mL of ammonia water inducer with the mass concentration of 25%, reacting for 30 minutes at 40 ℃, then heating to 55 ℃ for continuous reaction for 1 hour, and finally controlling the reaction to react for 45 minutes at 70 ℃ to generate organosilicon prepolymer comparative example No. 3;
(2) Mixing 0.1mol of phenol and 0.15mol of formaldehyde, dispersing in ethanol, adding 2mL of ammonia water with mass concentration of 25% as a catalyst, reacting for 1 hour at 70 ℃, mixing the organosilicon prepolymer obtained in the step (1) with the organosilicon prepolymer obtained in the comparative example No. 3, and continuing to react for 3 hours at 70 ℃, wherein the synthesized organosilicon prepolymer and the resin are not crosslinked successfully.
Comparative example 4
In comparison with example 1, only phenyltrichlorosilane was added in step (1), and the finally obtained electrical grade magnesite was designated as comparative example 4, in the same manner as in example 1.
(1) Firstly, 0.1mol of phenyl trichlorosilane is weighed, mixed and stirred in ethanol solution for 10 minutes, 2mL of ammonia water inducer with the mass concentration of 25% is added for reaction for 30 minutes at the temperature of 40 ℃, then the temperature is raised to 55 ℃ for continuous reaction for 1 hour, and finally the reaction is controlled to be carried out for 45 minutes at the temperature of 70 ℃ to generate organosilicon prepolymer comparative example No. 4;
(2) Mixing 0.1mol of phenol and 0.15mol of formaldehyde, dispersing in ethanol, adding 2mL of ammonia water with mass concentration of 25% as a catalyst, reacting for 1 hour at 70 ℃, mixing the organosilicon prepolymer obtained in the step (1) with the organosilicon prepolymer obtained in the comparative example No. 4, and continuing to react for 3 hours at 70 ℃, wherein the synthesized organosilicon prepolymer and the resin are not crosslinked successfully.
Comparative example 5
In comparison with example 1, only diphenyldichlorosilane was added in step (1), and the resulting electrical grade magnesite was obtained in the same manner as in example 1, and was designated as comparative example 5.
(1) Firstly, weighing 0.1mol of diphenyl dichlorosilane, mixing and stirring in an ethanol solution for 10 minutes, adding 2mL of ammonia water inducer with the mass concentration of 25%, reacting for 30 minutes at 40 ℃, then heating to 55 ℃ for continuous reaction for 1 hour, and finally controlling the reaction at 70 ℃ for 45 minutes to generate the organosilicon prepolymer comparative example No. 5;
(2) Mixing 0.1mol of phenol and 0.15mol of formaldehyde, dispersing in ethanol, adding 2mL of ammonia water with mass concentration of 25% as a catalyst, reacting for 1 hour at 70 ℃, mixing the organosilicon prepolymer obtained in the step (1) with the organosilicon prepolymer in the comparative example No. 5, and continuing to react for 3 hours at 70 ℃, wherein the synthesized organosilicon prepolymer and the resin are not crosslinked successfully.
Comparative example 6
In comparison with example 1, only methylphenyl dichlorosilane was added in step (1), and the electrical grade magnesite finally obtained in the same manner as in example 1 was designated as comparative example 6.
(1) Firstly, weighing 0.1mol of methyl phenyl dichlorosilane, mixing and stirring in an ethanol solution for 10 minutes, adding 2mL of ammonia water inducer with the mass concentration of 25%, reacting for 30 minutes at 40 ℃, then heating to 55 ℃ for continuous reaction for 1 hour, and finally controlling the reaction to react for 45 minutes at 70 ℃ to generate an organosilicon prepolymer of comparative example 6;
(2) Mixing 0.1mol of phenol and 0.15mol of formaldehyde, dispersing in ethanol, adding 2mL of ammonia water with mass concentration of 25% as a catalyst, reacting for 1 hour at 70 ℃, mixing the organosilicon prepolymer obtained in the step (1) with the organosilicon prepolymer obtained in the comparative example 6, and continuing to react for 3 hours at 70 ℃, wherein the synthesized organosilicon prepolymer and the resin are not crosslinked successfully.
Comparative example 7
In comparison with example 1, the final electrical grade magnesite obtained in step (1) was obtained by changing the reaction at 70℃for 45 minutes to 70℃for 15 minutes, and the procedure was otherwise the same as in example 1, and was designated as comparative example 7.
(1) Firstly, weighing 0.1mol of 3-aminopropyl triethoxysilane and 0.1mol of methyl triethoxysilane, mixing and stirring in an ethanol solution for 10 minutes, adding 2mL of ammonia water inducer with the mass concentration of 25%, reacting for 30 minutes at 40 ℃, then heating to 55 ℃ for continuous reaction for 1 hour, and finally controlling the reaction at 70 ℃ for 15 minutes to generate an organosilicon prepolymer comparative example No. 7;
(2) Mixing 0.1mol of phenol and 0.15mol of formaldehyde, dispersing in ethanol, adding 2mL of ammonia water with mass concentration of 25% as a catalyst, reacting for 1 hour at 70 ℃, mixing the organosilicon prepolymer obtained in the step (1) with the organosilicon prepolymer in comparative example 7, continuously reacting for 3 hours at 70 ℃, and removing ethanol and ammonia water by reduced pressure distillation to obtain organosilicon dampproof auxiliary in comparative example 7;
(3) Uniformly mixing the organic silicon dampproof auxiliary agent comparative example No. 7 and the diluent dimethylbenzene according to the mass ratio of 7:3 to prepare organic silicon dampproof auxiliary agent comparative example No. 7-dimethylbenzene mixed solution;
(4) Crushing and screening to obtain 40-325 mesh magnesia powder, weighing 200g of magnesia particles and 1.0g of the organosilicon dampproof auxiliary agent comparative example No. 7-dimethylbenzene mixed solution prepared in the step (3), spraying and mixing in a mixer, stirring at the rotating speed of 80r/min for 15 minutes, uniformly coating the organosilicon dampproof auxiliary agent comparative example No. 7-dimethylbenzene mixed solution on the surfaces of the magnesia particles, and marking as a material c;
(5) And (3) curing the material c obtained in the step (4) at a high temperature of 120 ℃ for 1 hour, and screening the cured material to obtain the modified magnesia.
Comparative example 8
In comparison with example 1, the final electrical grade magnesite obtained in step (1) was obtained in the same manner as in example 1 except that the reaction was changed from the reaction at 70℃for 45 minutes to the reaction at 70℃for 3 hours, and was designated as comparative example 8.
(1) Firstly, weighing 0.1mol of 3-aminopropyl triethoxysilane and 0.1mol of methyl triethoxysilane, mixing and stirring in an ethanol solution for 10 minutes, adding 2mL of ammonia water inducer with the mass concentration of 25%, reacting for 30 minutes at 40 ℃, then heating to 55 ℃ for continuous reaction for 1 hour, and finally controlling the reaction at 70 ℃ for 3 hours to generate an organosilicon prepolymer comparative example No. 8;
(2) Mixing 0.1mol of phenol and 0.15mol of formaldehyde, dispersing in ethanol, adding 2mL of ammonia water with mass concentration of 25% as a catalyst, reacting for 1 hour at 70 ℃, mixing the organosilicon prepolymer obtained in the step (1) with the organosilicon prepolymer in the comparative example No. 8, preserving heat at 70 ℃, and layering the organosilicon prepolymer and resin, so that the crosslinking reaction cannot be carried out.
Comparative example 9
In comparison with example 1, step (2) was directly carried out without going through step (1), and only resin was added as a moisture-proof auxiliary agent, and the electrical grade magnesite finally obtained in the same manner as in example 1 was designated as comparative example 9.
(1) Mixing 0.1mol of phenol and 0.15mol of formaldehyde, dispersing in ethanol, adding 2mL of ammonia water with mass concentration of 25% as a catalyst, reacting for 4 hours at 70 ℃, and removing ethanol and ammonia water by reduced pressure distillation to obtain resin A;
(2) Uniformly mixing the resin A and the diluent dimethylbenzene according to the mass ratio of 7:3 to prepare a resin-dimethylbenzene mixed solution;
(3) Crushing and screening to obtain 40-325 mesh magnesia powder, weighing 200g of magnesia particles, mixing with 1.0g of the resin-xylene mixed solution prepared in the step (2) in a mixer in a spraying manner, stirring for 15 minutes at the rotating speed of 80r/min, uniformly coating the resin-xylene mixed solution on the surfaces of the magnesia particles, and marking as a material d;
(4) And (3) curing the material d obtained in the step (3) at a high temperature of 120 ℃ for 1 hour, and screening the cured material to obtain the modified magnesia.
Since the silicone prepolymer synthesized in comparative example 3-comparative example 6 was not crosslinked successfully with the resin, it was demonstrated that the monomeric organosilane without terminal amino groups in the monomeric organosilicon of the synthetic silicone prepolymer was an unreasonable moisture-resistant auxiliary for silicone composite resins. In comparative example 8, since the reaction time was too long and the polymerization degree of the silicone oil was too high, delamination occurred directly during the crosslinking with the resin, indicating that the reaction time would affect the crosslinking of the silicone oil with the resin.
TABLE 1 insulation test
Note that: the above test criteria are in accordance with the reference: industry standard of the mechanical industry department, electrical grade magnesia powder, JB/T18508-1996.
As can be seen from Table 1, examples 1 to 5 have a normal insulation performance of 10 5 On the order of mΩ, the insulating capacity is higher than that of magnesia produced by the conventional process in comparative example 1. Examples 1-5 can still remain at 10 in terms of moisture and water insulation 5 M.OMEGA.level has excellent insulation performance even after soaking for 72h, while the wet insulation of magnesia prepared by the conventional process in comparative example 1 is reduced to 10 4 Omega, after 72h of immersion, was only 500 omega, whereas for comparative example 2, where only 3-aminopropyl triethoxysilane was added, the normal insulation was only 10 x 10 3 M omega, after soaking, has little insulating effect, probably because one side end group of 3-aminopropyl triethoxy silane is amino, end capping is easy to carry out in the polymerization process, the polymerization degree of silane is smaller, and good insulating effect is not achieved. In comparative example 7, the insulating property was relatively poor, probably because the time for polymerization of silicone oil was too short to reach a certain degree of polymerization, thereby exhibiting insulating properties similar to those of pure resins.
In summary, the moisture-proof auxiliary agent of the organic silicon composite resin is formed by combining the resin and the organic silicon, the curing performance of the resin is utilized to promote the curing of the organic silicon on the surface of the high-purity magnesia, the adhesiveness of the organic silicon on the surface of the magnesia can be promoted, and the electrical grade magnesia has excellent insulating performance and hydrophobic performance, and the insulating performance can be maintained even in a moist and water-immersed environment. The principle can be explained by the polycondensation of silicones in the presence of an inducer and a solvent to form a silicone polymer which is further transesterified with the low degree of polymerization resin to crosslink the silicone with the resin. In the curing process, the curing of the resin can further increase the adhesive force of the organosilicon on the surface of the magnesia, so that the modified magnesia has excellent performance; in the tubing process, the modified magnesia still has excellent fluidity even without adding inorganic materials as oil absorbent.
Claims (7)
1. An electrical grade magnesia with high hydrophobicity and high insulation is characterized in that: the interior of the electrical grade magnesia is magnesia particles, and the exterior of the electrical grade magnesia is a high-hydrophobicity organic silicon composite resin moistureproof auxiliary agent which is uniformly sprayed;
the preparation method of the high-hydrophobicity organic silicon composite resin moistureproof auxiliary agent comprises the following steps of:
1) Crushing and screening to obtain magnesia with 40-325 meshes;
2) Mixing and dissolving organic silane with an amino end group and other organic silane in solvent ethanol, wherein the organic silane with the amino end group is 3-aminopropyl triethoxy silane, the other organic silane is at least one of methyltriethoxysilane, phenyl triethoxy silane, dimethyl dichloro silane, phenyl trichloro silane, diphenyl dichloro silane and methyl phenyl dichloro silane, adding an inducer ammonia water, reacting for 30 minutes at 40 ℃, then heating to 55 ℃ for continuous reaction for 1 hour, finally controlling the reaction temperature to 70 ℃, and continuously reacting for 45 minutes to synthesize an organic silicon prepolymer;
3) Mixing phenol and formaldehyde according to a molar ratio of 1:1.5, dispersing in ethanol solvent, adding ammonia water as a catalyst, reacting for 1 hour at 70 ℃, adding and mixing the organosilicon prepolymer in the step 2) according to a molar ratio of 1:1 of organosilane with amino groups as end groups in the organosilicon prepolymer, continuously reacting for 3 hours at 70 ℃, and removing ethanol and ammonia water through reduced pressure distillation to obtain the high-hydrophobicity organosilicon composite resin moistureproof auxiliary agent;
and atomizing and spraying the magnesia with the high-hydrophobicity organic silicon composite resin moistureproof auxiliary agent, and curing for 1 hour at a high temperature of 120 ℃ to obtain the high-hydrophobicity high-insulation electrical grade magnesia.
2. The highly hydrophobic, highly insulating electrical grade magnesia according to claim 1, wherein: the mass ratio of the organic silicon composite resin moisture-proof auxiliary agent to the magnesia is 200:1.
3. The highly hydrophobic, highly insulating electrical grade magnesia according to claim 1, wherein: the molar ratio of the amino-terminated organosilane to the other organosilane was 1:1.
4. The highly hydrophobic, highly insulating electrical grade magnesia according to claim 1, wherein: in step 2), the molar volume ratio of the organosilane with the end group of amino group to the ammonia water is 0.05mol/mL.
5. The highly hydrophobic, highly insulating electrical grade magnesia according to claim 1, wherein: in step 3), the molar volume ratio of phenol to ammonia water was 0.05mol/mL.
6. The highly hydrophobic, highly insulating electrical grade magnesia according to claim 1, wherein: the mass concentration of the aqueous ammonia in step 2) and step 3) was 25%.
7. A method for producing highly hydrophobic, highly insulating electrical grade magnesia as claimed in any one of claims 1 to 6, wherein:
the method comprises the following specific steps:
1) Crushing and screening to obtain magnesia with 40-325 meshes;
2) Mixing and dissolving organic silane with an amino end group and other organic silane in solvent ethanol, wherein the organic silane with the amino end group is 3-aminopropyl triethoxy silane, the other organic silane is at least one of methyltriethoxysilane, phenyl triethoxy silane, dimethyl dichloro silane, phenyl trichloro silane, diphenyl dichloro silane and methyl phenyl dichloro silane, adding an inducer ammonia water, reacting for 30 minutes at 40 ℃, then heating to 55 ℃ for continuous reaction for 1 hour, finally controlling the reaction temperature to 70 ℃, and continuously reacting for 45 minutes to synthesize an organic silicon prepolymer;
3) Mixing phenol and formaldehyde according to a molar ratio of 1:1.5, dispersing in ethanol solvent, adding ammonia water as a catalyst, reacting for 1 hour at 70 ℃, adding and mixing the organosilicon prepolymer in the step 2) according to a molar ratio of 1:1 of organosilane with amino groups as end groups in the organosilicon prepolymer, continuously reacting for 3 hours at 70 ℃, and removing ethanol and ammonia water through reduced pressure distillation to obtain the organosilicon composite resin moistureproof auxiliary agent;
4) Spraying the organic silicon composite resin moisture-proof auxiliary agent and the magnesia of the step 1) in a mixer in a atomizing mode, stirring for 15 minutes at a stirring speed of 80r/min to obtain a material A;
5) And (3) curing the material A obtained in the step (4) at a high temperature of 120 ℃ for 1 hour, and screening the cured material to obtain the final high-hydrophobicity and high-insulation electrical grade magnesia.
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| DE102004029074A1 (en) * | 2004-06-16 | 2005-12-29 | Degussa Ag | Paint formulation for improving the surface properties |
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| US4110939A (en) * | 1977-06-13 | 1978-09-05 | The Carborundum Company | Cuprous oxide containing resin bonded abrasive article and process for manufacturing same |
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