CN115299460B - Composite mildew preventive, preparation method thereof and mildew-proof organic silicon sealant - Google Patents
Composite mildew preventive, preparation method thereof and mildew-proof organic silicon sealant Download PDFInfo
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
- A01N25/10—Macromolecular compounds
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P1/00—Disinfectants; Antimicrobial compounds or mixtures thereof
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
- C09J183/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0806—Silver
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Abstract
The invention particularly relates to a composite mildew preventive, a preparation method thereof and a mildew-proof sealant, wherein the composite mildew preventive comprises the following components: zinc oxide whiskers; the polyphenol amine layer is arranged on the zinc oxide whisker; and silver particles disposed on the polyaniline layer. The composite mildew preventive improves the mildew-proof effect by improving the silver content, and simultaneously has antibacterial property and heat resistance. The mildew-proof sealant is added with the composite mildew-proof agent, so that mildew resistance, antibacterial property and heat resistance can be considered, and meanwhile, the mechanical property of the composite mildew-proof sealant is not influenced.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a composite mildew preventive, a preparation method thereof and a mildew-proof organic silicon sealant.
Background
Aviation weaponry such as carrier-borne aircraft, helicopters, and the like, in marine and offshore environments, may use a large amount of silicone sealant for bonding and sealing. The organosilicon sealant has the advantages of excellent high and low temperature resistance, weather resistance, medium resistance and the like. However, the organic silicon sealant has low toxicity, and is easy to absorb dust due to electrostatic action, so that mold is easy to grow. Once the organic silicon sealant is mildewed, enzymes and organic acids generated in the mould propagation process can degrade the silicone rubber, thereby seriously affecting the reliability of aviation weapon equipment.
The existing mildew-proof organic silicon sealant is mainly aimed at a humid land environment, and the general idea is to add an organic or inorganic mildew-proof agent. The organic mildew preventive comprises quaternary ammonium salt, biguanide, isothiazolinone and the like, and has the advantages of instant sterilization and broad antibacterial spectrum. But has short service life and is easy to decompose at high temperature. The inorganic mildew preventive mainly comprises a metal ion type (silver, copper and zinc) antibacterial agent, nano titanium dioxide, nano zinc oxide, nano silver and the like, and has the advantages of good heat resistance and long-acting sterilization effect.
In the patent CN106084234A, CN111073592A, CN102485823A, organic silicon quaternary ammonium salt, guanidine compound and isothiazolinone compound are respectively adopted as mildew inhibitors, and the silicone adhesive obtained by adding the organic mildew inhibitors has excellent antibacterial mildew resistance, but the use temperature is often not more than 200 ℃, otherwise, the organic mildew inhibitors are decomposed, and the degradation products can accelerate the aging degradation of the silicone rubber so as to influence the performances of heat resistance, adhesiveness and the like of the sealant. In the patent CN103756630A, organic arsenide is used as a mildew inhibitor to play a role in mildew prevention and sterilization of a silicone sealant. Arsenic, however, is carcinogenic and also environmentally polluting. Based on the limitations of the use of organic antimildew agents, research on inorganic antimicrobial agents is also increasing. The patent CN104194713B adopts nano silver inorganic antibacterial agent to improve the mildew resistance of the organosilicon sealant, but the mildew resistance effect is not detailed. In the patent CN103773308B, an organic mildew inhibitor and a silver-loaded zeolite inorganic antibacterial agent are compounded to obtain a composite antibacterial mildew inhibitor, which can enable the organosilicon sealant to have a long-term efficient antibacterial mildew-proof effect, but the introduction of the organic mildew inhibitor enables small molecules generated in the decomposition process to influence the heat resistance of the silicone rubber. The antibacterial property of the organosilicon sealant is effectively improved by adopting the silver-loaded zirconium phosphate antibacterial agent in the patent CN103122238A, but the mildew-proof effect is poor. In addition, the mildew-proof antibacterial sealant is applied to civil occasions such as toilets, kitchens and the like, and has poor heat resistance.
In conclusion, the existing mildew preventive cannot be added into the organic silicon sealant to achieve the mildew preventive, antibacterial and high temperature resistant performance, and cannot meet the use requirements of aviation weapon equipment in marine and offshore environments.
Therefore, development of a mildew preventive capable of achieving a combination of mildew resistance, antibacterial properties and heat resistance is a problem to be solved by those skilled in the art.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a composite mildew preventive, a preparation method thereof and a mildew-proof sealant.
In order to achieve the above object, the present invention provides the following technical solutions.
The first aspect of the present invention provides a composite mildew preventive comprising:
zinc oxide whiskers;
the polyphenol amine layer is arranged on the zinc oxide whisker; and
silver particles disposed on the polyaniline layer.
In some embodiments of the invention, the silver content of the composite mildew inhibitor is 35% -45% and the conductivity is 4500S/cm-8500S/cm.
The second aspect of the invention provides a preparation method of a composite mildew inhibitor, which is characterized by comprising the following steps:
under alkaline condition, reacting phenols and amines on zinc oxide whisker to generate a polyphenol amine layer in the presence of strong oxidant, thereby obtaining modified zinc oxide whisker; and
the modified zinc oxide whiskers are mixed with a soluble silver salt solution, a reducing agent and subjected to oxidation-reduction reaction under alkaline conditions, thereby forming silver particles on the modified zinc oxide whiskers.
In some embodiments of the invention, the silver particles are nano silver particles.
In the present invention, the zinc oxide whisker is preferably a tetrapod-like zinc oxide whisker (T-ZnOw). T-ZnOw is a whisker-shaped monocrystal, and has better antibacterial activity compared with common zinc oxide and nano zinc oxide, because: on the one hand, zn 2+ The three-dimensional conductive network formed by the dispersed T-ZnOw space tetrapod-like structure moves to penetrate the cell membrane of bacteria and destroy the synthesis of protein in the bacteria; on the other hand, the active oxygen component generated by the T-ZnOw through photocatalysis has good bactericidal effect. While needleFor silver particles, the dissolved silver ions can combine with sulfhydryl (-SH) groups on protease in bacteria to cause the loss of the internal enzyme activity of bacteria, thereby playing a role in sterilization. The silver particles can further improve conduction band e of T-ZnOw CB -and valence band holes h VB + Reducing the separation efficiency of conduction band e CB -and valence band holes h VB + Thereby enhancing the formation of active oxygen components mainly comprising hydroxyl radicals OH and active oxygen ions O 2－ The two can destroy the reproductive capacity of bacteria or fungi in a short time, so that cells die, thereby achieving the aim of antibiosis. By utilizing the synergistic effect of the antibacterial action mechanisms of the two, the prepared composite mildew preventive obviously improves the mildew preventive performance of the organosilicon sealant after being added into the organosilicon sealant, and has no obvious influence on the performance of the organosilicon sealant.
On the other hand, the purpose of phenolic amine modification on T-ZnOw is achieved by arranging the polyphenol amine layer on the T-ZnOw, catechol and polyamine react to generate a polymer layer, and phenolic hydroxyl groups can be introduced on the surface of the T-ZnOw as a functional reaction platform, wherein the ortho-phenolic hydroxyl groups have the function of fixing silver particles. The method can realize the regulation and control of the silver content on the surface of the T-ZnOw, and the loss of a silver source is smaller. Compared with the reported method for depositing silver on the surface of T-ZnOw through dopamine modification, on one hand, the cost of phenolic amine modification is lower and less than one percent of dopamine modification is less; on the other hand, the deposition rate of phenols and amines is accelerated by using a strong oxidant, the deposition time is shortened to be within 1h, and the method is obviously superior to dopamine modification (the deposition time is not less than 4 h).
In some embodiments of the invention, the alkaline conditions are formed by the addition of a weak base. The weak base may be Tris buffer, sodium carbonate or sodium bicarbonate.
In some embodiments of the invention, the phenol is catechol, resorcinol, pyrogallol, gallic acid, or tannic acid;
in some embodiments of the invention, the amine is diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, or polyethyleneimine;
in some embodiments of the invention, the molar ratio of the phenols to the amines is 1:1 to 5:1, a step of;
in some embodiments of the invention, the strong oxidizer is ammonium persulfate, sodium peroxide, hydrogen peroxide, or copper oxide, preferably ammonium persulfate.
In some embodiments of the invention, the molar ratio of the phenols, the amines, and the strong oxidizing agent may be 1: (1-5): (0.5-4).
Ammonium persulfate is a strong oxidant capable of generating active oxygen radicals including OH, O in aqueous solution 2 And (3) the active oxygen free radicals have higher activity than oxygen, and can accelerate the oxidation of phenolic hydroxyl groups to quinone, so that the speed of forming a polyaniline layer by oxidizing and self-polymerizing catechol and amino groups is increased, and the reaction time can be shortened by using ammonium persulfate. The dosage of the ammonium persulfate has influence on the silver content and the conductivity of the composite mildew preventive, and the silver content and the conductivity of the composite mildew preventive can be increased by properly increasing the dosage of the ammonium persulfate.
In some embodiments of the invention, the soluble silver salt solution is a silver ammonia solution;
in some embodiments of the invention, the compound is glucose, sodium citrate, or sodium borohydride;
in some embodiments of the invention, the ratio of the molar amount of silver ions in the soluble silver salt solution to the molar amount of reducing agent is 1:1 to 1:3.
in some embodiments of the invention, the ratio of the mass of the modified zinc oxide whiskers, the mass of the silver salt in the soluble silver salt solution, and the mass of the reducing agent species is 1 (1-3): 2-8.
In some embodiments of the invention, the modified zinc oxide whiskers are mixed with a soluble silver salt solution, a reducing agent, and a dispersing agent. Under the action of the dispersing agent, silver particles are uniformly deposited on the surface of the T-ZnOw, so that agglomeration is avoided, and long-term and efficient antibacterial and mildew-proof effects of silver ions are realized through a slow release effect.
In some embodiments of the invention, the dispersant is polyvinylpyrrolidone.
In a third aspect, the present invention provides a mould proof sealant comprising a composite mould proof agent provided by the first aspect of the present invention or prepared by the preparation method provided by the second aspect of the present invention.
In some embodiments of the present invention, the sealant may be any one of a polysulfide sealant, a modified polysulfide sealant, a polythioether sealant, a fluorosilicone sealant, or a silicone sealant.
In some embodiments of the present invention, the mildew-resistant sealant is a mildew-resistant silicone sealant comprising, in parts by weight, the following components separately packaged:
component a comprises 100 parts of room temperature vulcanized silicone rubber, 30-50 parts of reinforcing filler, 1-5 parts of heat-resistant additive and 1-4 parts of the composite mildew inhibitor according to claim 1 or 2 or the composite mildew inhibitor obtained according to the preparation method of any one of claims 3-7;
the component B comprises 0.6-3 parts of cross-linking agent; and
component C comprises 0.3 to 1.5 parts of catalyst.
In some embodiments of the invention, the room temperature vulcanizing silicone rubber is an alpha, omega-dihydroxy polydimethylsiloxane, an alpha, omega-dihydroxy polymethylphenylsiloxane, a vinyl terminated methyl silicone rubber, and the viscosity is 2000-20000 mPa.s.
In some embodiments of the present invention, the reinforcing filler comprises one or more of white carbon, nano calcium carbonate, zinc oxide, quartz powder, and diatomaceous earth.
In some embodiments of the invention, the heat resistant additive comprises one or more of iron oxide red, cerium oxide, iron oxalate, iron oxide yellow, iron-containing polysiloxanes, and fumed titanium dioxide.
In some embodiments of the invention, the cross-linking agent is one or more of ethyl orthosilicate, polyethyl orthosilicate, and hydrogen-containing silicone oil;
in some embodiments of the invention, the catalyst is one or more of dibutyl tin dilaurate, dibutyl tin diacetate, dibutyl tin dioctanoate, stannous octoate, butyl titanate, titanium acetylacetonate complex, and the like.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention provides a composite mildew preventive, which improves the mildew preventive effect by improving the silver content and simultaneously has antibacterial property and heat resistance.
The mildew-proof effect of the composite mildew-proof agent prepared by phenolic amine modification is superior to that of the composite mildew-proof agent prepared by dopamine modification.
The composite mildew preventive prepared by phenolic amine modification has high conductivity and good silver particle deposition effect.
2. The invention provides a preparation method of a composite mildew inhibitor, which has low cost and high efficiency and has the prospect of industrial amplification and application.
3. The mildew-proof sealant is added with the composite mildew-proof agent, so that the mildew-proof property, the antibacterial property and the heat resistance can be considered, and the mechanical property of the mildew-proof sealant is not influenced.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) of T-ZnOw.
Fig. 2 is an SEM image of the composite mildew preventive.
FIG. 3 is an X-ray diffraction (XRD) pattern of T-ZnOw and the composite mildew inhibitor.
Detailed Description
In order to make the contents of the present invention more easily understood, the technical scheme of the present invention will be further described with reference to the specific embodiments, but the present invention is not limited thereto. All techniques implemented based on the above description of the invention are intended to be included within the scope of the invention. Unless otherwise indicated, the raw materials and reagents used in the examples were all commercially available. The reagents, instruments or procedures not described herein are those routinely determinable by one of ordinary skill in the art.
Preparation of composite mildew preventive
Example 1
(1) After 12g T-ZnOw is cleaned by ultrasonic in deionized water, the solution is placed in a mixed solution of 15mM catechol and 5mM tetraethylenepentamine, the pH of the solution is further adjusted to 9.5 by Tris, and then 5mM ammonium persulfate is added for continuous stirring reaction for 1h, so that tetrapod-shaped zinc oxide whiskers with a polyaniline layer deposited on the surface, namely, phenol amine modified tetrapod-shaped zinc oxide whiskers, are obtained;
(2) Preparing 1.5L of silver nitrate solution with the concentration of 8.4g/L, and titrating with ammonia water until the color of the solution is clarified again to prepare silver-ammonia solution;
(3) Adding the phenolic amine modified four-needle zinc oxide whisker obtained in the step 1 into the silver-ammonia solution obtained in the step 2, adding 3.75g of polyvinylpyrrolidone and 3.2g of sodium hydroxide, stirring for 5min, adding 1.5L of glucose solution with the concentration of 17.2g/L dropwise by using a constant pressure dropping funnel, reacting for 3h, washing and drying to obtain the phenolic amine modified composite mildew inhibitor.
According to the measurement, the silver content of the composite mildew inhibitor is about 36%, and the silver content measurement method is used for judging by measuring the quality change of zinc oxide whiskers before and after silver plating. The conductivity was about 4600S/cm, as measured by the four-probe method after tabletting the composite mildew inhibitor powder.
The Scanning Electron Microscope (SEM) images of the T-ZnOw and the composite mildew preventive in this example are shown in FIGS. 1 and 2, demonstrating that silver particles are deposited on the T-ZnOw surface.
FIG. 3 is an X-ray diffraction (XRD) pattern of T-ZnOw and the composite mildew preventive, showing five characteristic crystal peaks (111), (200), (220), (311), (222) of silver, demonstrating that the silver on the surface of T-ZnOw exists in a simple substance state.
Example 2
The procedure is as in example 1, except that the silver nitrate concentration in step (2) is changed to 12.6g/L and the glucose concentration in step (3) is changed to 26.7g/L. The silver content of the composite mildew inhibitor is about 44% and the conductivity is about 8440S/cm.
Example 3
The procedure is as in example 1, except that the 5mM ammonium persulfate in step (1) is replaced with 15mM.
The silver content of the composite mildew inhibitor is about 38% and the conductivity is 5000S/cm.
Using the composite mold inhibitor prepared in examples 1 to 3, mold-proof silicone sealants of examples 4 to 6 were prepared according to the following general methods.
Preparation of mildew-proof organosilicon sealant
The preparation raw materials comprise the following components in parts by weight: 100 parts of hydroxyl-terminated polysiloxane raw rubber, 40 parts of white carbon black, 5 parts of zinc oxide, 5 parts of iron oxide red, 3 parts of a composite mildew inhibitor, 3 parts of a cross-linking agent ethyl orthosilicate and 0.5 part of a catalyst tin dilaurate.
The preparation method of the mildew-proof organic silicon sealant specifically comprises the following steps:
a) Mixing hydroxyl-terminated methyl silicone rubber, white carbon black, zinc oxide, iron oxide red and a composite mildew inhibitor by a kneader to obtain a coarse mixed base rubber;
b) Uniformly mixing the coarse mixed base rubber with a three-roller grinder for 3 times to obtain a mildew-proof organic silicon sealant component A;
c) The component A, the component B (cross-linking agent) and the component C (catalyst) are packaged separately according to a certain proportion (100: (0.2-2): (0.1 to 0.5)) to obtain the mildew-proof organosilicon sealant.
Example 4
The composite mildew preventive of example 1 was used.
Example 5
The composite mildew preventive of example 2 was used.
Example 6
The composite mildew preventive of example 3 was used.
Comparative example 1
The preparation method of the mildew-proof organic silicon sealant comprises the following raw materials in parts by weight: 100 parts of hydroxyl-terminated polysiloxane raw rubber, 40 parts of white carbon black, 5 parts of zinc oxide, 5 parts of iron oxide red, 3 parts of N- (2-benzimidazolyl) -methyl carbamate (BCM) organic mildew inhibitor, 3 parts of cross-linking agent ethyl orthosilicate and 0.5 part of catalyst tin dilaurate.
The preparation method of the mildew-proof organic silicon sealant specifically comprises the following steps:
a) Mixing hydroxyl-terminated methyl silicone rubber, white carbon black, zinc oxide, iron oxide red and BCM organic mildew inhibitor by a kneader to obtain a coarse mixed base rubber;
b) Uniformly mixing the coarse mixed base rubber with a three-roller grinder for 3 times to obtain a mildew-proof organic silicon sealant component A;
c) The component A, the component B (cross-linking agent) and the component C (catalyst) are packaged separately according to a certain proportion (100: 0.4:0.2 Mold-proof organosilicon sealant is obtained.
Comparative example 2
The procedure was as in comparative example 1, except that the BCM organic mildew inhibitor was removed and no mildew inhibitor was added.
Comparative example 3
The procedure was as in comparative example 1, substituting BCM organic mildewcide for T-ZnOw.
Comparative example 4
The procedure is as in comparative example 1, substituting step (1) with: after 12g T-ZnOw is cleaned by ultrasonic in deionized water, the cleaned solution is placed in 2g/L dopamine hydrochloride water solution, the pH value of the solution is further adjusted to 8.5 by 1.2g/L Tris, and the reaction is continuously stirred for 4 hours, so that the T-ZnOw with the polydopamine layer deposited on the surface is obtained. According to measurement, the silver content of the composite mildew inhibitor prepared by modifying the dopamine is about 30%, and the conductivity is about 2600S/cm. Under the same conditions, the silver plating efficiency of dopamine modification is lower than that of phenolic amine modification, and the silver source utilization rate is relatively lower.
Comparative example 5
The procedure was as in example 4, except that the amount of the composite mold preventive was changed to 5 parts.
Performance test:
the organosilicon sealant component A, B and the organosilicon sealant component C are uniformly mixed according to the proportion, then a test piece is pressed, and the test piece is taken out after being solidified for 7 days at the constant temperature and humidity of 23 ℃ and 50% humidity. The mechanical property test reference standard GB/T528-2009, the aging property test reference standard GB/T3512 and the mold grade judgment reference standard GJB 150.10A-2009 of the organic silicon sealant are shown in the specific test results in Table 1.
TABLE 1 comparison of the Performance of the mildew-resistant silicone sealants of the inventive and comparative examples
As can be seen from Table 1, the silicone sealant of comparative example 2, to which no mold inhibitor was added, had the lowest mold inhibition level. After the mildew preventive is added, the mildew preventive grade of the organic silicon sealant is improved to a certain extent. In comparative example 1, in which the organic mildew inhibitor was added, the mildew-proof rating reached 0 level, but the aged film exhibited an embrittled state, indicating that the organic mildew inhibitor severely affected the heat resistance of the sealant. In comparative example 3, in which T-ZnOw is added, the mildew-proof effect is generally improved from 3 to 2, and the fact that the mildew-proof effect of the pure T-ZnOw is poor is demonstrated. As can be seen from comparative example 4, the mildew-proof effect of the organosilicon sealant modified by adding dopamine is 1 level, and the organosilicon sealant has a certain mildew-proof effect, and the mildew-proof agent does not affect the mechanical properties of the organosilicon sealant before and after aging. In the examples 4 to 6 added with the composite mildew inhibitor, the mildew-proof grade can reach 0 to 1 grade, and the mechanical properties of the organosilicon sealant are not affected before and after aging. In addition, the mildew-proof grade of 0-1 grade is still maintained after aging, which shows that the composite mildew-proof agent has good thermal stability and service life. As can be seen from comparative example 5, the excessive amount of the composite mildew preventive has a certain influence on the mechanical properties of the silicone sealant, while agglomeration leads to deterioration of the mildew preventive, which is lower than level 0 in examples. The mildew-proof effect of the compound mildew-proof agent prepared by phenolic amine modification is superior to that of the compound mildew-proof agent prepared by dopamine modification, and the compound mildew-proof agent has advantages in terms of cost and time, and has industrial amplification and application prospects.
The present invention is not limited to the above-mentioned embodiments, and any changes or substitutions that can be easily understood by those skilled in the art within the technical scope of the present invention are intended to be included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (10)
1. A composite mildew inhibitor, comprising:
zinc oxide whiskers;
the polyphenol amine layer is arranged on the zinc oxide whisker; and
silver particles disposed on the polyaniline layer;
the silver content of the composite mildew preventive is 35% -45%, and the conductivity of the composite mildew preventive is 4500S/cm-8500S/cm.
2. The method for preparing the composite mildew preventive according to claim 1, comprising:
under alkaline condition, reacting phenols and amines on zinc oxide whisker to generate a polyphenol amine layer in the presence of strong oxidant, thereby obtaining modified zinc oxide whisker; and
the modified zinc oxide whiskers are mixed with a soluble silver salt solution, a reducing agent and subjected to oxidation-reduction reaction under alkaline conditions, thereby forming silver particles on the modified zinc oxide whiskers.
3. The method according to claim 2, wherein,
the phenols are catechol, resorcinol, pyrogallol, gallic acid or tannic acid;
the amine is diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine or polyethyleneimine;
the molar ratio of the phenols to the amines is 1:1 to 5:1, a step of;
the strong oxidant is ammonium persulfate, sodium peroxide, hydrogen peroxide or copper oxide.
4. A process according to claim 2 or 3, wherein,
the soluble silver salt solution is silver ammonia solution;
the reducing agent is glucose, sodium citrate or sodium borohydride;
the ratio of the molar quantity of silver ions in the soluble silver salt solution to the molar quantity of the reducing agent is 1:1-1:3.
5. A production method according to claim 2 or 3, wherein the ratio of the mass of the modified zinc oxide whisker, the mass of the silver salt in the soluble silver salt solution and the mass of the reducing agent is 1 (1-3): 2-8.
6. A method of preparation according to claim 2 or 3, wherein the modified zinc oxide whiskers are mixed with a soluble silver salt solution, a reducing agent and a dispersing agent.
7. The method of claim 6, wherein the dispersant is polyvinylpyrrolidone.
8. A mold-proof sealant comprising the composite mold-proof agent according to claim 1 or the composite mold-proof agent obtained by the production method according to any one of claims 2 to 7.
9. The mildew-resistant sealant according to claim 8, wherein the mildew-resistant sealant is a mildew-resistant silicone sealant comprising, in parts by weight, the following components separately packaged:
component a comprises 100 parts of room temperature vulcanized silicone rubber, 30-50 parts of reinforcing filler, 1-5 parts of heat-resistant additive and 1-4 parts of the composite mildew inhibitor according to claim 1 or the composite mildew inhibitor obtained by the preparation method according to any one of claims 2-7;
the component B comprises 0.6-3 parts of cross-linking agent; and
component C comprises 0.3 to 1.5 parts of catalyst.
10. A mold-proof sealant according to claim 9, wherein,
the room temperature vulcanized silicone rubber is alpha, omega-dihydroxy polydimethylsiloxane, alpha, omega-dihydroxy polymethylphenylsiloxane and vinyl-terminated methyl silicone rubber, and the viscosity of the room temperature vulcanized silicone rubber is 2000-20000 mPa.s;
the reinforcing filler comprises one or more of white carbon black, nano calcium carbonate, zinc oxide, quartz powder and diatomite;
the heat-resistant additive comprises one or more of iron oxide red, cerium oxide, iron oxalate, iron oxide yellow, iron-containing polysiloxane and gas-phase titanium dioxide;
the cross-linking agent is one or more of tetraethoxysilane, polyethyl orthosilicate and hydrogen-containing silicone oil;
the catalyst is one or more of dibutyl tin dilaurate, dibutyl tin diacetate, dibutyl tin dioctanoate, stannous octoate, butyl titanate, acetylacetone titanium complex and other organic metal catalysts.
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