CN115975470A - Modified silica ceramic resin and preparation method thereof - Google Patents
Modified silica ceramic resin and preparation method thereof Download PDFInfo
- Publication number
- CN115975470A CN115975470A CN202211101320.7A CN202211101320A CN115975470A CN 115975470 A CN115975470 A CN 115975470A CN 202211101320 A CN202211101320 A CN 202211101320A CN 115975470 A CN115975470 A CN 115975470A
- Authority
- CN
- China
- Prior art keywords
- resin
- boric acid
- doped polyaniline
- stirring
- ammonium persulfate
- 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
Landscapes
- Silicon Polymers (AREA)
Abstract
The invention discloses a modified silica ceramic resin and a preparation method thereof, wherein the modified silica ceramic resin comprises 40-50 parts by weight of silicon resin, 50-70 parts by weight of waterborne epoxy resin and 1-3 parts by weight of boric acid doped polyaniline, the silicon resin is obtained by adding styrene for crosslinking after co-hydrolyzing tetraethoxysilane and gamma-methacryloxypropyl trimethoxy silane, and the boric acid doped polyaniline is synthesized by a chemical oxidation method by using boric acid as a dopant and ammonium persulfate as an initiator. According to the invention, the waterborne epoxy resin and the silicon resin are compounded, the waterborne epoxy coating system has the advantages of high adhesive force, excellent corrosion resistance of a coating film and good construction performance, the defects of the silicon resin in the aspects of curing property, adhesion property, solvent resistance, mechanical strength and the like can be perfectly supplemented, and the added boric acid is doped with the polyaniline, so that the corrosion resistance and weather resistance of the resin coating are further improved.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a modified silica ceramic resin and a preparation method thereof.
Background
The silicone resin is a semi-inorganic high polymer with a highly cross-linked structure, and has the dual characteristics of organic resin and inorganic material due to the special composition and molecular structure. The silicone resin belongs to thermosetting plastics, the most outstanding performance of the silicone resin is excellent thermal oxidation stability, after being heated at 350 ℃ for 24 hours, the mass loss rate of the silicone resin is lower than 20 percent, and the mass loss rate of common organic resin reaches 70 to 90 percent: another outstanding property of silicone is excellent electrical insulation, with an electrical strength of 50MV/m, a volume resistance of 10131015Q-cm, a relative dielectric constant of 3, and a dielectric loss factor of about 10 -3 The good insulation performance of the cable can be kept in a wide temperature and frequency range; in addition, silicone resin has excellent moisture resistance, water resistance, rust resistance, cold resistance, ozone resistance and weather resistance, and has good corrosion resistance to most of aqueous chemical agents (such as dilute mineral acid), and thus, is widely used.
However, silicone resins are insufficient in curability, adhesiveness, solvent resistance, mechanical strength, and the like, and thus limit the range of applications. Different organic synthetic resins have different advantages and disadvantages, and the deficiency of silicone resin is just the advantage of some organic synthetic resins. If organic silicon is introduced into organic synthetic resin or the organic synthetic resin is used for modifying the silicon resin, novel resin with excellent performances of the silicon resin and the organic resin can be formed, the application value of the novel resin is further improved, and the application field of the novel resin is expanded.
Disclosure of Invention
The invention aims to provide a modified silica ceramic resin and a preparation method thereof.
The purpose of the invention can be realized by the following technical scheme:
a modified silica ceramic resin comprises 40-50 parts by weight of silicone resin, 50-70 parts by weight of waterborne epoxy resin and 1-3 parts by weight of boric acid doped polyaniline;
the silicon resin is obtained by adding styrene for crosslinking after the joint hydrolysis of tetraethoxysilane and gamma-methacryloxypropyltrimethoxysilane;
the boric acid doped polyaniline is synthesized by a chemical oxidation method by using boric acid as a dopant and ammonium persulfate as an initiator.
Preferably, the preparation of the silicone resin comprises the steps of:
(1) Mixing deionized water and absolute ethyl alcohol according to a mass ratio of 1:2, adding citric acid, and ultrasonically stirring until the citric acid is dissolved;
(2) Then adding ethyl orthosilicate and gamma-methacryloxypropyltrimethoxysilane into the solution, and stirring and reacting for 6-8h at the temperature of 35-45 ℃;
(3) Adding styrene and an initiator benzoyl peroxide into a reaction system, keeping the temperature, stirring and reacting for 3-4h, and then aging for 24h at normal temperature to obtain the silicone resin.
Preferably, the preparation of the boric acid doped polyaniline comprises the following steps:
A. adding ammonium persulfate into deionized water, stirring until the ammonium persulfate is completely dissolved to obtain ammonium persulfate solution
B. Adding boric acid into deionized water, stirring until the boric acid is completely dissolved, adding aniline while stirring, dropwise adding an ammonium persulfate solution after the aniline is completely dissolved, controlling the reaction temperature to be 4-6 ℃, and reacting for 1-3h;
C. and after the reaction is finished, carrying out suction filtration, washing with deionized water to be neutral, and drying filter residues in a constant-temperature drying oven to obtain the boric acid doped polyaniline.
A preparation method of modified silicon-oxygen ceramic resin comprises the following steps:
s1, putting boric acid doped polyaniline into a ball mill, fully grinding, adding the ground boric acid doped polyaniline into silicon resin, and performing ultrasonic dispersion for 5-10min to obtain mixed slurry;
s2, adding the waterborne epoxy resin into the mixed slurry, and stirring for 1-2 hours at 200-300 r/min to obtain the modified silica ceramic resin.
Preferably, the boric acid-doped polyaniline is ground to 200-300 mesh in step S1.
The invention has the beneficial effects that:
according to the invention, the waterborne epoxy resin and the silicon resin are compounded, the waterborne epoxy coating system has the advantages of high adhesive force, excellent corrosion resistance of a coating film and good construction performance, and can perfectly supplement the defects of the silicon resin in the aspects of curing property, adhesion property, solvent resistance, mechanical strength and the like. The Polyaniline (PANI) has good oxidation-reduction capability, and a passivation film is generated on the metal surface in the conversion process of an oxidation state (PANI-Ox) and a reduction state (PANI-Re); the boric acid doped polyaniline (PANI-BA) has a special nanorod structure, and the surface of the nanorod structure has certain roughness, so that the hydrophobicity of the coating is improved, and the permeation of a medium is prevented to a certain degree. The silicon resin is prepared by hydrolyzing alkoxy silicon (KH-570) with a conjugated structural group C = C as a silane coupling agent together with Tetraethoxysilane (TEOS), introducing an unsaturated bond into the structure of inorganic silicon, and then crosslinking with styrene to obtain the bonding type silicon resin with a phenyl conjugated group, so that boric acid doped polyaniline can be better dispersed in a composite system.
Of course, it is not necessary for any product in which the invention is practiced to achieve all of the above-described advantages at the same time.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A modified silica ceramic resin comprises 40 parts by weight of silicone resin, 50 parts by weight of aqueous epoxy resin and 1 part by weight of boric acid doped polyaniline;
the preparation of the silicone resin comprises the following steps:
(1) Mixing deionized water and absolute ethyl alcohol according to a mass ratio of 1:2, adding citric acid, and ultrasonically stirring until the citric acid is dissolved;
(2) Then adding ethyl orthosilicate and gamma-methacryloxypropyl trimethoxy silane into the solution, and stirring to react for 6-8h at the temperature of 35-45 ℃;
(3) Adding styrene and an initiator benzoyl peroxide into a reaction system, keeping the temperature, stirring and reacting for 3 hours, and then aging for 24 hours at normal temperature to obtain the silicone resin.
The preparation of the boric acid doped polyaniline comprises the following steps:
A. adding ammonium persulfate into deionized water, stirring until the ammonium persulfate is completely dissolved to obtain an ammonium persulfate solution
B. Adding boric acid into deionized water, stirring until the boric acid is completely dissolved, adding aniline while stirring, dropwise adding an ammonium persulfate solution after the aniline is completely dissolved, controlling the reaction temperature to be 4 ℃, and reacting for 1h;
C. and after the reaction is finished, carrying out suction filtration, washing with deionized water to be neutral, and drying filter residues in a constant-temperature drying oven to obtain the boric acid doped polyaniline.
The preparation method of the modified silicon-oxygen ceramic resin comprises the following steps:
s1, putting boric acid doped polyaniline into a ball mill, grinding to 200 meshes, adding the boric acid doped polyaniline into silicon resin, and performing ultrasonic dispersion for 5min to obtain mixed slurry;
s2, adding the water-based epoxy resin into the mixed slurry, and stirring for 1h at 200 revolutions per minute to obtain the modified silicon-oxygen ceramic resin.
Example 2
A modified silica ceramic resin comprises 45 parts by weight of silicone resin, 60 parts by weight of water-based epoxy resin and 2 parts by weight of boric acid doped polyaniline;
the preparation of the silicone resin comprises the following steps:
(1) Mixing deionized water and absolute ethyl alcohol according to a mass ratio of 1:2, adding citric acid, and ultrasonically stirring until the citric acid is dissolved;
(2) Then adding ethyl orthosilicate and gamma-methacryloxypropyl trimethoxysilane into the solution, and stirring for reaction for 7 hours at the temperature of 40 ℃;
(3) Adding styrene and an initiator benzoyl peroxide into the reaction system, keeping the temperature, stirring and reacting for 3 hours, and then aging for 24 hours at normal temperature to obtain the silicone resin.
The preparation of the boric acid doped polyaniline comprises the following steps:
A. adding ammonium persulfate into deionized water, stirring until the ammonium persulfate is completely dissolved to obtain an ammonium persulfate solution
B. Adding boric acid into deionized water, stirring until the boric acid is completely dissolved, adding aniline while stirring, dropwise adding an ammonium persulfate solution after the aniline is completely dissolved, controlling the reaction temperature to be 5 ℃, and reacting for 2 hours;
C. and after the reaction is finished, carrying out suction filtration, washing with deionized water to be neutral, and drying filter residues in a constant-temperature drying oven to obtain the boric acid doped polyaniline.
The preparation method of the modified silicon-oxygen ceramic resin comprises the following steps:
s1, putting boric acid doped polyaniline into a ball mill, grinding to 250 meshes, adding the boric acid doped polyaniline into silicon resin, and performing ultrasonic dispersion for 8min to obtain mixed slurry;
and S2, adding the water-based epoxy resin into the mixed slurry, and stirring at 250 revolutions per minute for 1.5 hours to obtain the modified silicon-oxygen ceramic resin.
Example 3
A modified silica ceramic resin comprises 50 parts by weight of silicone resin, 70 parts by weight of water-based epoxy resin and 3 parts by weight of boric acid doped polyaniline;
the preparation of the silicone resin comprises the following steps:
(1) Mixing deionized water and absolute ethyl alcohol according to a mass ratio of 1:2, adding citric acid, and ultrasonically stirring until the citric acid is dissolved;
(2) Then adding ethyl orthosilicate and gamma-methacryloxypropyl trimethoxysilane into the solution, and stirring the mixture to react for 8 hours at the temperature of 45 ℃;
(3) Adding styrene and an initiator benzoyl peroxide into the reaction system, keeping the temperature, stirring and reacting for 4 hours, and then aging for 24 hours at normal temperature to obtain the silicone resin.
The preparation of the boric acid doped polyaniline comprises the following steps:
A. adding ammonium persulfate into deionized water, stirring until the ammonium persulfate is completely dissolved to obtain an ammonium persulfate solution
B. Adding boric acid into deionized water, stirring until the boric acid is completely dissolved, adding aniline while stirring, dropwise adding an ammonium persulfate solution after the aniline is completely dissolved, controlling the reaction temperature to be 6 ℃, and reacting for 3 hours;
C. and after the reaction is finished, carrying out suction filtration, washing with deionized water to be neutral, and drying filter residues in a constant-temperature drying oven to obtain the boric acid doped polyaniline.
The preparation method of the modified silicon-oxygen ceramic resin comprises the following steps:
s1, putting boric acid doped polyaniline into a ball mill, grinding to 300 meshes, adding the ground boric acid doped polyaniline into silicon resin, and performing ultrasonic dispersion for 10min to obtain mixed slurry;
s2, adding the waterborne epoxy resin into the mixed slurry, and stirring for 2 hours at 300 r/min to obtain the modified silica ceramic resin.
Performance detection
The cleaned 10 × 1mm stainless steel substrate was immersed in the resin prepared in examples 1 to 3 for 1min, and coated with a film by a pulling method at a pulling rate of 4mm/s. And flatly placing the prepared wet gel film, leveling the gel film on the surface of the substrate, naturally drying for ten minutes, and placing the gel film into a drying oven at the temperature of 140 ℃ for treatment for two hours to obtain the composite coating.
The composite coatings obtained were tested as follows: 1) Hardness test of the sample plate: testing according to GB/T6739-2006 Pencil method for measuring paint film hardness by color paint and varnish; 2) Impact resistance test of the sample plate: testing according to GB/T1732-1993 'paint film impact resistance determination'; 3) Adhesion test of the panels: testing according to GB/T9286-1998 test for marking the grids of paint films of colored paint and varnish; 4) Acid, alkali and brine resistance of the sample plate: part 2 of the determination of the liquid resistance of paints and varnishes in accordance with GB/T30648.2-2015: "determination of liquid resistance of paints and varnishes": and (4) testing by a water immersion method. The data obtained are shown in table 1 below:
TABLE 1 coating Performance test results
As can be seen from Table 1, the coating formed by coating the modified silica ceramic resin prepared by the invention has excellent adhesion, solvent resistance and mechanical strength, and simultaneously has higher corrosion resistance and weather resistance. The waterborne epoxy resin and the silicon resin are compounded, the performances of the waterborne epoxy resin and the silicon resin are complementary, and the added boric acid doped polyaniline can effectively improve the corrosion resistance and weather resistance of the coating.
The foregoing is merely exemplary and illustrative of the principles of the present invention and various modifications, additions and substitutions of the specific embodiments described herein may be made by those skilled in the art without departing from the principles of the present invention or exceeding the scope of the claims set forth herein.
Claims (5)
1. A modified silica ceramic resin is characterized in that: the modified silica ceramic resin comprises 40-50 parts by weight of silicone resin, 50-70 parts by weight of waterborne epoxy resin and 1-3 parts by weight of boric acid doped polyaniline;
the silicon resin is obtained by adding styrene for crosslinking after the joint hydrolysis of tetraethoxysilane and gamma-methacryloxypropyltrimethoxysilane;
the boric acid doped polyaniline is synthesized by a chemical oxidation method by using boric acid as a dopant and ammonium persulfate as an initiator.
2. The modified silicone ceramic resin of claim 1, wherein: the preparation of the silicone resin comprises the following steps:
(1) Mixing deionized water and absolute ethyl alcohol according to a mass ratio of 1:2, adding citric acid, and ultrasonically stirring until the citric acid is dissolved;
(2) Then adding ethyl orthosilicate and gamma-methacryloxypropyltrimethoxysilane into the solution, and stirring and reacting for 6-8h at the temperature of 35-45 ℃;
(3) Adding styrene and an initiator benzoyl peroxide into the reaction system, keeping the temperature, stirring and reacting for 3-4h, and then aging for 24h at normal temperature to obtain the silicone resin.
3. The modified silicone ceramic resin of claim 1, wherein: the preparation method of the boric acid doped polyaniline comprises the following steps:
A. adding ammonium persulfate into deionized water, stirring until the ammonium persulfate is completely dissolved to obtain an ammonium persulfate solution
B. Adding boric acid into deionized water, stirring until the boric acid is completely dissolved, adding aniline while stirring, dropwise adding an ammonium persulfate solution after the aniline is completely dissolved, controlling the reaction temperature to be 4-6 ℃, and reacting for 1-3h;
C. and after the reaction is finished, performing suction filtration, washing the reaction product with deionized water to be neutral, and drying filter residues in a constant-temperature drying oven to obtain the boric acid doped polyaniline.
4. A process for the preparation of a modified siloxanic resin according to any one of claims 1 to 3, characterized in that: the method comprises the following steps:
s1, putting boric acid doped polyaniline into a ball mill, fully grinding, adding the boric acid doped polyaniline into silicon resin, and performing ultrasonic dispersion for 5-10min to obtain mixed slurry;
s2, adding the water-based epoxy resin into the mixed slurry, and stirring for 1-2 hours at 200-300 r/min to obtain the modified silicon-oxygen ceramic resin.
5. The method for preparing modified silicone ceramic resin according to claim 4, wherein in step S1, the boric acid-doped polyaniline is ground to 200-300 mesh.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211101320.7A CN115975470A (en) | 2022-09-09 | 2022-09-09 | Modified silica ceramic resin and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211101320.7A CN115975470A (en) | 2022-09-09 | 2022-09-09 | Modified silica ceramic resin and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115975470A true CN115975470A (en) | 2023-04-18 |
Family
ID=85958714
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211101320.7A Pending CN115975470A (en) | 2022-09-09 | 2022-09-09 | Modified silica ceramic resin and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115975470A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116716015A (en) * | 2023-06-27 | 2023-09-08 | 上海青济新材料发展有限公司 | Container, epoxy anticorrosive paint and preparation method thereof |
-
2022
- 2022-09-09 CN CN202211101320.7A patent/CN115975470A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116716015A (en) * | 2023-06-27 | 2023-09-08 | 上海青济新材料发展有限公司 | Container, epoxy anticorrosive paint and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104109439B (en) | True mineral varnish of a kind of insulation and preparation method thereof | |
| CN108034334B (en) | Water-based organic silicon-fluorine modified graphene oxide/epoxy resin coating and preparation method thereof | |
| CN109536937B (en) | High-corrosion-resistance galvanized steel sheet and preparation method thereof | |
| CN108570273B (en) | Solvent-free graphene oxide-glass flake anticorrosive paint and preparation method thereof | |
| CN112239625A (en) | Silicon dioxide-graphene oxide/polyurethane acrylic resin anticorrosion coating | |
| CN115975470A (en) | Modified silica ceramic resin and preparation method thereof | |
| CN108250941B (en) | Low-surface-energy material with micro-nano groove structure and preparation method thereof | |
| CN112011250A (en) | Low-temperature fast-curing environment-friendly insulating coating for non-oriented electrical steel | |
| CN113698850A (en) | Wear-resistant corrosion-resistant super-hydrophobic composite coating and preparation method thereof | |
| CN113773497B (en) | High-temperature-resistant modified silicone adhesive and application thereof in flexible mica plate | |
| CN102153754B (en) | Silicone resin, latex paint thereof, preparation methods of silicone resin and latex paint thereof and coating | |
| CN111748219B (en) | Surface modification method of conductive material and application of conductive material in polyacrylate coating | |
| CN111303727B (en) | Solvent-free super-thick-paste organic-inorganic hybrid nano modified heavy-duty anticorrosive paint and preparation method thereof | |
| CN110355844B (en) | Water-based epoxy composite system for wood and bamboo protection and application thereof | |
| CN115477893B (en) | Preparation method of water-based alkyd anticorrosive paint | |
| CN112745766A (en) | Outdoor floor bi-component water-based asphalt anticorrosive paint and preparation method thereof | |
| CN103680700B (en) | Enameled wire containing polyimide modified silane coupling agent coating | |
| CN111363468B (en) | Paint spraying process for surface of automobile support | |
| CN115926070A (en) | Preparation method of modified organic silicon resin of acrylate | |
| CN113136013B (en) | Acrylic acid modified vinyl organic silicon resin and preparation method thereof | |
| CN113881392A (en) | Preparation method of deacidification type organic silicon adhesive | |
| CN111777917A (en) | Preparation method of modified etched basalt scale/epoxy resin composite coating | |
| CN111647334A (en) | Laminated scaly heavy-duty anticorrosive paint and preparation method thereof | |
| CN116376420B (en) | Fluorine-containing coating and preparation method and application thereof | |
| CN116496679B (en) | Multifunctional environment-friendly paint and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication |