CN112778967B - Mildew-proof antibacterial silicone sealant composition and preparation method thereof - Google Patents

Mildew-proof antibacterial silicone sealant composition and preparation method thereof Download PDF

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CN112778967B
CN112778967B CN202011562946.9A CN202011562946A CN112778967B CN 112778967 B CN112778967 B CN 112778967B CN 202011562946 A CN202011562946 A CN 202011562946A CN 112778967 B CN112778967 B CN 112778967B
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parts
mass
stirring
mildew
mpa
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CN112778967A (en
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戴飞亮
付子恩
蒋金博
周波雄
罗元章
洪展鹏
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Guangzhou Baiyun Technology Co ltd
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Guangzhou Baiyun Chemical Industry Co Ltd
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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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
    • C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
    • C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
    • C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
    • 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
    • C09J11/08—Macromolecular additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Health & Medical Sciences (AREA)
  • Sealing Material Composition (AREA)

Abstract

The invention relates to the field of materials, in particular to a mildew-proof antibacterial silicone sealant composition and a preparation method thereof. According to the invention, 2- (3, 4-epoxycyclohexane) ethyltrimethoxysilane, 3- (2, 3-epoxypropoxy) propyltrimethoxysilane or isocyanate propyltriethoxysilane are selected as modifiers to chemically modify chitosan oligosaccharide with antibacterial activity, and siloxane groups are introduced into the structure of the chitosan oligosaccharide, so that the chitosan oligosaccharide has the basis of chemically modifying the silicone sealant without influencing the mildew-proof antibacterial activity, the mildew-proof antibacterial effective duration of the silicone sealant can be greatly prolonged, and the physical properties such as the adhesion, toughness and strength of the silicone sealant can not be obviously negatively influenced.

Description

Mildew-proof antibacterial silicone sealant composition and preparation method thereof
Technical Field
The invention relates to the field of materials, in particular to a mildew-proof antibacterial silicone sealant composition and a preparation method thereof.
Background
The adhesive is widely applied in the current society, is one of indispensable materials for national economic development, and has a large amount of applications in various industries such as electronics, electricity, building materials, automobile machinery and the like. Room Temperature Vulcanizing (RTV) condensation type silicone sealants are widely used for building materials such as interior materials due to their wide adhesion and convenience in construction operation.
However, RTV silicone sealants have good bioaffinity, including affinity for microorganisms, and thus are prone to slippery substances in parts that are soaked for long periods of time, which is caused by the proliferation and growth of microorganisms on the surface of the colloid. If the silicone sealant is not subjected to mildew-proof or bacteriostatic treatment, microorganisms are accumulated in the sealant for a long time, so that the appearance is blackened if the microorganisms are accumulated, and the performance of the sealant is invalid if the microorganisms are accumulated.
The existing mildew-proof antibacterial sealant is usually prepared by adding an inorganic or organic antibacterial agent in a physical compounding way, the physically compounded mildew-proof antibacterial sealant has good antibacterial effect within an initial period of time, however, the antibacterial and mildew-proof effects are obviously reduced after long-time use, because the physically compounded antibacterial agent can be lost in the using process, the content of the physically compounded antibacterial agent in a colloid is reduced, and the antibacterial and mildew-proof effects of the colloid are gradually lost.
Disclosure of Invention
Therefore, the mildew-proof and antibacterial silicone sealant composition with long-acting antibacterial and mildew-proof effects and the preparation method thereof are needed.
The invention provides a mildew-proof antibacterial silicone sealant composition which comprises, by mass, 40-50 parts of alpha, omega-dihydroxy polydimethylsiloxane, 2-3 parts of a mildew-proof antibacterial agent and a sealant auxiliary material;
the mildew-proof antibacterial agent is prepared by chemically modifying chitosan oligosaccharide by a modifier, wherein the modifier is at least one of 2- (3, 4-epoxycyclohexane) ethyltrimethoxysilane, 3- (2, 3-epoxypropoxy) propyltrimethoxysilane and isocyanate propyltriethoxysilane, and the mildew-proof antibacterial agent is connected with at least part of the alpha, omega-dihydroxy polydimethylsiloxane through chemical bonds.
In one embodiment, the chitosan oligosaccharide is used in an amount of 40-60 parts by mass, and the modifier is used in an amount of 10-15 parts by mass.
In one embodiment, the preparation method of the mildew-proof antibacterial agent comprises the following steps:
adding an organic solvent and the chitosan oligosaccharide into a reaction container, controlling the reaction temperature to be 30-40 ℃, then dropwise adding the modifier into the reaction system, keeping for 40-60 min after dropwise adding, then heating to 100-120 ℃, and then removing the solvent to obtain the mildew-proof antibacterial agent.
In one embodiment, the paint further comprises 0.1-30 parts by mass of polydimethylsiloxane.
In one embodiment, the polydimethylsiloxane has a viscosity of 300mPa s to 10000mPa s at 25 +/-0.5 ℃.
In one embodiment, the viscosity of the α, ω -dihydroxypolydimethylsiloxane is from 20000mPa · s to 100000mPa · s at 25 ± 0.5 ℃.
In one embodiment, the sealant adjuvant comprises at least one of a cross-linking agent, a coupling agent, a catalyst, and a filler.
In one embodiment, the cross-linking agent is at least one of methyltributanoxime silane, vinyltributoxime silane, tetrabutoximino silane, methyltrimethoxy silane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, ethyl silicate, methyl silicate, propyl silicate, methyltriacetoxy silane; the amount of the cross-linking agent is 3-5 parts by mass.
In one embodiment, the coupling agent is at least one of aminopropyltrimethoxysilane, aminopropyltriethoxysilane, aminoethylaminopropyltrimethoxysilane, aminoethylaminopropyltriethoxysilane, ureidopropyltriethoxysilane, glycidoxypropyltrimethoxysilane, glycidoxypropyltriethoxysilane, methacryloxypropyltrimethoxysilane, methacryloxypropyltriethoxysilane; the amount of the coupling agent is 0.5-2 parts by mass.
In one embodiment, the catalyst is at least one of dibutyl tin diacetate, dibutyl tin dilaurate, stannous octoate; the amount of the catalyst is 0.5-4 parts by mass.
In one embodiment, the filler is at least one of fumed silica, precipitated silica, nano-active calcium carbonate, heavy carbonic acid, silica micropowder, alumina, aluminum hydroxide and zinc oxide; the amount of the filler is 40-60 parts by mass.
According to the invention, 2- (3, 4-epoxycyclohexane) ethyltrimethoxysilane, 3- (2, 3-epoxypropoxy) propyltrimethoxysilane or isocyanate propyltriethoxysilane are selected as modifiers to chemically modify chitosan oligosaccharide with antibacterial activity, and siloxane groups are introduced into the structure of the chitosan oligosaccharide, so that the chitosan oligosaccharide has the basis of chemically modifying the silicone sealant without influencing the mildew-proof antibacterial activity, the mildew-proof antibacterial effective duration of the silicone sealant can be greatly prolonged, and the physical properties such as the adhesion, toughness and strength of the silicone sealant can not be obviously negatively influenced.
In another aspect of the present invention, a method for preparing the aforementioned mildew-proof antibacterial silicone sealant composition is provided, wherein the components are mixed under a vacuum state.
Detailed Description
In order that the invention may be more fully understood, reference will now be made to the accompanying examples. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature. In the description of the invention, "a plurality" means at least two, e.g., two, three, etc., unless explicitly specified otherwise. In the description of the present invention, "a plurality" means at least one, e.g., one, two, etc., unless specifically limited otherwise.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The invention provides a mildew-proof antibacterial silicone sealant composition which comprises, by mass, 40-50 parts of alpha, omega-dihydroxy polydimethylsiloxane, 2-3 parts of a mildew-proof antibacterial agent and a sealant auxiliary material; preferably, the anti-mildew and anti-bacterial agent comprises 42-48 parts of alpha, omega-dihydroxy polydimethylsiloxane and 2.3-2.9 parts of a mildew-proof and anti-bacterial agent; further preferably, the antibacterial agent comprises 44-46 parts of alpha, omega-dihydroxy polydimethylsiloxane and 2.5-2.7 parts of a mildew-proof antibacterial agent.
The mildew-proof antibacterial agent is prepared by chemically modifying chitosan oligosaccharide by a modifier, wherein the modifier is at least one of 2- (3, 4-epoxycyclohexane) ethyltrimethoxysilane, 3- (2, 3-epoxypropoxy) propyltrimethoxysilane and isocyanate propyltriethoxysilane, and the mildew-proof antibacterial agent is connected with at least part of the alpha, omega-dihydroxy polydimethylsiloxane through chemical bonds.
In a specific example, the amount of the chitosan oligosaccharide is 40-60 parts by mass, and the amount of the modifier is 10-15 parts by mass; preferably, the dosage of the chitosan oligosaccharide is 45-55 parts, the dosage of the modifier is 12-14 parts, further preferably, the dosage of the chitosan oligosaccharide is 48-52 parts, and the dosage of the modifier is 13 parts. The dosage of the chitosan oligosaccharide and the modifier is controlled within a certain range, so that the modification degree of the chitosan oligosaccharide can be effectively controlled, the influence of low modification degree on subsequent application is avoided, or the influence of the mildew-proof antibacterial activity of the chitosan oligosaccharide due to the reaction of the modifier and hydroxyl groups of the chitosan oligosaccharide caused by high modification degree is avoided.
In one specific example, the method of preparing the mildewproof antibacterial agent comprises the following steps:
adding an organic solvent and chitosan oligosaccharide into a reaction container, controlling the reaction temperature to be 30-40 ℃, then dropwise adding a modifier into the reaction system, keeping for 40-60 min after dropwise adding, then heating to 100-120 ℃, and then removing the solvent to obtain the mildew-proof antibacterial agent.
In a specific example, the modifier is controlled to be added within 60-80 min when being added.
In one specific example, the desolvation treatment is carried out under the vacuum degree of-0.90 MPa for 120min to 180 min.
In a specific example, the organic solvent is at least one of toluene, xylene, dimethyl sulfoxide, dimethylformamide and dimethylacetamide, and it is understood that the solvents listed here are effective solvents, and are not limited to the present embodiment, and other suitable organic solvents can also be used in the present embodiment.
In a specific example, the silicone rubber composition further comprises 0.1-30 parts by mass of polydimethylsiloxane, preferably 10-25 parts by mass of polydimethylsiloxane, and further preferably 15-20 parts by mass of polydimethylsiloxane.
In a specific example, the polydimethylsiloxane has a viscosity of 300 to 10000 mPas at 25. + -. 0.5 ℃, preferably 800 to 6000 mPas, and more preferably 2000 to 4000 mPas. A suitable viscosity range helps to control the sealant hardness within a reasonable range.
In a specific example, the α, ω -dihydroxypolydimethylsiloxane has a viscosity of 20000 to 100000mPa · s at 25 ± 0.5 ℃, preferably a viscosity of 30000 to 80000mPa · s, more preferably a viscosity of 50000 to 70000mPa · s. A suitable viscosity range helps to control the sealant hardness within a reasonable range.
In one particular example, the sealant adjuvant includes at least one of a cross-linking agent, a coupling agent, a catalyst, and a filler.
In a specific example, the cross-linking agent is at least one of methyltributanoxime silane, vinyltributoxime silane, tetrabutoximino silane, methyltrimethoxy silane, methyltriethoxy silane, vinyltrimethoxysilane, vinyltriethoxysilane, ethyl silicate, methyl silicate, propyl silicate, methyltriacetoxy silane; the amount of the cross-linking agent is 3-5 parts by mass.
In a specific example, the coupling agent is at least one of aminopropyltrimethoxysilane, aminopropyltriethoxysilane, aminoethylaminopropyltrimethoxysilane, aminoethylaminopropyltriethoxysilane, ureidopropyltriethoxysilane, glycidoxypropyltrimethoxysilane, glycidoxypropyltriethoxysilane, methacryloxypropyltrimethoxysilane, methacryloxypropyltriethoxysilane; the amount of the coupling agent is 0.5-2 parts by mass.
In one specific example, the catalyst is at least one of dibutyl tin diacetate, dibutyl tin dilaurate, stannous octoate; the amount of the catalyst is 0.5-4 parts by mass.
In a specific example, the filler is at least one of fumed silica, precipitated silica, nano activated calcium carbonate, heavy carbonic acid, silica micropowder, alumina, aluminum hydroxide and zinc oxide; the amount of the filler is 40-60 parts by mass.
The components are set within the proper mass portion range, so that the mildew-proof and antibacterial performance of the silicone sealant is improved to the maximum extent, and the basic physical properties of the sealant, such as adhesiveness, toughness, strength and the like, are maintained.
According to the invention, 2- (3, 4-epoxycyclohexane) ethyltrimethoxysilane, 3- (2, 3-epoxypropoxy) propyltrimethoxysilane or isocyanate propyltriethoxysilane are selected as modifiers to chemically modify chitosan oligosaccharide with antibacterial activity, and siloxane groups are introduced into the structure of the chitosan oligosaccharide, so that the chitosan oligosaccharide has the basis of chemically modifying the silicone sealant without influencing the mildew-proof antibacterial activity, the mildew-proof antibacterial effective duration of the silicone sealant can be greatly prolonged, and the physical properties such as the adhesion, toughness and strength of the silicone sealant can not be obviously negatively influenced.
In another aspect of the present invention, a method for preparing the aforementioned mildew-proof antibacterial silicone sealant composition is provided, wherein the components are mixed under a vacuum state.
In one specific example, the method comprises the following steps:
a) adding alpha, omega-dihydroxy polydimethylsiloxane into a reaction vessel, setting the vacuum degree to be below-0.90 MPa, and stirring to remove bubbles;
b) recovering normal pressure, adding the cross-linking agent, stirring, setting the vacuum degree below-0.95 MPa, and continuing stirring;
c) recovering normal pressure, adding coupling agent and mildew-proof antibacterial agent, setting vacuum degree below-0.95 MPa, and stirring;
d) recovering normal pressure, adding a catalyst, setting the vacuum degree to be below-0.95 MPa, and stirring to obtain the mildew-proof antibacterial silicone sealant.
In a specific example, the stirring speed of the step a) is 30RPM to 50RPM, and the stirring time is 20min to 30 min.
In a specific example, the stirring speed of step b) is 20RPM to 30RPM, the stirring time before the setting of the vacuum degree is 10min to 20min, and the stirring time after the setting of the vacuum degree is 10min to 20 min.
In a specific example, the stirring speed of the step c) is 30RPM to 50RPM, and the stirring time is 15min to 20 min.
In a specific example, the step d) is carried out for two times of stirring, the first stirring rotating speed is 5RPM to 10RPM, and the stirring time is 5min to 10 min; the second stirring speed is 20RPM to 30RPM, and the stirring time is 20min to 30 min.
The present invention will be described in further detail with reference to specific examples and comparative examples. It is understood that the following examples are specific to the apparatus and materials used, and in other specific examples, the present invention is not limited thereto, and may be, for example, not limited to stirring and dispersing using a planetary disperser.
Example 1
a) Adding 100 parts by mass of toluene and 50 parts by mass of chitosan oligosaccharide into a reaction kettle, controlling the reaction temperature to be 35 ℃, then dropwise adding 13 parts by mass of 2- (3, 4-epoxycyclohexane) ethyltrimethoxysilane into the reaction system, controlling the dropwise adding within 70min to be finished, keeping for 50min after the dropwise adding is finished, then heating to 100 ℃, and then carrying out desolventizing treatment at the vacuum degree of-0.90 MPa for 160min to obtain the mildew-proof antibacterial agent;
b) adding 45 parts by mass of alpha, omega-dihydroxy polydimethylsiloxane and 15 parts by mass of polydimethylsiloxane into a planetary dispersion machine, setting the vacuum degree to be-0.90 MPa, stirring to remove bubbles, wherein the stirring speed is 40RPM, and the stirring time is 25 min;
recovering normal pressure, adding 4 parts by mass of cross-linking agent methyl tributyl ketoxime silane, stirring at the rotating speed of 25RPM for 15min, setting the vacuum degree to be-0.95 MPa, and continuing stirring at the original speed for 20 min;
recovering normal pressure, adding 1.5 parts by mass of coupling agent aminopropyl trimethoxy silane and 2.6 parts by mass of the mildew-proof antibacterial agent prepared in the step a), setting the vacuum degree to be-0.95 MPa, and then stirring at the stirring speed of 40RPM for 20 min;
and recovering the normal pressure, adding 1 part by mass of catalyst dibutyltin diacetate, setting the vacuum degree to be-0.95 MPa, adjusting the stirring speed to be 7RPM, stirring for 10min, then adjusting the stirring speed to be 25RPM, and stirring for 25min to obtain the mildew-proof antibacterial silicone sealant.
Example 2
a) Adding 100 parts by mass of toluene and 50 parts by mass of chitosan oligosaccharide into a reaction kettle, controlling the reaction temperature to be 35 ℃, then dropwise adding 13 parts by mass of 3- (2, 3-epoxypropoxy) propyl trimethoxy silane into the reaction system, controlling the dropwise adding within 70min to be finished, keeping for 50min after the dropwise adding is finished, then heating to 100 ℃, and then carrying out desolventizing treatment at the vacuum degree of-0.90 MPa for 160min to obtain the mildew-proof antibacterial agent;
b) adding 45 parts by mass of alpha, omega-dihydroxy polydimethylsiloxane and 15 parts by mass of polydimethylsiloxane into a planetary dispersion machine, setting the vacuum degree to be-0.90 MPa, stirring to remove bubbles, wherein the stirring speed is 40RPM, and the stirring time is 25 min;
recovering normal pressure, adding 4 parts by mass of cross-linking agent methyl tributyl ketoxime silane, stirring at the rotating speed of 25RPM for 15min, setting the vacuum degree to be-0.95 MPa, and continuing stirring at the original speed for 20 min;
recovering normal pressure, adding 1.5 parts by mass of coupling agent aminopropyl trimethoxy silane and 2.6 parts by mass of the mildew-proof antibacterial agent prepared in the step a), setting the vacuum degree to be-0.95 MPa, and then stirring at the stirring speed of 40RPM for 20 min;
and recovering the normal pressure, adding 1 part by mass of catalyst dibutyltin diacetate, setting the vacuum degree to be-0.95 MPa, adjusting the stirring speed to be 7RPM, stirring for 10min, then adjusting the stirring speed to be 25RPM, and stirring for 25min to obtain the mildew-proof antibacterial silicone sealant.
Example 3
a) Adding 100 parts by mass of toluene and 50 parts by mass of chitosan oligosaccharide into a reaction kettle, controlling the reaction temperature to be 35 ℃, then dropwise adding 13 parts by mass of isocyanate propyl triethoxysilane into the reaction system, controlling the dropwise adding to be completed within 70min, keeping for 50min after the dropwise adding is completed, then heating to 100 ℃, and then carrying out desolventizing treatment under the vacuum degree of-0.90 MPa for 160min to obtain the mildew-proof antibacterial agent;
b) adding 45 parts by mass of alpha, omega-dihydroxy polydimethylsiloxane and 15 parts by mass of polydimethylsiloxane into a planetary dispersion machine, setting the vacuum degree to be-0.90 MPa, stirring to remove bubbles, wherein the stirring speed is 40RPM, and the stirring time is 25 min;
recovering normal pressure, adding 4 parts by mass of cross-linking agent methyl tributyl ketoxime silane, stirring at the rotating speed of 25RPM for 15min, setting the vacuum degree to be-0.95 MPa, and continuing stirring at the original speed for 20 min;
recovering normal pressure, adding 1.5 parts by mass of coupling agent aminopropyl trimethoxy silane and 2.6 parts by mass of the mildew-proof antibacterial agent prepared in the step a), setting the vacuum degree to be-0.95 MPa, and then stirring at the stirring speed of 40RPM for 20 min;
and recovering the normal pressure, adding 1 part by mass of catalyst dibutyltin diacetate, setting the vacuum degree to be-0.95 MPa, adjusting the stirring speed to be 7RPM, stirring for 10min, then adjusting the stirring speed to be 25RPM, and stirring for 25min to obtain the mildew-proof antibacterial silicone sealant.
Example 4
a) Adding 100 parts by mass of toluene and 55 parts by mass of chitosan oligosaccharide into a reaction kettle, controlling the reaction temperature to be 35 ℃, then dropwise adding 12 parts by mass of 2- (3, 4-epoxycyclohexane) ethyltrimethoxysilane into the reaction system, controlling the dropwise adding within 70min to be finished, keeping for 50min after the dropwise adding is finished, then heating to 100 ℃, and then carrying out desolventizing treatment at the vacuum degree of-0.90 MPa for 160min to obtain the mildew-proof antibacterial agent;
b) adding 45 parts by mass of alpha, omega-dihydroxy polydimethylsiloxane and 15 parts by mass of polydimethylsiloxane into a planetary dispersion machine, setting the vacuum degree to be-0.90 MPa, stirring to remove bubbles, wherein the stirring speed is 40RPM, and the stirring time is 25 min;
recovering normal pressure, adding 4 parts by mass of cross-linking agent methyl tributyl ketoxime silane, stirring at the rotating speed of 25RPM for 15min, setting the vacuum degree to be-0.95 MPa, and continuing stirring at the original speed for 20 min;
recovering normal pressure, adding 1.5 parts by mass of coupling agent aminopropyl trimethoxy silane and 2.6 parts by mass of the mildew-proof antibacterial agent prepared in the step a), setting the vacuum degree to be-0.95 MPa, and then stirring at the stirring speed of 40RPM for 20 min;
and recovering the normal pressure, adding 1 part by mass of catalyst dibutyltin diacetate, setting the vacuum degree to be-0.95 MPa, adjusting the stirring speed to be 7RPM, stirring for 10min, then adjusting the stirring speed to be 25RPM, and stirring for 25min to obtain the mildew-proof antibacterial silicone sealant.
Example 5
a) Adding 100 parts by mass of toluene and 50 parts by mass of chitosan oligosaccharide into a reaction kettle, controlling the reaction temperature to be 35 ℃, then dropwise adding 13 parts by mass of 2- (3, 4-epoxycyclohexane) ethyltrimethoxysilane into the reaction system, controlling the dropwise adding within 70min to be finished, keeping for 50min after the dropwise adding is finished, then heating to 100 ℃, and then carrying out desolventizing treatment at the vacuum degree of-0.90 MPa for 160min to obtain the mildew-proof antibacterial agent;
b) adding 42 parts by mass of alpha, omega-dihydroxy polydimethylsiloxane and 10 parts by mass of polydimethylsiloxane into a planetary dispersion machine, setting the vacuum degree to be-0.90 MPa, stirring to remove bubbles, wherein the stirring speed is 40RPM, and the stirring time is 25 min;
recovering normal pressure, adding 4 parts by mass of cross-linking agent methyl tributyl ketoxime silane, stirring at the rotating speed of 25RPM for 15min, setting the vacuum degree to be-0.95 MPa, and continuing stirring at the original speed for 20 min;
recovering normal pressure, adding 1.5 parts by mass of coupling agent aminopropyl trimethoxy silane and 2.6 parts by mass of the mildew-proof antibacterial agent prepared in the step a), setting the vacuum degree to be-0.95 MPa, and then stirring at the stirring speed of 40RPM for 20 min;
and recovering the normal pressure, adding 1 part by mass of catalyst dibutyltin diacetate, setting the vacuum degree to be-0.95 MPa, adjusting the stirring speed to be 7RPM, stirring for 10min, then adjusting the stirring speed to be 25RPM, and stirring for 25min to obtain the mildew-proof antibacterial silicone sealant.
Example 6
a) Adding 100 parts by mass of toluene and 45 parts by mass of chitosan oligosaccharide into a reaction kettle, controlling the reaction temperature to be 35 ℃, then dropwise adding 12 parts by mass of 2- (3, 4-epoxycyclohexane) ethyltrimethoxysilane into the reaction system, controlling the dropwise adding within 70min to be finished, keeping for 50min after the dropwise adding is finished, then heating to 100 ℃, and then carrying out desolventizing treatment at the vacuum degree of-0.90 MPa for 160min to obtain the mildew-proof antibacterial agent;
b) adding 48 parts by mass of alpha, omega-dihydroxy polydimethylsiloxane and 10 parts by mass of polydimethylsiloxane into a planetary dispersion machine, setting the vacuum degree to be-0.90 MPa, stirring to remove bubbles, wherein the stirring speed is 40RPM, and the stirring time is 25 min;
recovering normal pressure, adding 4 parts by mass of cross-linking agent methyl tributyl ketoxime silane, stirring at the rotating speed of 25RPM for 15min, setting the vacuum degree to be-0.95 MPa, and continuing stirring at the original speed for 20 min;
restoring the normal pressure, adding 1.5 parts by mass of a coupling agent aminopropyltrimethoxysilane and 2.3 parts by mass of the mildewproof antibacterial agent prepared in the step a), setting the vacuum degree to be-0.95 MPa, and then stirring at the rotating speed of 40RPM for 20 min;
and recovering the normal pressure, adding 1 part by mass of catalyst dibutyltin diacetate, setting the vacuum degree to be-0.95 MPa, adjusting the stirring speed to be 7RPM, stirring for 10min, then adjusting the stirring speed to be 25RPM, and stirring for 25min to obtain the mildew-proof antibacterial silicone sealant.
Example 7
a) Adding 100 parts by mass of toluene and 40 parts by mass of chitosan oligosaccharide into a reaction kettle, controlling the reaction temperature to be 35 ℃, then dropwise adding 15 parts by mass of 2- (3, 4-epoxycyclohexane) ethyltrimethoxysilane into the reaction system, controlling the dropwise adding within 70min to be finished, keeping for 50min after the dropwise adding is finished, then heating to 100 ℃, and then carrying out desolventizing treatment at the vacuum degree of-0.90 MPa for 160min to obtain the mildew-proof antibacterial agent;
b) adding 50 parts by mass of alpha, omega-dihydroxy polydimethylsiloxane and 5 parts by mass of polydimethylsiloxane into a planetary dispersion machine, setting the vacuum degree to be-0.90 MPa, stirring to remove bubbles, wherein the stirring speed is 40RPM, and the stirring time is 25 min;
recovering normal pressure, adding 4 parts by mass of cross-linking agent methyl tributyl ketoxime silane, stirring at the rotating speed of 25RPM for 15min, setting the vacuum degree to be-0.95 MPa, and continuing stirring at the original speed for 20 min;
recovering normal pressure, adding 1.5 parts by mass of coupling agent aminopropyl trimethoxy silane and 2 parts by mass of the mildew-proof antibacterial agent prepared in the step a), setting the vacuum degree to be-0.95 MPa, and then stirring at the stirring speed of 40RPM for 20 min;
and recovering the normal pressure, adding 1 part by mass of catalyst dibutyltin diacetate, setting the vacuum degree to be-0.95 MPa, adjusting the stirring speed to be 7RPM, stirring for 10min, then adjusting the stirring speed to be 25RPM, and stirring for 25min to obtain the mildew-proof antibacterial silicone sealant.
Example 8
a) Adding 100 parts by mass of toluene and 50 parts by mass of chitosan oligosaccharide into a reaction kettle, controlling the reaction temperature to be 35 ℃, then dropwise adding 13 parts by mass of 2- (3, 4-epoxycyclohexane) ethyltrimethoxysilane into the reaction system, controlling the dropwise adding within 70min to be finished, keeping for 50min after the dropwise adding is finished, then heating to 100 ℃, and then carrying out desolventizing treatment at the vacuum degree of-0.90 MPa for 160min to obtain the mildew-proof antibacterial agent;
b) adding 45 parts by mass of alpha, omega-dihydroxy polydimethylsiloxane into a planetary dispersion machine, setting the vacuum degree to be-0.90 MPa, stirring to remove bubbles, wherein the stirring speed is 40RPM, and the stirring time is 25 min;
recovering normal pressure, adding 4 parts by mass of cross-linking agent methyl tributyl ketoxime silane, stirring at the rotating speed of 25RPM for 15min, setting the vacuum degree to be-0.95 MPa, and continuing stirring at the original speed for 20 min;
recovering normal pressure, adding 1.5 parts by mass of coupling agent aminopropyl trimethoxy silane and 2.6 parts by mass of the mildew-proof antibacterial agent prepared in the step a), setting the vacuum degree to be-0.95 MPa, and then stirring at the stirring speed of 40RPM for 20 min;
and recovering the normal pressure, adding 1 part by mass of catalyst dibutyltin diacetate, setting the vacuum degree to be-0.95 MPa, adjusting the stirring speed to be 7RPM, stirring for 10min, then adjusting the stirring speed to be 25RPM, and stirring for 25min to obtain the mildew-proof antibacterial silicone sealant.
Comparative example 1
a) Adding 100 parts by mass of toluene and 50 parts by mass of chitosan oligosaccharide into a reaction kettle, controlling the reaction temperature to be 35 ℃, then dropwise adding 5 parts by mass of 2- (3, 4-epoxycyclohexane) ethyltrimethoxysilane into the reaction system, controlling the dropwise adding within 70min to be finished, keeping for 50min after the dropwise adding is finished, then heating to 100 ℃, and then carrying out desolventizing treatment at the vacuum degree of-0.90 MPa for 160min to obtain the mildew-proof antibacterial agent;
b) adding 45 parts by mass of alpha, omega-dihydroxy polydimethylsiloxane and 15 parts by mass of polydimethylsiloxane into a planetary dispersion machine, setting the vacuum degree to be-0.90 MPa, stirring to remove bubbles, wherein the stirring speed is 40RPM, and the stirring time is 25 min;
recovering normal pressure, adding 4 parts by mass of cross-linking agent methyl tributyl ketoxime silane, stirring at the rotating speed of 25RPM for 15min, setting the vacuum degree to be-0.95 MPa, and continuing stirring at the original speed for 20 min;
restoring the normal pressure, adding 1.5 parts by mass of a coupling agent aminopropyltrimethoxysilane and 2.6 parts by mass of the mildewproof antibacterial agent prepared in the step a), setting the vacuum degree to be-0.95 MPa, and then stirring at the rotating speed of 40RPM for 20 min;
and recovering the normal pressure, adding 1 part by mass of catalyst dibutyltin diacetate, setting the vacuum degree to be-0.95 MPa, adjusting the stirring speed to be 7RPM, stirring for 10min, then adjusting the stirring speed to be 25RPM, and stirring for 25min to obtain the mildew-proof antibacterial silicone sealant.
Comparative example 2
a) Adding 100 parts by mass of toluene and 50 parts by mass of chitosan oligosaccharide into a reaction kettle, controlling the reaction temperature to be 35 ℃, then dropwise adding 20 parts by mass of 2- (3, 4-epoxycyclohexane) ethyltrimethoxysilane into the reaction system, controlling the dropwise adding within 70min to be finished, keeping for 50min after the dropwise adding is finished, then heating to 100 ℃, and then carrying out desolventizing treatment at the vacuum degree of-0.90 MPa for 160min to obtain the mildew-proof antibacterial agent;
b) adding 45 parts by mass of alpha, omega-dihydroxy polydimethylsiloxane and 15 parts by mass of polydimethylsiloxane into a planetary dispersion machine, setting the vacuum degree to be-0.90 MPa, stirring to remove bubbles, wherein the stirring speed is 40RPM, and the stirring time is 25 min;
recovering normal pressure, adding 4 parts by mass of cross-linking agent methyl tributyl ketoxime silane, stirring at the rotating speed of 25RPM for 15min, setting the vacuum degree to be-0.95 MPa, and continuing stirring at the original speed for 20 min;
recovering normal pressure, adding 1.5 parts by mass of coupling agent aminopropyl trimethoxy silane and 2.6 parts by mass of the mildew-proof antibacterial agent prepared in the step a), setting the vacuum degree to be-0.95 MPa, and then stirring at the stirring speed of 40RPM for 20 min;
and recovering the normal pressure, adding 1 part by mass of catalyst dibutyltin diacetate, setting the vacuum degree to be-0.95 MPa, adjusting the stirring speed to be 7RPM, stirring for 10min, then adjusting the stirring speed to be 25RPM, and stirring for 25min to obtain the mildew-proof antibacterial silicone sealant.
Comparative example 3
a) Adding 100 parts by mass of toluene and 50 parts by mass of chitosan oligosaccharide into a reaction kettle, controlling the reaction temperature to be 35 ℃, then dropwise adding 13 parts by mass of 2- (3, 4-epoxycyclohexane) ethyltrimethoxysilane into the reaction system, controlling the dropwise adding within 70min to be finished, keeping for 50min after the dropwise adding is finished, then heating to 100 ℃, and then carrying out desolventizing treatment at the vacuum degree of-0.90 MPa for 160min to obtain the mildew-proof antibacterial agent;
b) adding 45 parts by mass of alpha, omega-dihydroxy polydimethylsiloxane and 35 parts by mass of polydimethylsiloxane into a planetary dispersion machine, setting the vacuum degree to be-0.90 MPa, stirring to remove bubbles, wherein the stirring speed is 40RPM, and the stirring time is 25 min;
recovering normal pressure, adding 4 parts by mass of cross-linking agent methyl tributyl ketoxime silane, stirring at the rotating speed of 25RPM for 15min, setting the vacuum degree to be-0.95 MPa, and continuing stirring at the original speed for 20 min;
recovering normal pressure, adding 1.5 parts by mass of coupling agent aminopropyl trimethoxy silane and 2.6 parts by mass of the mildew-proof antibacterial agent prepared in the step a), setting the vacuum degree to be-0.95 MPa, and then stirring at the stirring speed of 40RPM for 20 min;
and recovering the normal pressure, adding 1 part by mass of catalyst dibutyltin diacetate, setting the vacuum degree to be-0.95 MPa, adjusting the stirring speed to be 7RPM, stirring for 10min, then adjusting the stirring speed to be 25RPM, and stirring for 25min to obtain the mildew-proof antibacterial silicone sealant.
Comparative example 4
a) Adding 100 parts by mass of toluene and 50 parts by mass of chitosan oligosaccharide into a reaction kettle, controlling the reaction temperature to be 50 ℃, then dropwise adding 13 parts by mass of 2- (3, 4-epoxycyclohexane) ethyltrimethoxysilane into the reaction system, controlling the dropwise adding within 70min to be finished, keeping for 50min after the dropwise adding is finished, then heating to 100 ℃, and then carrying out desolventizing treatment at the vacuum degree of-0.90 MPa for 160min to obtain the mildew-proof antibacterial agent;
b) adding 45 parts by mass of alpha, omega-dihydroxy polydimethylsiloxane and 15 parts by mass of polydimethylsiloxane into a planetary dispersion machine, setting the vacuum degree to be-0.90 MPa, stirring to remove bubbles, wherein the stirring speed is 40RPM, and the stirring time is 25 min;
recovering normal pressure, adding 4 parts by mass of cross-linking agent methyl tributyl ketoxime silane, stirring at the rotating speed of 25RPM for 15min, setting the vacuum degree to be-0.95 MPa, and continuing stirring at the original speed for 20 min;
recovering normal pressure, adding 1.5 parts by mass of coupling agent aminopropyl trimethoxy silane and 2.6 parts by mass of the mildew-proof antibacterial agent prepared in the step a), setting the vacuum degree to be-0.95 MPa, and then stirring at the stirring speed of 40RPM for 20 min;
and recovering the normal pressure, adding 1 part by mass of catalyst dibutyltin diacetate, setting the vacuum degree to be-0.95 MPa, adjusting the stirring speed to be 7RPM, stirring for 10min, then adjusting the stirring speed to be 25RPM, and stirring for 25min to obtain the mildew-proof antibacterial silicone sealant.
Comparative example 5
Adding 45 parts by mass of alpha, omega-dihydroxy polydimethylsiloxane and 15 parts by mass of polydimethylsiloxane into a planetary dispersion machine, setting the vacuum degree to be-0.90 MPa, stirring to remove bubbles, wherein the stirring speed is 40RPM, and the stirring time is 25 min;
recovering normal pressure, adding 4 parts by mass of cross-linking agent methyl tributyl ketoxime silane, stirring at the rotating speed of 25RPM for 15min, setting the vacuum degree to be-0.95 MPa, and continuing stirring at the original speed for 20 min;
recovering normal pressure, adding 1.5 parts by mass of coupling agent aminopropyl trimethoxysilane, 2.6 parts by mass of chitosan oligosaccharide and 2- (3, 4-epoxycyclohexane) ethyl trimethoxysilane (the mass ratio of the chitosan oligosaccharide to the 2- (3, 4-epoxycyclohexane) ethyl trimethoxysilane is 50:13), setting the vacuum degree to be-0.95 MPa, and then stirring at the stirring speed of 40RPM for 20 min;
and recovering the normal pressure, adding 1 part by mass of catalyst dibutyltin diacetate, setting the vacuum degree to be-0.95 MPa, adjusting the stirring speed to be 7RPM, stirring for 10min, then adjusting the stirring speed to be 25RPM, and stirring for 25min to obtain the mildew-proof antibacterial silicone sealant.
Comparative example 6
Adding 45 parts by mass of alpha, omega-dihydroxy polydimethylsiloxane and 15 parts by mass of polydimethylsiloxane into a planetary dispersion machine, setting the vacuum degree to be-0.90 MPa, stirring to remove bubbles, wherein the stirring speed is 40RPM, and the stirring time is 25 min;
recovering normal pressure, adding 4 parts by mass of cross-linking agent methyl tributyl ketoxime silane, stirring at the rotating speed of 25RPM for 15min, setting the vacuum degree to be-0.95 MPa, and continuing stirring at the original speed for 20 min;
recovering normal pressure, adding 1.5 parts by mass of coupling agent aminopropyl trimethoxysilane and 2.6 parts by mass of 1, 2-benzisothiazole-3-ketone, setting the vacuum degree to be-0.95 MPa, and then stirring at the stirring speed of 40RPM for 20 min;
and recovering the normal pressure, adding 1 part by mass of catalyst dibutyltin diacetate, setting the vacuum degree to be-0.95 MPa, adjusting the stirring speed to be 7RPM, stirring for 10min, then adjusting the stirring speed to be 25RPM, and stirring for 25min to obtain the mildew-proof antibacterial silicone sealant.
Comparative example 7
Adding 45 parts by mass of alpha, omega-dihydroxy polydimethylsiloxane and 15 parts by mass of polydimethylsiloxane into a planetary dispersion machine, setting the vacuum degree to be-0.90 MPa, stirring to remove bubbles, wherein the stirring speed is 40RPM, and the stirring time is 25 min;
recovering normal pressure, adding 4 parts by mass of cross-linking agent methyl tributyl ketoxime silane, stirring at the rotating speed of 25RPM for 15min, setting the vacuum degree to be-0.95 MPa, and continuing stirring at the original speed for 20 min;
recovering normal pressure, adding 1.5 parts by mass of coupling agent aminopropyl trimethoxysilane and 2.6 parts by mass of nano-silver particles, setting the vacuum degree to be-0.95 MPa, and then stirring at the stirring speed of 40RPM for 20 min;
and recovering the normal pressure, adding 1 part by mass of catalyst dibutyltin diacetate, setting the vacuum degree to be-0.95 MPa, adjusting the stirring speed to be 7RPM, stirring for 10min, then adjusting the stirring speed to be 25RPM, and stirring for 25min to obtain the mildew-proof antibacterial silicone sealant.
And (3) performance testing:
the phi 2 x 2mm adhesive film of the antibacterial and mildewproof RTV condensed type silicone sealant prepared in the above examples and comparative examples after being cured for 28 days at 23 +/-3 ℃ and 50 +/-5% RH is used as a test object, and the antibacterial performance of the adhesive film is tested according to the standard of GB/T20944.2-2007 evaluation of antibacterial performance of textiles. The main innovation point of the invention is the long-acting antibacterial retention capacity, and in order to accelerate the simulation of the antibacterial performance of the silicone sealant after long-term immersion, the invention considers the ratio of the antibacterial rate of the glue film after 1000 times of hot water boiling to the antibacterial rate before hot water boiling, namely the antibacterial retention rate. The hardness test was carried out according to the GB/T531.1-2008 Press hardness test method for vulcanized rubber or thermoplastic rubber. Peel adhesion was performed according to the standard GB/T13477.18.2002 test method for building sealants, part 18.
TABLE 1
Figure BDA0002859831090000181
Figure BDA0002859831090000191
TABLE 2
Example 1 Comparative example 2 Comparative example 3 Comparative example 4
Inhibition of Staphylococcus aureus/%) 98 89 92 93
Inhibition of E.coli/%) 91 81 85 87
Shore hardness/HSA 32 36 23 37
Peeling force/(N/m) 178 167 153 178
TABLE 3
Comparative example 1 5 6 7
Staphylococcus aureus bacteriostatic retention/%) 70 65 60 55
Escherichia coli bacteriostatic retention/%) 47 43 39 29
Shore hardness/HSA 34 33 37 41
Peeling force/(N/m) 167 180 165 155
As can be seen from Table 1, in examples 1-3, after chitosan oligosaccharide is chemically modified by 2- (3, 4-epoxycyclohexane) ethyltrimethoxysilane, 3- (2, 3-epoxypropoxy) propyltrimethoxysilane and isocyanate propyltriethoxysilane, the adhesive film can keep a high antibacterial retention rate after being boiled in hot water for 1000 times; as can be seen from Table 3, the bacteriostatic retention rate is greatly reduced when chitosan oligosaccharide and a modifier are introduced into a system in the comparative example 5 by adopting physical blending, the bacteriostatic retention rate is also greatly reduced when organic antibacterial agents and inorganic antibacterial agents which are common in the market are respectively adopted in the comparative examples 6 and 7 and are also subjected to physical blending, and the bacteriostatic retention rate of an adhesive film is also greatly reduced after the adhesive film is boiled in hot water for 1000 times; as can be seen from comparative example 1 in Table 3, when the amount of the modifier is too small, the modification degree is too low, and the chitosan oligosaccharide which can be grafted to the sealant is too small, which results in that part of the chitosan oligosaccharide is still added to the system in a physically blended form, so the bacteriostasis retention rate is not as good as that of each example in which the amount of the modifier is set within a reasonable range. The results show that the chitosan oligosaccharide can be grafted into the sealant in a chemical bond manner by selecting a proper modifier and setting a reasonable dosage range, so that the mildew-proof and antibacterial properties of the sealant are greatly prolonged, and the basic properties of the sealant, such as hardness, adhesiveness and the like, can be kept within the required range.
In addition, the choice of modifier has a certain effect on the performance of the sealant, as in example 3 where isocyanatopropyltriethoxysilane was used as the modifier, the adhesion performance was slightly inferior to that of 2- (3, 4-epoxycyclohexane) ethyltrimethoxysilane and 3- (2, 3-epoxypropoxy) propyltrimethoxysilane modified examples 1 and 2.
As can be seen from Table 2, in comparative example 2, too much modifier is added, which results in too high modification degree, and the active groups of the chitosan oligosaccharide are blocked, which directly results in the reduction of the bacteriostasis rate of bacteria; in the comparative example 3, the use amount of the polydimethylsiloxane is too much, so that the hardness of the sealant is too low to reach the use standard; in comparative example 7, when the antifungal/antibacterial agent was prepared, the reaction temperature was too high, resulting in the participation of the hydroxyl groups on the chitosan oligosaccharide in the reaction, and the active groups of the chitosan oligosaccharide were blocked, thus decreasing the antibacterial rate.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (10)

1. The mildew-proof antibacterial silicone sealant composition is characterized by comprising 40-50 parts of alpha, omega-dihydroxy polydimethylsiloxane, 2-3 parts of mildew-proof antibacterial agent and sealant auxiliary materials in parts by mass;
the preparation method of the mildew-proof antibacterial agent comprises the following steps:
adding an organic solvent and chitosan oligosaccharide into a reaction container, controlling the reaction temperature to be 30-40 ℃, then dropwise adding a modifier into the reaction system, keeping the temperature for 40-60 min after dropwise adding, then heating to 100-120 ℃, and then removing the solvent to obtain the mildew-proof antibacterial agent;
the dosage of the chitosan oligosaccharide is 40-60 parts, and the dosage of the modifier is 10-15 parts; the modifier is at least one of 2- (3, 4-epoxycyclohexane) ethyl trimethoxy silane, 3- (2, 3-epoxypropoxy) propyl trimethoxy silane and isocyanate propyl triethoxy silane, and the mildew-proof antibacterial agent is connected with at least part of the alpha, omega-dihydroxy polydimethylsiloxane through chemical bonds.
2. The composition as claimed in claim 1, wherein the amount of the chitosan oligosaccharide is 45-55 parts by weight, and the amount of the modifier is 12-14 parts by weight.
3. The composition of claim 1, wherein the addition of the modifier is controlled to be completed within 60 to 80 min.
4. The composition according to claim 1, further comprising 0.1 to 30 parts by mass of polydimethylsiloxane.
5. The composition according to claim 4, wherein the polydimethylsiloxane has a viscosity of from 300 to 10000 mPa-s at 25 ± 0.5 ℃.
6. The composition of claim 5, wherein the α, ω -dihydroxypolydimethylsiloxane has a viscosity of 20000 to 100000 mPa-s at 25 ± 0.5 ℃.
7. The composition of any one of claims 1 to 6, wherein the sealant adjuvant comprises at least one of a cross-linking agent, a coupling agent, a catalyst and a filler.
8. The composition of claim 7, wherein the cross-linking agent is at least one of methyltributanoxime silane, vinyltributoxime silane, tetrabutoximino silane, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, ethyl silicate, methyl silicate, propyl silicate, methyltriacetoxysilane; the dosage of the cross-linking agent is 3-5 parts by mass;
the coupling agent is at least one of aminopropyltrimethoxysilane, aminopropyltriethoxysilane, aminoethylaminopropyltrimethoxysilane, aminoethylaminopropyltriethoxysilane, urea propyl triethoxysilane, glycidoxypropyltrimethoxysilane, glycidoxypropyltriethoxysilane, methacryloxypropyltrimethoxysilane and methacryloxypropyltriethoxysilane; the using amount of the coupling agent is 0.5-2 parts by mass;
the catalyst is at least one of dibutyltin diacetate, dibutyltin dilaurate and stannous octoate; the amount of the catalyst is 0.5-4 parts by mass.
9. The composition of claim 7, wherein the filler is at least one of fumed silica, precipitated silica, nano-activated calcium carbonate, silica fume, alumina, aluminum hydroxide, and zinc oxide; the amount of the filler is 40-60 parts by mass.
10. A method for preparing a composition according to any one of claims 1 to 9, wherein the components are mixed under vacuum.
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