CN115652295A - Method for in-situ synthesis of interpenetrating organic network and silicon network composite passive film - Google Patents
Method for in-situ synthesis of interpenetrating organic network and silicon network composite passive film Download PDFInfo
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- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 39
- 239000010703 silicon Substances 0.000 title claims abstract description 39
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- 238000011065 in-situ storage Methods 0.000 title claims abstract description 17
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- 230000015572 biosynthetic process Effects 0.000 title description 10
- 238000003786 synthesis reaction Methods 0.000 title description 8
- 238000002161 passivation Methods 0.000 claims abstract description 52
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- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 7
- 239000001913 cellulose Substances 0.000 claims description 7
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- AYLBVKUPVXVTSO-UHFFFAOYSA-N n,n-diphenylnitramide Chemical compound C=1C=CC=CC=1N([N+](=O)[O-])C1=CC=CC=C1 AYLBVKUPVXVTSO-UHFFFAOYSA-N 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 239000004115 Sodium Silicate Substances 0.000 claims description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 6
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- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 6
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical compound CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims description 4
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims description 4
- 239000000467 phytic acid Substances 0.000 claims description 4
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- 229940068041 phytic acid Drugs 0.000 claims description 4
- 235000010288 sodium nitrite Nutrition 0.000 claims description 4
- HYHCSLBZRBJJCH-UHFFFAOYSA-N sodium polysulfide Chemical compound [Na+].S HYHCSLBZRBJJCH-UHFFFAOYSA-N 0.000 claims description 4
- 150000004992 toluidines Chemical class 0.000 claims description 4
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 claims description 3
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- 239000007864 aqueous solution Substances 0.000 claims 1
- HFUSECPXGUISGB-UHFFFAOYSA-N benzoyl benzenecarboperoxoate;2-tert-butylperoxy-2-methylpropane Chemical compound CC(C)(C)OOC(C)(C)C.C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 HFUSECPXGUISGB-UHFFFAOYSA-N 0.000 claims 1
- 230000007797 corrosion Effects 0.000 abstract description 15
- 238000005260 corrosion Methods 0.000 abstract description 15
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 abstract description 14
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- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 6
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Abstract
The invention provides a method for synthesizing an interpenetrating organic network-silicon network composite passive film in situ, which comprises the following steps: mixing a silicon source and a first solvent to obtain a first solution; mixing an organic material with a second solvent, and adding an initiator to obtain a second solution; mixing the first solution and the second solution, and adding a terminator to obtain a passivation solution; and (3) soaking carbon steel in the passivation solution, and drying to obtain the interpenetrating organic network-silicon network composite passivation film. The method reduces the cost of silane passivation, improves the corrosion resistance of the silane passivation film, improves the ductility of the silane film and reduces the cracking phenomenon during preparation.
Description
Technical Field
The invention belongs to the field of passivation treatment, relates to a method for synthesizing a passivation film, and particularly relates to a method for synthesizing an interpenetrating organic network-silicon network composite passivation film in situ.
Background
The surface passivation treatment of the carbon steel can greatly improve the service life of the carbon steel and save a large amount of capital every year. At present, chromate is generally used for passivating carbon steel, but because hexavalent chromium is contained in chromate, is carcinogenic and has serious threat to human health and environment, the hexavalent chromium passivation technology is limited by countries all over the world or even abandoned. At present, a great deal of research is carried out on processing carbon steel by adopting a silane passivation mode, but the corrosion resistance of the obtained film layer cannot meet the use requirement, and the low price is also one of the main factors for limiting the development of the film layer.
The interpenetrating polymer network, especially organic/inorganic interpenetrating polymer network material, overcomes the performance defects of single material and traditional composite material, and makes the material possess the advantages of both inorganic material, such as rigidity and high heat stability, and polymer material, such as elasticity, dielectricity, ductility and machinability, and has additional performance raised owing to the interpenetrating network structure formed between the two components.
Disclosure of Invention
In order to solve the technical problems, the application provides a method for synthesizing the interpenetrating organic network-silicon network composite passivation film in situ, which reduces the cost of silane passivation, improves the corrosion resistance of the silane passivation film, also improves the ductility of the silane film, and reduces the phenomenon of cracking during preparation.
In order to achieve the technical effect, the invention adopts the following technical scheme:
the invention provides a method for synthesizing an interpenetrating organic network-silicon network composite passive film in situ, which comprises the following steps:
mixing a silicon source and a first solvent to obtain a first solution;
mixing an organic material with a second solvent, and adding an initiator to obtain a second solution;
mixing the first solution and the second solution, and adding a terminator to obtain a passivation solution;
and (3) soaking carbon steel in the passivation solution, and drying to obtain the interpenetrating organic network-silicon network composite passivation film.
In the invention, the organic network and the silicon network are compounded to form the organic network-silicon network compound passive film when the passive film is prepared. The introduction of the organic network structure reduces the preparation cost of the silane film on one hand and improves the corrosion resistance of the silane film on the other hand. Meanwhile, due to the addition of the organic matter, the ductility of the silane film and the stability of the passivation solution are improved, and the phenomenon of layering after long-term storage is relieved. The in-situ synthesis method is adopted, so that the production steps are simplified.
As a preferable technical scheme of the invention, the silicon source comprises sodium silicate and/or tetraethoxysilane.
Preferably, the first solvent comprises an aqueous alcohol solution, and the mass ratio of the alcohol to the water is 3 to 7.
Preferably, the alcohol comprises any one of methanol, ethanol or isopropanol, or a combination of at least two of these, typical but non-limiting examples being: a combination of methanol and ethanol, a combination of ethanol and isopropanol, a combination of isopropanol and methanol, or a combination of methanol, ethanol and isopropanol, and the like.
Preferably, the mass ratio of the silicon source to the first solvent is 1.
In a preferred embodiment of the present invention, the silicon source and the first solvent are mixed with stirring.
Preferably, the stirring rate is 300 to 800rpm, such as 350rpm, 400rpm, 450rpm, 500rpm, 550rpm, 600rpm, 650rpm, 700rpm, 750rpm, and the like, but is not limited to the recited values, and other values not recited within the range of values are equally applicable.
Preferably, the stirring time is 1 to 3 hours, such as 1.2 hours, 1.5 hours, 1.8 hours, 2 hours, 2.2 hours, 2.5 hours, or 2.8 hours, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
As a preferred embodiment of the present invention, the organic material comprises any one of cellulose, polyvinyl alcohol, alginic acid, phytic acid or polyethylene glycol or a combination of at least two of the following, typical but non-limiting examples of the combination are: a combination of cellulose and polyvinyl alcohol, a combination of polyvinyl alcohol and alginic acid, a combination of alginic acid and phytic acid, a combination of phytic acid and polyethylene glycol, a combination of polyethylene glycol and cellulose, or a combination of cellulose, polyvinyl alcohol, and alginic acid, and the like.
Preferably, the second solvent comprises water.
Preferably, the mass ratio of the organic material to the silicon source is 1 to 2, such as 1.1.
Preferably, the mass ratio of the organic material to the second solvent is 1.
As a preferred embodiment of the present invention, the initiator comprises any one or a combination of at least two of azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate, 1-diphenyl-2-trinitrophenylhydrazine, toluidine, N-nitrodiphenylamine, benzoyl peroxide t-butyl peroxide, or methyl ethyl ketone peroxide, and the combination is exemplified by, but not limited to: azodiisobutyronitrile and azodiisoheptonitrile, azodiisoheptonitrile and dimethyl azodiisobutyrate, dimethyl azodiisobutyrate and 1-diphenyl-2-trinitrophenylhydrazine, 1-diphenyl-2-trinitrophenylhydrazine and toluidine, toluidine and N-nitrodiphenylamine, N-nitrodiphenylamine and benzoyl peroxide, benzoyl peroxide and tert-butyl benzoyl peroxide, or methyl ethyl ketone peroxide, and the like.
Preferably, the mass ratio of the organic material to the initiator is 1.
As a preferable technical scheme of the invention, the initiator is added and then stirred.
Preferably, the stirring rate is 300 to 800rpm, such as 350rpm, 400rpm, 450rpm, 500rpm, 550rpm, 600rpm, 650rpm, 700rpm, 750rpm, and the like, but is not limited to the recited values, and other values not recited within the range of values are equally applicable.
Preferably, the temperature of the agitation is 50 to 80 ℃, such as 55 ℃,60 ℃, 65 ℃, 70 ℃ or 75 ℃, but not limited to the recited values, and other values not recited within the range of values are equally applicable.
As a preferred embodiment of the present invention, the terminating agent comprises any one or a combination of at least two of hydroquinone, p-tert-butylcatechol, sodium dimethyldithiocarbamate, sodium polysulfide or sodium nitrite, typical but non-limiting examples of which are: combinations of hydroquinone and p-tert-butylcatechol, p-tert-butylcatechol and sodium dimethyldithiocarbamate, sodium dimethyldithiocarbamate and sodium polysulfide, sodium polysulfide and sodium nitrite, or sodium nitrite and hydroquinone, and the like.
Preferably, the mass ratio of the organic material to the terminating agent is 1.
In the present invention, the terminator acts to block the polymerization reaction of the organic material and prevent it from being excessively polymerized to cause curing and loss of its usability.
In the invention, the terminating agent can be added at the same time of adding the silane coupling agent after the first solution and the second solution are mixed, the terminating agent can prevent the excessive polymerization of organic matters, and the silane coupling agent can increase the combination degree between an organic network and an inorganic network in a bridging mode.
As a preferable technical scheme of the invention, the terminator is added and then stirred.
Preferably, the stirring rate is 300 to 800rpm, such as 350rpm, 400rpm, 450rpm, 500rpm, 550rpm, 600rpm, 650rpm, 700rpm, 750rpm, and the like, but is not limited to the recited values, and other values not recited within the range of values are equally applicable.
Preferably, the stirring time is 1 to 3 hours, such as 1.2 hours, 1.5 hours, 1.8 hours, 2 hours, 2.2 hours, 2.5 hours, 2.8 hours, etc., but is not limited to the recited values, and other values not recited in the range of values are also applicable.
In a preferred embodiment of the present invention, the soaking time is 1-10 min, such as 2min, 3min, 4min, 5min, 6min, 7min, 8min or 9min, but not limited to the recited values, and other values not recited in the range of the recited values are also applicable.
In a preferred embodiment of the present invention, the temperature of the drying is 100 to 150 ℃, such as 105 ℃, 110 ℃, 115 ℃, 120 ℃, 125 ℃, 130 ℃, 135 ℃, 140 ℃ or 145 ℃, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the drying time is 10-60 min, such as 15min, 20min, 25min, 30min, 35min, 40min, 45min, 50min or 55min, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) The invention provides a method for synthesizing an interpenetrating organic network-silicon network composite passivation film in situ, which reduces the cost of silane passivation and improves the corrosion resistance of a silane passivation film;
(2) The invention provides a method for in-situ synthesis of an interpenetrating organic network-silicon network composite passivation film, which improves the ductility of a silane film, reduces the cracking phenomenon during preparation and also improves the stability of a passivation solution.
Detailed Description
For the purpose of facilitating an understanding of the present invention, the present invention will now be described by way of examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitation of the present invention.
Example 1
The embodiment provides a method for in-situ synthesis of an interpenetrating organic network-silicon network composite passive film, which comprises the following steps:
adding 20g of tetraethoxysilane into 80g of ethanol-water mixed solution with the alcohol-water ratio of 3;
adding 20g of polyvinyl alcohol into 80g of water, adding 0.1g of azobisisobutyronitrile and 0.1g of 1-diphenyl-2-trinitrophenylhydrazine, stirring at 60 ℃ for 500r/min until the mixture is slightly viscous, and obtaining a second solution 2;
pouring the first solution into the second solution, uniformly mixing, adding 0.1g of hydroquinone and a silane coupling agent, and continuously stirring for 1h at 500r/min to obtain a passivation solution;
and (3) soaking the carbon steel in the passivation solution for 2min, taking out the carbon steel, and drying the carbon steel for 30min at 120 ℃ to obtain the interpenetrating organic network-silicon network composite passivation film.
Example 2
The embodiment provides a method for in-situ synthesis of an interpenetrating organic network-silicon network composite passive film, which comprises the following steps:
adding 20g of tetraethoxysilane into 80g of ethanol-water mixed solution with the alcohol-water ratio of 5;
adding 20g of cellulose into 80g of water, adding 0.1g of dimethyl azodiisobutyrate and 0.1g of 1-diphenyl-2-trinitrophenylhydrazine, stirring at 60 ℃ and 500r/min until the mixture is slightly viscous to obtain a second solution;
pouring the first solution into the second solution, uniformly mixing, adding 0.1g of p-tert-butylcatechol and a silane coupling agent, and continuously stirring for 1h at 500r/min to obtain a passivation solution;
and (3) soaking the carbon steel in the passivation solution for 2min, taking out the carbon steel, and drying the carbon steel for 30min at 120 ℃ to obtain the interpenetrating organic network-silicon network composite passivation film.
Example 3
The embodiment provides a method for synthesizing an interpenetrating organic network-silicon network composite passive film in situ, which comprises the following steps:
adding 20g of sodium silicate into 80g of ethanol-water mixed solution with the alcohol-water ratio of 7;
adding 20g of polyvinyl alcohol into 80g of water, adding 0.1g of N-nitrodiphenylamine and 0.1g of benzoyl peroxide, and stirring at 60 ℃ for 500r/min until the mixture is slightly viscous to obtain a second solution;
pouring the first solution into the second solution, mixing uniformly, adding 0.1g of sodium dimethyldithiocarbamate and a silane coupling agent, and continuously stirring for 1h at 500r/min to obtain a passivation solution;
and (3) soaking the carbon steel in the passivation solution for 2min, taking out the carbon steel, and drying the carbon steel for 20min at 120 ℃ to obtain the interpenetrating organic network-silicon network composite passivation film.
Example 4
The embodiment provides a method for synthesizing an interpenetrating organic network-silicon network composite passive film in situ, which comprises the following steps:
adding 20g of sodium silicate into 80g of ethanol-water mixed solution with the alcohol-water ratio of 7;
adding 20g of polyethylene glycol into 80g of water, adding 0.1g of N-nitrodiphenylamine and 0.1g of benzoyl peroxide, and stirring at 60 ℃ at 500r/min until the mixture is slightly viscous to obtain a second solution;
pouring the first solution into the second solution, mixing uniformly, adding 0.1g of sodium dimethyldithiocarbamate and a silane coupling agent, and continuously stirring for 1h at 500r/min to obtain a passivation solution;
and (3) soaking the carbon steel in the passivation solution for 2min, taking out the carbon steel, and drying the carbon steel for 20min at 120 ℃ to obtain the interpenetrating organic network-silicon network composite passivation film.
Comparative example 1
The present comparative example provides a method of in situ synthesis of an interpenetrating organic network-silicon network composite passive film, the method comprising:
adding 20g of tetraethoxysilane into 80g of ethanol-water mixed solution with the alcohol-water ratio of 3;
adding 20g of polyvinyl alcohol into 80g of water, adding 0.1g of N-nitrodiphenylamine and 0.1g of benzoyl peroxide, and stirring at 60 ℃ at 500r/min until the mixture is slightly viscous to obtain a second solution;
pouring the first solution into the second solution, adding a silane coupling agent, uniformly mixing, and continuously stirring for 1h at 500r/min to obtain a passivation solution;
and (3) soaking the carbon steel in the passivation solution for 2min, taking out the carbon steel, and drying the carbon steel for 20min at 120 ℃ to obtain the interpenetrating organic network-silicon network composite passivation film.
Comparative example 2
The present comparative example provides a method for in situ synthesis of an interpenetrating organic network-silicon network composite passive film, comprising:
adding 20g of tetraethoxysilane into 80g of ethanol-water mixed solution with the alcohol-water ratio of 3;
adding 20g of cellulose into 80g of water, stirring at 60 ℃ for 500r/min to obtain a second solution;
pouring the first solution into the second solution, uniformly mixing, adding 0.1g of sodium dimethyldithiocarbamate and a silane coupling agent, and continuously stirring for 1h at 500r/min to obtain a passivation solution;
and (3) soaking the carbon steel in the passivation solution for 2min, taking out the carbon steel, and drying the carbon steel for 20min at 120 ℃ to obtain the interpenetrating organic network-silicon network composite passivation film.
Comparative example 3
The present comparative example provides a method of in situ synthesis of an interpenetrating organic network-silicon network composite passive film, the method comprising:
adding 10g of sodium silicate into 80g of ethanol-water mixed solution with the alcohol-water ratio of 3;
adding 20g of alginic acid into 80g of water, stirring at 60 ℃ for 500r/min to obtain a second solution;
pouring the first solution into the second solution, mixing uniformly, adding 0.1g of sodium dimethyldithiocarbamate and a silane coupling agent, and continuously stirring for 1h at 500r/min to obtain a passivation solution;
and (3) soaking the carbon steel in the passivation solution for 2min, taking out the carbon steel, and drying the carbon steel for 20min at 120 ℃ to obtain the interpenetrating organic network-silicon network composite passivation film.
Comparative example 4
The comparative example was the same as example 1 except that carbon steel was directly immersed in the first solution.
Comparative example 5
The comparative example was conducted under the same conditions as in example 1 except that the carbon steel was directly immersed in the second solution.
The passivation films prepared in examples 1 to 4 and comparative examples 1 to 5 were subjected to a salt spray test, and the storage stability of the passivation solution was tested, and the results are shown in table 1.
The method for testing the stability of the passivation solution comprises the following steps: and (4) standing. And (3) taking 50mL of the passivation solution by using a 100mL measuring cylinder, standing, and considering that the stability is lost when any one of three conditions of the layering volume of more than 5mL, the precipitation volume of more than 5mL and the viscosity rise to the condition that the film cannot be formed is achieved.
The method for testing the film bonding performance comprises the following steps: the bonding strength of the coating is tested according to GB/T13936-2014 determination method for bonding tensile shear strength of vulcanized rubber and metal. The adhesion strength is greater than 2MPa, which is considered good, otherwise the adhesion strength is low.
The method for testing the uniformity of the film layer comprises the following steps: the film layer is uniform by using a portable thickness gauge and taking the difference between the thickest part and the thinnest part as less than 1mm and no obvious bubbles and depressions.
The corrosion resistance test method comprises the following steps: at 25 ℃, taking pH =7 and 3.5% sodium chloride as a solution, performing corrosion test by using a salt spray tester, and taking the time when phenomena such as obvious general corrosion, filiform corrosion, crevice corrosion and the like or pitting corrosion occur as a standard for judging corrosion resistance
TABLE 1
In comparative example 1, no terminator was added, which resulted in excessive polymerization of the organic phase, rapid increase in the overall viscosity, decrease in the stability of the passivation solution, increase in the difficulty of film formation, and decrease in the corrosion resistance.
Comparative example 2 in which no initiator was added, the organic phase was not polymerized, the overall viscosity was low, it was difficult to form a film and bubbles and depressions were easily introduced, resulting in non-uniform film, difficulty in controlling thickness, and decreased corrosion resistance
Comparative example 3, in which no initiator was added and the sodium silicate content was low, resulted in less silane inorganic network formation, poor film-forming property, low adhesive strength and reduced corrosion resistance
The applicant states that the present invention is illustrated by the above examples to show the detailed process equipment and process flow of the present invention, but the present invention is not limited to the above detailed process equipment and process flow, i.e. it does not mean that the present invention must rely on the above detailed process equipment and process flow to be implemented. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. A method for synthesizing an interpenetrating organic network-silicon network composite passive film in situ is characterized by comprising the following steps:
mixing a silicon source and a first solvent to obtain a first solution;
mixing an organic material with a second solvent, and adding an initiator to obtain a second solution;
mixing the first solution and the second solution, and adding a terminator to obtain a passivation solution;
and (3) soaking carbon steel in the passivation solution, and drying to obtain the interpenetrating organic network-silicon network composite passivation film.
2. The method of claim 1, wherein the silicon source comprises sodium silicate and/or ethyl orthosilicate;
preferably, the first solvent comprises an aqueous solution of alcohol, and the mass ratio of the alcohol to the water is 3-7;
preferably, the alcohol comprises any one of methanol, ethanol or isopropanol or a combination of at least two thereof;
preferably, the mass ratio of the silicon source to the first solvent is 1.
3. The method according to claim 1 or 2, wherein the silicon source is mixed with the first solvent under stirring;
preferably, the stirring speed is 300-800 rpm;
preferably, the stirring time is 1 to 3 hours.
4. The method according to any one of claims 1 to 3, wherein the organic material comprises any one of cellulose, polyvinyl alcohol, alginic acid, phytic acid or polyethylene glycol or a combination of at least two thereof;
preferably, the second solvent comprises water;
preferably, the mass ratio of the organic material to the silicon source is 1 to 2;
preferably, the mass ratio of the organic material to the second solvent is 1.
5. The method of any one of claims 1 to 4, wherein the initiator comprises any one of azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate, 1-diphenyl-2-trinitrophenylhydrazine, toluidine, N-nitrodiphenylamine, benzoyl peroxide tert-butyl peroxide, or methyl ethyl ketone peroxide, or a combination of at least two thereof;
preferably, the mass ratio of the organic material to the initiator is 1.
6. A process according to any one of claims 1 to 5, characterised in that the initiator is added followed by stirring;
preferably, the stirring speed is 300-800 rpm;
preferably, the temperature of the stirring is 50 to 80 ℃.
7. The method of any one of claims 1 to 6, wherein the terminating agent comprises any one of hydroquinone, p-tert-butylcatechol, sodium dimethyldithiocarbamate, sodium polysulfide or sodium nitrite, or a combination of at least two thereof;
preferably, the mass ratio of the organic material to the terminator is 1.
8. The method according to any one of claims 1 to 7, wherein the terminator is added followed by stirring;
preferably, the stirring speed is 300-800 rpm;
preferably, the stirring time is 1 to 3 hours.
9. The method according to any one of claims 1 to 8, wherein the soaking time is 1 to 10min.
10. The method according to any one of claims 1 to 9, wherein the temperature of the drying is 100 to 150 ℃;
preferably, the drying time is 10-60 min.
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