CN113493614A - High-efficiency bonding bi-component room temperature vulcanized silicone rubber and preparation method thereof - Google Patents

High-efficiency bonding bi-component room temperature vulcanized silicone rubber and preparation method thereof Download PDF

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CN113493614A
CN113493614A CN202110885651.3A CN202110885651A CN113493614A CN 113493614 A CN113493614 A CN 113493614A CN 202110885651 A CN202110885651 A CN 202110885651A CN 113493614 A CN113493614 A CN 113493614A
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silicone rubber
silane
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CN113493614B (en
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刘学林
陈慧鹏
何帅
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Guangdong Jusi New Material Technology Co ltd
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of 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; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C—CHEMISTRY; METALLURGY
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    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • 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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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
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    • 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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Abstract

The invention discloses a high-efficiency bonding bi-component room temperature vulcanized silicone rubber and a preparation method thereof, wherein a component A and a component B are mixed and used, wherein the raw material of the component A comprises multi-alkoxy silane end-capped polydimethylsiloxane, filler, a stabilizer, a tackifier, a catalyst and a flame retardant, and the raw material of the component B comprises hydroxyl/methyl end-capped polydimethylsiloxane, filler, a cross-linking agent and a deep-layer curing accelerator. The high-efficiency bonding bi-component room temperature vulcanized silicone rubber obtained by the invention has the advantages of high hardness, good bonding effect and high bonding strength.

Description

High-efficiency bonding bi-component room temperature vulcanized silicone rubber and preparation method thereof
Technical Field
The invention relates to the technical field of rubber, in particular to high-efficiency bonding bi-component room temperature vulcanized silicone rubber and a preparation method thereof.
Background
The traditional condensed type room temperature vulcanized silicone rubber for bonding and sealing is divided into single component and double component. The single component has the advantages of simple and convenient use process, good operability and wide application range of adhesion, but has obvious and outstanding defects, namely, the curing speed is slow, and the production and assembly efficiency is greatly influenced. With the increase of the demand, the single component cannot meet the current production rhythm, and the two components are used in many industries, especially in some application industries requiring quick bonding, sealing and assembling or quick bonding and fixing of large parts and large areas.
The two-component condensed type room temperature vulcanized silicone rubber has the advantage of fast curing, can improve the production efficiency, but the common two-component bonded silicone rubber in the market at present can not meet the production requirement. The two-component adhesive comprises a 10:1 silicone structural sealant and a 1:1 addition type two-component adhesive silicone rubber which are commonly used in the market. The 10:1 two-component silicone structural sealant has the defects of obvious viscosity difference between A, B two components, large mixing ratio difference, uneven mixing risk in use, high price of sizing equipment, high cost and the like; the addition type two-component bonding sealant of 1:1 has the defects of poor bonding property, easy poisoning of a catalyst, limitation on the application environment and bonding base materials, sometimes heating and curing, high energy consumption and the like, so that the conventional two-component bonding type silica gel on the market still has many defects, such as the problems of poor flame retardance and the like, which can not well meet the production and assembly efficiency and requirements, and further development of the two-component bonding sealant is limited.
In order to solve the problems of deep curing, bonding effect and flame retardance of the existing double-component room temperature vulcanized silicone rubber, the technology provides 1:1 condensed type double-component room temperature vulcanized silicone rubber and a preparation method thereof.
Patent CN102002241B provides a two-component condensed type room temperature vulcanized silicone rubber, the raw materials of which include hydroxy-terminated polydimethylsiloxane, plasticizer, filler, cross-linking agent, tackifier, and catalyst, but its hardness, bonding effect and bonding strength after curing are poor, and it fails to meet the market demand.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a high-efficiency bonding bi-component room temperature vulcanized silicone rubber and a preparation method thereof.
The 1:1 dealcoholized condensed type double-component room temperature vulcanized silicone rubber currently on the market has the defects of inconsistent internal and external curing, poor deep curing, poor adhesion to plastic resin base materials with low surface energy, insufficient flame retardance and tensile strength and the like. The product has good bonding effect on common base materials and certain low-specific-surface-energy hard-bonded plastics and resin base materials due to the addition of the self-made modified silane, has good deep curing characteristic in a short curing time due to the addition of the self-made deep curing agent, and better meets the application requirements of customers on large-area bonding or rapid bonding and fixing of large workpieces.
In order to solve the technical problem, the technical scheme adopted by the invention is as follows:
the high-efficiency bonding bi-component room temperature vulcanized silicone rubber is formed by mixing a component A and a component B according to the mass ratio of 1: 1.
The preparation method of the high-efficiency bonding bi-component room temperature vulcanized silicone rubber comprises the following steps: mixing the component A and the component B to obtain the composition.
The component A comprises the following raw materials in parts by weight:
Figure BDA0003194045390000021
the component B comprises the following raw materials in parts by weight:
Figure BDA0003194045390000022
the polyalkoxy silane end-capped polydimethylsiloxane is a modified polymer which is prepared by taking hydroxyl-terminated polydimethylsiloxane as a basic adhesive and performing end-capping modification and combination on the hydroxyl-terminated polydimethylsiloxane by using one or a mixture of more of tetramethoxy silane, tetraethoxy silane, methyltrimethoxy silane, methyltriethoxy silane, methyldimethoxy silane and methyldiethoxy silane as a modifier.
The poly-alkoxy silane end-capped polydimethylsiloxane plays an important role in the storage stability of products, and has an obvious effect of improving the rapid curing of the products.
The stabilizer is one or a mixture of hexamethyldisilazane, hexamethylcyclotrisilazane, divinyltetramethyldisilazane, p-toluenesulfonyl isocyanate, isocyanatopropyltriethoxysilane, molecular sieve and anhydrous calcium chloride.
The stabilizer is used for removing trace moisture or redundant hydroxyl in the system so as to improve the storage stability of the product.
The filler is one or a mixture of more of active nano calcium carbonate, active heavy calcium carbonate, light calcium carbonate, heavy calcium carbonate, fumed silica, precipitated silica, surface-treated hydrophobic silica and active silica micropowder.
The tackifier can be one or more of gamma-aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, bis (trimethoxysilylpropyl) amine, bis (triethoxysilylpropyl) amine or hydrolyzed oligomers thereof; or epoxy silane or acyl silane, such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3- (methacryloyloxy) propyltrimethoxysilane, 3- (methacryloyloxy) propyltriethoxysilane, 3- (acryloyloxy) propyltrimethoxysilane, or hydrolyzed oligomer thereof; the silane coupling agent can also be prepared by compounding and modifying the silane coupling agent.
The tackifier is added to improve the adhesion of the product to base materials such as stainless steel, galvanized iron, spraying hardware, plastics, resin and the like.
The catalyst is one or more of dibutyl tin dilaurate, dibutyl tin diacetate, dioctyl tin dilaurate, stannous octoate, dimethyl tin dineodecanoate, triisobutyl tin octanoate, methyl tin mercaptide, butyl tin mercaptide, octyl tin mercaptide, monobutyl tin maleate, mono octyl butyl tin maleate, octyl tin maleate, di-neodecanoate tin dilaurate and dodecyl tin mercaptide; or one or more of chelate compounds of organotin such as di-n-butyl tin bis (ethylacetoacetate), di-n-butyl tin bis (acetylacetonate) and the like.
The hydroxyl/methyl-terminated polydimethylsiloxane is one or a mixture of alpha, omega-dihydroxyl polysiloxane, single-end alkoxy modified polydimethylsiloxane and dimethyl polysiloxane.
The cross-linking agent is one or a mixture of more of polyethyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane or hydrolyzed oligomer thereof, polymethyltriethoxysilane, tetraethoxysilane or oligomer thereof, propyl orthosilicate or oligomer thereof, tetramethoxysilane or oligomer thereof.
Preferably, the cross-linking agent is an oligomer of vinyltriethoxysilane and/or tetraethoxysilane.
The deep curing accelerator consists of water, hydroxyl silicone oil, precipitated white carbon black and acid-base salt;
the acid-base salt is one or a mixture of acetic acid, octanoic acid, oxalic acid, citric acid, hydrochloric acid, ethylenediamine, n-butylamine, hexylamine, dodecylamine and sodium hydroxide.
The components and the system adopted by the deep curing accelerator play an important role in accelerating deep curing.
The number of hydrogen bond acceptors and the number of rotatable chemical bonds in the dibutyl phosphate can promote the modification of the alpha, omega-dihydroxy polysiloxane by the methyltrimethoxysilane to a sufficient degree; the reaction activity of the nitrogen-hydrogen bond in the triethylamine is beneficial to the end-capping reaction of the alpha, omega-dihydroxy polysiloxane, so that the sufficient degree and the reaction rate of the end-capping reaction can be further enhanced when the dibutyl phosphate and the triethylamine are used as synergists for the silane end-capping treatment of the alpha, omega-dihydroxy polysiloxane, and the efficient bonding bi-component room-temperature vulcanized silicone rubber with high hardness, good bonding effect and high bonding strength can be obtained subsequently.
The invention prepares the modified silane with good wettability with the active nano calcium carbonate and the active heavy calcium carbonate by reacting N- (2-aminoethyl) -3-aminopropyl trimethoxy silane and 3-methacryloxypropyl methyl dimethoxy silane in advance, improves the service reliability of the poly-alkoxy silane end-capped polydimethylsiloxane, and prepares the component A together with bis (trimethoxysilylpropyl) amine and di-N-butyl ethyl diacetylacetate tin to obtain the high-efficiency bonding bi-component room temperature vulcanized silicone rubber with high hardness, good bonding effect and high bonding strength.
According to the invention, methyltrimethoxysilane is used as a modifier to modify alpha, omega-dihydroxy polysiloxane, so that the polyalkoxysilane terminated polydimethylsiloxane with good compatibility with active nano calcium carbonate and active heavy calcium carbonate is obtained, and the polyalkoxysilane terminated polydimethylsiloxane is used as the component A and is mixed with the component B to obtain the high-efficiency bonding bi-component room temperature vulcanized silicone rubber with high hardness, good bonding effect and high bonding strength.
The preparation method of the component A comprises the following steps: putting 95-105 parts by weight of dimethoxy-terminated polydimethylsiloxane a into a planetary stirrer, adding 50-80 parts by weight of active nano calcium carbonate and 20-40 parts by weight of active heavy calcium carbonate, and stirring for 30-50min at the rotation speed of 1000-1300rpm under the condition that the vacuum degree is (-0.09) - (-0.1) MPa; then, 0.5 to 3 weight portions of anhydrous calcium chloride, 1 to 3 weight portions of modified silane I, 2 to 3 weight portions of bis (trimethoxysilylpropyl) amine and 0.1 to 1 weight portion of di-n-butyl tin ethyl diacetylacetate are added in sequence, and the mixture is stirred for 40 to 60 minutes at the rotation speed of 600-900rpm under the condition that the vacuum degree is (-0.09) - (-0.1) MPa, and then the mixture is discharged, thus obtaining the component A.
The preparation method of the component B comprises the following steps: putting 80-85 parts by weight of alpha, omega-dihydroxypolysiloxane and 15-20 parts by weight of dimethylpolysiloxane into a planetary stirrer, adding 60-100 parts by weight of active nano calcium carbonate and 10-20 parts by weight of active heavy calcium carbonate powder, and stirring for 30-60min at the rotating speed of 1000-1300rpm under the condition that the vacuum degree is (-0.09) - (-0.1) MPa; then adding 1-5 parts by weight of polyethyltriethoxysilane, 2-5 parts by weight of ethyl orthosilicate and 3-15 parts by weight of deep curing accelerator I, stirring at the rotation speed of 700-900rpm for 40-60min under the condition that the vacuum degree is (-0.09) - (-0.1) MPa, and discharging to obtain the component B.
The preparation method of the dimethoxy-terminated polydimethylsiloxane a comprises the following steps: 1050-; then adding 1.6-2.5 parts by weight of dibutyl phosphate, and stirring for 25-50min at the rotating speed of 400-600rpm under the protection of nitrogen; then 0.7-1.2 weight parts of triethylamine is added, and the mixture is stirred for 50-70min at the rotating speed of 600rpm under the protection of nitrogen; finally, heating to 110-130 ℃, and reducing the pressure for 1-2h under the condition that the vacuum degree is (-0.09) - (-0.1) MPa to obtain the dimethyl silicone polymer a terminated by the dimethoxy; the dibutyl phosphate and the triethylamine are used as synergists for preparing the dimethoxy-terminated polydimethylsiloxane a;
the preparation method of the modified silane I comprises the following steps: adding 0.8-1.2mol of N- (2-aminoethyl) -3-aminopropyltrimethoxysilane into a reaction kettle, heating to 88-93 ℃, adding 0.8-1.2mol of 3-methacryloxypropylmethyldimethoxysilane, and reacting at 88-93 ℃ for 11-13h to obtain modified silane I;
the preparation method of the deep curing accelerator I comprises the following steps: putting 90-110 parts by weight of dimethyl silicone oil, 38-42 parts by weight of precipitated silica, 5-7 parts by weight of hexamethyldisilazane and 1-3 parts by weight of water into a kneader, stirring for 1-2h at the rotation speed of 600rpm at 20-30 ℃, then heating to 140 ℃ and 160 ℃, and reducing the pressure for 2-3h under the condition that the vacuum degree is (-0.09) - (-0.1) MPa, finally adding 3-5 parts by weight of hydroxyl silicone oil and stirring for 30-60min at the rotation speed of 600rpm at 300-.
Further preferably, the component A also comprises a flame retardant.
Further preferably, the preparation method of the component A comprises the following steps: putting 95-105 parts by weight of dimethoxy-terminated polydimethylsiloxane a into a planetary stirrer, adding 50-80 parts by weight of active nano calcium carbonate and 20-40 parts by weight of active heavy calcium carbonate, and stirring for 30-50min at the rotation speed of 1000-1300rpm under the condition that the vacuum degree is (-0.09) - (-0.1) MPa; then, 0.5 to 3 weight portions of anhydrous calcium chloride, 1 to 3 weight portions of modified silane I, 2 to 3 weight portions of bis (trimethoxysilylpropyl) amine, 0.1 to 1 weight portion of di-n-butyl tin ethyl diacetylacetate and 4 to 8 weight portions of flame retardant are added in sequence, and the mixture is stirred for 40 to 60 minutes at the rotation speed of 600 plus 900rpm under the condition that the vacuum degree is (-0.09) - (-0.1) MPa, and then the mixture is discharged, thus obtaining the component A.
The preparation method of the flame retardant comprises the following steps:
h1, performing steam explosion treatment on the mixed starch to obtain modified starch A; the mixed starch is at least two of corn starch, cassava starch, sweet potato starch and mung bean starch;
h2, placing the modified starch A in sulfur dioxide atmosphere and stirring, and simultaneously performing ultraviolet irradiation treatment to obtain modified starch B;
h3, mixing the modified starch B, the coupling agent, the inorganic modifier and the organic modifier, and then mixing to obtain a flame retardant;
h4 crushing the flame retardant, sieving and drying to obtain the flame retardant.
The coupling agent is at least one of trifluoropropylmethyl cyclotrisiloxane and dimethyl diacetoxysilane.
The inorganic modifier is at least one of aluminum silicate and zinc borate.
The organic modifier is at least one of polycarbonate resin and polyoxyethylene sorbitan trioleate.
The invention firstly reacts N- (2-aminoethyl) -3-aminopropyltrimethoxysilane and 3-methacryloxypropylmethyldimethoxysilane to prepare the modified silane with good wettability with the active nano calcium carbonate, the active heavy calcium carbonate and the anhydrous calcium chloride, and the component A is prepared together with bis (trimethoxysilylpropyl) amine and di-N-butyl diacetyl ethyl acetate tin, so that the high-efficiency bonding bi-component room temperature vulcanized silicone rubber with high hardness, good bonding effect and high bonding strength is obtained.
Corn starch and tapioca starch have complex spatial three-dimensional structures and abundant amylopectin groups, wherein tapioca starch can be used as a "binder" between an inorganic filler and an organic matrix due to its unique peak viscosity. According to the invention, after the spatial structures of corn starch and cassava starch are broken through a steam explosion mode, the corn starch and the cassava starch are recombined in a reducing atmosphere of sulfur dioxide, and modified starch with higher wettability is obtained under the promotion action of ultraviolet specific wavelength energy, wherein the modified starch can effectively and durably combine inorganic flame retardants, namely aluminum silicate and zinc borate, with an organic silicon sulfide rubber system taking alkoxy silane terminated polydimethylsiloxane as a main body, so that the silicon sulfide rubber with extremely high service reliability and flame retardant capability is obtained.
The fluorine-silicon atom ratio in the trifluoropropylmethyl cyclotrisiloxane and the relative orientation of the silicon atom in the dimethyldiacetoxysilane and an ester bond can ensure that the aluminum silicate and the zinc borate can be firmly locked in the space network structure of the modified starch due to electric negative attraction, improve the service reliability, and can also cooperate with an organic modifier to further enhance the mechanical toughness of the space network structure of the modified starch, thereby improving the macroscopic mechanical properties of the vulcanized silicone rubber including tensile strength.
The polycarbonate resin has good flame retardance and oxidation resistance, high mechanical strength, high elastic coefficient and high impact strength, and can effectively enhance the mechanical strength of a space network structure of the modified starch when being compounded with polyoxyethylene sorbitan trioleate to be used as an organic modifier for preparing the flame retardant, and meanwhile, the polycarbonate resin has good compatibility with the inorganic modifier, so that good flame retardant property is obtained.
Preferably, the preparation method of the flame retardant comprises the following steps:
h1 performing steam explosion treatment on the mixed starch by adopting the pressure of 4.5-5MPa for 65-80s to obtain modified starch A; the mixed starch is a mixture of two or more of corn starch, cassava starch, sweet potato starch and mung bean starch;
h2, placing the modified starch A in a sulfur dioxide atmosphere with the temperature of 75-85 ℃, stirring at the rotating speed of 20-50rpm for 70-90min, and simultaneously performing ultraviolet irradiation treatment with the wavelength of 200-205nm and the power of 120-140W to obtain modified starch B;
h3, mixing the modified starch B, the coupling agent, the inorganic modifier and the organic modifier according to the mass ratio of (45-56): 20-23): 13-16): 16-18, and then mixing for 18-23min under the conditions that the temperature is 70-85 ℃, the pressure is 10-13MPa and the rotating speed is 30-60rpm to obtain a flame retardant;
h4 crushing the flame retardant body, sieving with a 400-sand 500-mesh sieve, and drying at 70-75 ℃ under 3-6kPa for 12-20H to obtain the flame retardant.
The coupling agent is a mixture of trifluoropropylmethyl cyclotrisiloxane and dimethyl diacetoxysilane according to the mass ratio of (1-3) to (1-3).
The inorganic modifier is a mixture of aluminum silicate and zinc borate according to the mass ratio of (1-5) to (1-5).
The organic modifier is a mixture of polycarbonate resin and polyoxyethylene sorbitan trioleate according to the mass ratio of (1-3) to (1-3).
More preferably, the organic modifier is a mixture of a polycarbonate resin and polyoxyethylene sorbitan trioleate in a mass ratio of 1: 1.
The invention has the beneficial effects that:
1. the efficient bonding bi-component room temperature vulcanized silicone rubber with high hardness, good bonding effect and high bonding strength is obtained by using raw materials such as alpha, omega-dihydroxypolysiloxane, methyltrimethoxysilane, precipitated white carbon black, hexamethyldisilazane and the like.
2. Methyl trimethoxy silane is used as a modifier to perform end-capping modification on alpha, omega-dihydroxy polysiloxane, and dibutyl phosphate and triethylamine are used as synergists at the same time, so that the polyalkoxy silane end-capped polydimethylsiloxane with good compatibility with active nano calcium carbonate and active heavy calcium carbonate is obtained, the service reliability of the polyalkoxy silane end-capped polydimethylsiloxane is enhanced, and the polyalkoxy silane end-capped polydimethylsiloxane can be used for the high-efficiency bonding bi-component room-temperature vulcanized silicone rubber and a preparation method thereof.
3. Starch, trifluoropropylmethyl cyclotrisiloxane, dimethyl diacetoxysilane, aluminum silicate, zinc borate, polycarbonate resin and polyoxyethylene sorbitan trioleate are taken as raw materials, the obtained flame retardant and the vulcanized silicone rubber system have good compatibility, and the vulcanized silicone rubber with higher flame retardance and tensile strength can be obtained.
Detailed Description
The invention will now be described in further detail with reference to specific embodiments thereof, but it should not be understood that the scope of the subject matter of the invention is limited to the examples described below.
Introduction of some raw materials in this application:
α, ω -dihydroxypolysiloxane, CAS: 31692-79-2, viscosity (25 ℃): 10000mPa s, manufacturer: polymer Dynamix, USA.
Methyltrimethoxysilane, CAS: 1185-55-3, manufacturer: polymer Dynamix, usa, refractive index: 1.370.
dimethicone, CAS: 9016-00-6, viscosity (25 ℃): 100 mPas, manufacturer: polymer Dynamix, USA, meets the regulation of HG/T2366-92.
White carbon black, CAS: 14464-46-1, specific surface area: 200m/g, manufacturer: belgium Solvay, the embodiment adopts precipitated silica.
Dimethicone, CAS: 63148-62-9, viscosity (25 ℃): 500 mPas, manufacturer: polymer Dynamix, USA.
N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, CAS: 1760-24-3, manufacturer: polymer Dynamix, USA.
3-methacryloxypropylmethyldimethoxysilane, CAS: 14513-34-9, manufacturer: polymer Dynamix, USA.
Tetraethoxysilane, CAS: 78-10-4, manufacturer: polymer Dynamix, USA.
Corn starch, manufacturer: the Erlan Biocycle has impurity content less than or equal to 3%, and the model is as follows: industrial grade.
Tapioca starch, manufacturer: the Erlan Biocycle has impurity content less than or equal to 3%, and the model is as follows: industrial grade.
Trifluoropropylmethylcyclotrisiloxane, CAS: 2374-14-3, manufacturer: polymer Dynamix, USA.
Dimethyldiacetoxysilane, CAS: 2182-66-3, manufacturer: polymer Dynamix, USA.
Aluminum silicate, CAS: 12141-46-7, manufacturer: doudosia chemical Co., Ltd, particle size: 1000 meshes and the purity is more than or equal to 99 percent.
Zinc borate, CAS: 1332-07-6, manufacturer: doudosia chemical Co., Ltd, particle size: 1100 meshes and the purity is more than or equal to 98.5 percent.
Polycarbonate resin, CAS: 24936-68-3, manufacturer: polymer Dynamix, us, molecular weight: 25000.
polyoxyethylene sorbitan trioleate, CAS: 9005-70-3, manufacturer: chemical company, Kyoeisha, molecular weight: 2300.
example 1
The high-efficiency bonding bi-component room temperature vulcanized silicone rubber is formed by mixing a component A and a component B according to the mass ratio of 1: 1.
The preparation method of the component A comprises the following steps: putting 100 parts by weight of dimethoxy-terminated polydimethylsiloxane a into a planetary stirrer, adding 80 parts by weight of active nano calcium carbonate and 40 parts by weight of active heavy calcium carbonate, and stirring for 40min at the rotating speed of 1200rpm under the condition that the vacuum degree is-0.1 MPa; then sequentially adding 2 parts by weight of anhydrous calcium chloride, 2 parts by weight of modified silane I, 2 parts by weight of bis (trimethoxysilylpropyl) amine and 1 part by weight of di-n-butyl tin ethyl diacetylacetate, stirring for 50min at the rotating speed of 800rpm under the condition that the vacuum degree is-0.1 MPa, and discharging to obtain the component A.
The preparation method of the component B comprises the following steps: putting 85 parts by weight of alpha, omega-dihydroxyl polysiloxane and 15 parts by weight of dimethyl polysiloxane into a planetary stirrer, adding 100 parts by weight of active nano calcium carbonate and 20 parts by weight of active heavy calcium carbonate powder, and stirring for 40min at the rotating speed of 1200rpm under the condition that the vacuum degree is-0.1 MPa; then adding 3 parts by weight of polyethyltriethoxysilane, 3 parts by weight of ethyl orthosilicate and 15 parts by weight of deep curing accelerator I, stirring for 50min at 900rpm under the condition that the vacuum degree is-0.1 MPa, and discharging to obtain a component B; the viscosity (25 ℃) of the alpha, omega-dihydroxy polysiloxane is 10000 mPas; the viscosity (25 ℃) of the dimethylpolysiloxane was 500 mPas.
The preparation method of the dimethoxy-terminated polydimethylsiloxane a comprises the following steps: putting 1000 parts by weight of alpha, omega-dihydroxypolysiloxane and 30 parts by weight of methyltrimethoxysilane into a reaction kettle and stirring at the rotating speed of 500rpm for 25 min; then adding 2 parts by weight of dibutyl phosphate, and stirring for 30min at the rotating speed of 500rpm under the protection of nitrogen; adding 1 part by weight of triethylamine, and stirring for 60min at the rotating speed of 500rpm under the protection of nitrogen; finally, heating to 120 ℃, and reducing the pressure for 1h under the condition that the vacuum degree is-0.1 MPa to obtain the dimethyl silicone polymer a terminated by the dimethoxy; the dibutyl phosphate and the triethylamine are used as synergists for preparing the dimethyl silicone polymer a with the dimethoxy end capping; the viscosity of the alpha, omega-dihydroxypolysiloxane (25 ℃) is 10000 mPas.
The preparation method of the modified silane I comprises the following steps: adding 1mol of N- (2-aminoethyl) -3-aminopropyltrimethoxysilane into a reaction kettle, heating to 90 ℃, adding 1mol of 3-methacryloxypropylmethyldimethoxysilane, and reacting at 90 ℃ for 12 hours to obtain modified silane I.
The preparation method of the deep curing accelerator I comprises the following steps: putting 100 parts by weight of dimethyl silicone oil, 40 parts by weight of precipitated silica white, 6 parts by weight of hexamethyldisilazane and 2 parts by weight of water into a kneader, stirring at 25 ℃ for 1h at the rotating speed of 500rpm, heating to 150 ℃, and reducing the pressure for 2h under the condition that the vacuum degree is-0.1 MPa, finally adding 4 parts by weight of hydroxyl silicone oil and stirring at the rotating speed of 500rpm for 40min to obtain the deep curing accelerator I; the viscosity (25 ℃) of the dimethylsilicone fluid was 100 mPas.
The preparation method of the high-efficiency bonding bi-component room temperature vulcanized silicone rubber comprises the following steps: mixing the component A and the component B to obtain the composition.
Test example 1
And (3) hardness testing: according to GB/T531.1-2008 "method for Press hardness test of vulcanized or thermoplastic rubber part 1: the hardness of the vulcanized silicone rubber obtained in example 1 was measured by the shore durometer method (shore hardness). A scale is selected and a Shore A type durometer is adopted. The pressing foot has a diameter of 18mm and a middle hole with a diameter of 3mm, and the pressing needle is a hard steel bar with a diameter of 1.25 mm. For each example, 3 specimens were tested and the test results were averaged over the three specimens. The test results are shown in table 1.
TABLE 1 hardness of the vulcanized Silicone rubber
Figure BDA0003194045390000111
Test example 2
Testing the bonding effect: the vulcanized silicone rubber obtained in example 1 was extruded and coated on the surface of a substrate to obtain a layer of adhesive having a thickness of 0.2cm, a width of 2cm and a length of 3cm, and then the substrate coated with the two-component silicone rubber was quickly covered on a clean and dry ordinary tempered glass and lightly pressed to ensure sufficient contact between the surface of the tempered glass and the sealant, and the adhesion effect was tested at 25 ℃ and a relative humidity of 60%. The base materials are respectively PC (polycarbonate), ABS (terpolymer of three monomers of acrylonitrile, butadiene and styrene), PVC (polyvinyl chloride), stainless steel and galvanized iron.
For each example, 3 specimens were tested and the test results were averaged over the three specimens. The test results are shown in table 2.
TABLE 2 bonding Effect of vulcanized Silicone rubber
Figure BDA0003194045390000121
Test example 3
Adhesive strength test: the adhesion strength of the vulcanized silicone rubber obtained in example 1 was tested according to GB/T11211-2009 "determination of adhesion strength of vulcanized rubber or thermoplastic rubber to Metal two-plate method". The thickness of the sample was 3mm, the diameter was 35mm, the measurement accuracy was 0.1mm, and the thickness of the metal plate was 10 mm. Testing the sample by using a tensile machine after adjusting the sample for 24 hours in an environment with the temperature of 23 ℃ and the relative humidity of 60 percent, wherein the moving speed of the clamp is 30 mm/min.
For each example, 3 specimens were tested and the test results were averaged over the three specimens. The test results are shown in table 3.
TABLE 3 adhesive Strength of vulcanized Silicone rubber
Figure BDA0003194045390000122
Example 2
The high-efficiency bonding bi-component room temperature vulcanized silicone rubber is formed by mixing a component A and a component B according to the mass ratio of 1: 1.
The preparation method of the component A comprises the following steps: putting 100 parts by weight of dimethoxy-terminated polydimethylsiloxane a into a planetary stirrer, adding 80 parts by weight of active nano calcium carbonate and 40 parts by weight of active heavy calcium carbonate, and stirring for 40min at the rotating speed of 1200rpm under the condition that the vacuum degree is-0.1 MPa; then sequentially adding 2 parts by weight of anhydrous calcium chloride, 2 parts by weight of modified silane I, 2 parts by weight of bis (trimethoxysilylpropyl) amine, 1 part by weight of di-n-butyl tin ethyl diacetylacetate and 4 parts by weight of flame retardant, stirring for 50min at the rotating speed of 800rpm under the condition that the vacuum degree is-0.1 MPa, and discharging to obtain the component A.
The preparation method of the component B comprises the following steps: putting 85 parts by weight of alpha, omega-dihydroxyl polysiloxane and 15 parts by weight of dimethyl polysiloxane into a planetary stirrer, adding 100 parts by weight of active nano calcium carbonate and 20 parts by weight of active heavy calcium carbonate powder, and stirring for 40min at the rotating speed of 1200rpm under the condition that the vacuum degree is-0.1 MPa; then adding 3 parts by weight of polyethyltriethoxysilane, 3 parts by weight of ethyl orthosilicate and 15 parts by weight of deep curing accelerator I, stirring for 50min at 900rpm under the condition that the vacuum degree is-0.1 MPa, and discharging to obtain a component B; the viscosity (25 ℃) of the alpha, omega-dihydroxy polysiloxane is 10000 mPas; the viscosity (25 ℃) of the dimethylpolysiloxane was 500 mPas.
The preparation method of the dimethoxy-terminated polydimethylsiloxane a comprises the following steps: putting 1000 parts by weight of alpha, omega-dihydroxypolysiloxane and 30 parts by weight of methyltrimethoxysilane into a reaction kettle and stirring at the rotating speed of 500rpm for 25 min; then adding 2 parts by weight of dibutyl phosphate, and stirring for 30min at the rotating speed of 500rpm under the protection of nitrogen; adding 1 part by weight of triethylamine, and stirring for 60min at the rotating speed of 500rpm under the protection of nitrogen; finally, heating to 120 ℃, and reducing the pressure for 1h under the condition that the vacuum degree is-0.1 MPa to obtain the dimethyl silicone polymer a terminated by the dimethoxy; the dibutyl phosphate and the triethylamine are used as synergists for preparing the dimethyl silicone polymer a with the dimethoxy end capping; the viscosity of the alpha, omega-dihydroxypolysiloxane (25 ℃) is 10000 mPas.
The preparation method of the modified silane I comprises the following steps: adding 1mol of N- (2-aminoethyl) -3-aminopropyltrimethoxysilane into a reaction kettle, heating to 90 ℃, adding 1mol of 3-methacryloxypropylmethyldimethoxysilane, and reacting at 90 ℃ for 12 hours to obtain the modified silane I.
The preparation method of the flame retardant comprises the following steps:
h1 performing steam explosion treatment on the mixed starch by adopting the pressure of 4.8MPa for 75s to obtain modified starch A; the mixed starch is a mixture of corn starch and cassava starch in a mass ratio of 2: 1;
h2, placing the modified starch A in a sulfur dioxide atmosphere at the temperature of 80 ℃, stirring at the rotating speed of 40rpm for 80min, and simultaneously performing ultraviolet irradiation treatment with the wavelength of 203nm and the power of 130W to obtain modified starch B;
h3, mixing the modified starch B, the coupling agent, the inorganic modifier and the organic modifier according to the mass ratio of 50:22:15:17, and then mixing for 20min under the conditions that the temperature is 80 ℃, the pressure is 12MPa and the rotating speed is 50rpm to obtain a flame retardant;
h4 crushing the flame retardant body, sieving the crushed flame retardant body by a sieve of 500 meshes, and drying the crushed flame retardant body for 15 hours at the temperature of 75 ℃ and under the air pressure of 5kPa to obtain the flame retardant.
The coupling agent is a mixture of trifluoropropylmethyl cyclotrisiloxane and dimethyl diacetoxysilane in a mass ratio of 2: 1.
The inorganic modifier is a mixture of aluminum silicate and zinc borate according to the mass ratio of 2: 3.
The organic modifier is a mixture of polycarbonate resin and polyoxyethylene sorbitan trioleate in a mass ratio of 1: 1.
The preparation method of the deep curing accelerator I comprises the following steps: putting 100 parts by weight of dimethyl silicone oil, 40 parts by weight of precipitated silica white, 6 parts by weight of hexamethyldisilazane and 2 parts by weight of water into a kneader, stirring at 25 ℃ for 1h at the rotating speed of 500rpm, heating to 150 ℃, and reducing the pressure for 2h under the condition that the vacuum degree is-0.1 MPa, finally adding 4 parts by weight of hydroxyl silicone oil and stirring at the rotating speed of 500rpm for 40min to obtain the deep curing accelerator I; the viscosity (25 ℃) of the dimethylpolysiloxane was 500 mPas.
The preparation method of the high-efficiency bonding bi-component room temperature vulcanized silicone rubber comprises the following steps: mixing the component A and the component B to obtain the composition.
Example 3
Substantially the same as in example 2, except that,
the preparation method of the flame retardant comprises the following steps:
h1 performing steam explosion treatment on the mixed starch by adopting the pressure of 4.8MPa for 75s to obtain modified starch A; the mixed starch is a mixture of corn starch and cassava starch in a mass ratio of 2: 1;
h2, placing the modified starch A in a sulfur dioxide atmosphere at the temperature of 80 ℃, stirring at the rotating speed of 40rpm for 80min, and simultaneously performing ultraviolet irradiation treatment with the wavelength of 203nm and the power of 130W to obtain modified starch B;
h3, mixing the modified starch B, the coupling agent, the inorganic modifier and the organic modifier according to the mass ratio of 50:22:15:17, and then mixing for 20min under the conditions that the temperature is 80 ℃, the pressure is 12MPa and the rotating speed is 50rpm to obtain a flame retardant;
h4 crushing the flame retardant body, sieving the crushed flame retardant body by a sieve of 500 meshes, and drying the crushed flame retardant body for 15 hours at the temperature of 75 ℃ and under the air pressure of 5kPa to obtain the flame retardant.
The coupling agent is a mixture of trifluoropropylmethyl cyclotrisiloxane and dimethyl diacetoxysilane in a mass ratio of 2: 1.
The inorganic modifier is a mixture of aluminum silicate and zinc borate according to the mass ratio of 2: 3.
The organic modifier is polycarbonate resin.
Example 4
Substantially the same as in example 2, except that,
the preparation method of the flame retardant comprises the following steps:
h1 performing steam explosion treatment on the mixed starch by adopting the pressure of 4.8MPa for 75s to obtain modified starch A; the mixed starch is a mixture of corn starch and cassava starch in a mass ratio of 2: 1;
h2, placing the modified starch A in a sulfur dioxide atmosphere at the temperature of 80 ℃, stirring at the rotating speed of 40rpm for 80min, and simultaneously performing ultraviolet irradiation treatment with the wavelength of 203nm and the power of 130W to obtain modified starch B;
h3, mixing the modified starch B, the coupling agent, the inorganic modifier and the organic modifier according to the mass ratio of 50:22:15:17, and then mixing for 20min under the conditions that the temperature is 80 ℃, the pressure is 12MPa and the rotating speed is 50rpm to obtain a flame retardant;
h4 crushing the flame retardant body, sieving the crushed flame retardant body by a sieve of 500 meshes, and drying the crushed flame retardant body for 15 hours at the temperature of 75 ℃ and under the air pressure of 5kPa to obtain the flame retardant.
The coupling agent is a mixture of trifluoropropylmethyl cyclotrisiloxane and dimethyl diacetoxysilane in a mass ratio of 2: 1.
The inorganic modifier is a mixture of aluminum silicate and zinc borate according to the mass ratio of 2: 3.
The organic modifier is polyoxyethylene sorbitan trioleate.
Example 5
Substantially the same as in example 2, except that,
the preparation method of the flame retardant comprises the following steps:
h1 performing steam explosion treatment on the mixed starch by adopting the pressure of 4.8MPa for 75s to obtain modified starch A; the mixed starch is a mixture of corn starch and cassava starch in a mass ratio of 2: 1;
h2, placing the modified starch A in a sulfur dioxide atmosphere at the temperature of 80 ℃, stirring at the rotating speed of 40rpm for 80min, and simultaneously performing ultraviolet irradiation treatment with the wavelength of 203nm and the power of 130W to obtain modified starch B;
h3, mixing the modified starch B, the coupling agent and the inorganic modifier according to the mass ratio of 50:22:15, and then mixing for 20min under the conditions that the temperature is 80 ℃, the pressure is 12MPa and the rotating speed is 50rpm to obtain a flame retardant;
h4 crushing the flame retardant body, sieving the crushed flame retardant body by a sieve of 500 meshes, and drying the crushed flame retardant body for 15 hours at the temperature of 75 ℃ and under the air pressure of 5kPa to obtain the flame retardant.
The coupling agent is a mixture of trifluoropropylmethyl cyclotrisiloxane and dimethyl diacetoxysilane in a mass ratio of 2: 1.
The inorganic modifier is a mixture of aluminum silicate and zinc borate according to the mass ratio of 2: 3.
Example 6
Substantially the same as in example 2, except that,
the preparation method of the flame retardant comprises the following steps:
h1 performing steam explosion treatment on the mixed starch by adopting the pressure of 4.8MPa for 75s to obtain modified starch A; the mixed starch is a mixture of corn starch and cassava starch in a mass ratio of 2: 1;
h2, placing the modified starch A in a sulfur dioxide atmosphere at the temperature of 80 ℃, stirring at the rotating speed of 40rpm for 80min, and simultaneously performing ultraviolet irradiation treatment with the wavelength of 203nm and the power of 130W to obtain modified starch B;
h3, mixing the modified starch B, the coupling agent and the organic modifier according to the mass ratio of 50:22:17, and then mixing for 20min under the conditions that the temperature is 80 ℃, the pressure is 12MPa and the rotating speed is 50rpm to obtain a flame retardant;
h4 crushing the flame retardant body, sieving the crushed flame retardant body by a sieve of 500 meshes, and drying the crushed flame retardant body for 15 hours at the temperature of 75 ℃ and under the air pressure of 5kPa to obtain the flame retardant.
The coupling agent is a mixture of trifluoropropylmethyl cyclotrisiloxane and dimethyl diacetoxysilane in a mass ratio of 2: 1.
The organic modifier is a mixture of polycarbonate resin and polyoxyethylene sorbitan trioleate in a mass ratio of 1: 1.
Example 7
Substantially the same as in example 2, except that,
the preparation method of the flame retardant comprises the following steps:
h1 performing steam explosion treatment on the mixed starch by adopting the pressure of 4.8MPa for 75s to obtain modified starch A; the mixed starch is a mixture of corn starch and cassava starch in a mass ratio of 2: 1;
h2 stirring the modified starch A at 80 ℃ and 40rpm for 80min, and simultaneously irradiating by using ultraviolet rays with the wavelength of 203nm and the power of 130W to obtain modified starch B;
h3, mixing the modified starch B, the coupling agent, the inorganic modifier and the organic modifier according to the mass ratio of 50:22:15:17, and then mixing for 20min under the conditions that the temperature is 80 ℃, the pressure is 12MPa and the rotating speed is 50rpm to obtain a flame retardant;
h4 crushing the flame retardant body, sieving the crushed flame retardant body by a sieve of 500 meshes, and drying the crushed flame retardant body for 15 hours at the temperature of 75 ℃ and under the air pressure of 5kPa to obtain the flame retardant.
The coupling agent is a mixture of trifluoropropylmethyl cyclotrisiloxane and dimethyl diacetoxysilane in a mass ratio of 2: 1.
The inorganic modifier is a mixture of aluminum silicate and zinc borate according to the mass ratio of 2: 3.
The organic modifier is a mixture of polycarbonate resin and polyoxyethylene sorbitan trioleate in a mass ratio of 1: 1.
Example 8
Substantially the same as in example 2, except that,
the preparation method of the flame retardant comprises the following steps:
h1 performing steam explosion treatment on the mixed starch by adopting the pressure of 4.8MPa for 75s to obtain modified starch A; the mixed starch is a mixture of corn starch and cassava starch in a mass ratio of 2: 1;
h2, placing the modified starch A in a sulfur dioxide atmosphere at the temperature of 80 ℃, and stirring at the rotating speed of 40rpm for 80min to obtain modified starch B;
h3, mixing the modified starch B, the coupling agent, the inorganic modifier and the organic modifier according to the mass ratio of 50:22:15:17, and then mixing for 20min under the conditions that the temperature is 80 ℃, the pressure is 12MPa and the rotating speed is 50rpm to obtain a flame retardant;
h4 crushing the flame retardant body, sieving the crushed flame retardant body by a sieve of 500 meshes, and drying the crushed flame retardant body for 15 hours at the temperature of 75 ℃ and under the air pressure of 5kPa to obtain the flame retardant.
The coupling agent is a mixture of trifluoropropylmethyl cyclotrisiloxane and dimethyl diacetoxysilane in a mass ratio of 2: 1.
The inorganic modifier is a mixture of aluminum silicate and zinc borate according to the mass ratio of 2: 3.
The organic modifier is a mixture of polycarbonate resin and polyoxyethylene sorbitan trioleate in a mass ratio of 1: 1.
Example 9
Substantially the same as in example 2, except that,
the preparation method of the flame retardant comprises the following steps:
h1 placing the mixed starch in sulfur dioxide atmosphere at 80 ℃, stirring at 40rpm for 80min, and simultaneously performing ultraviolet irradiation treatment with the wavelength of 203nm and the power of 130W to obtain modified starch B; the mixed starch is a mixture of corn starch and cassava starch in a mass ratio of 2: 1;
h2, mixing the modified starch B, the coupling agent, the inorganic modifier and the organic modifier according to the mass ratio of 50:22:15:17, and then mixing for 20min under the conditions that the temperature is 80 ℃, the pressure is 12MPa and the rotating speed is 50rpm to obtain a flame retardant;
h4 crushing the flame retardant body, sieving the crushed flame retardant body by a sieve of 500 meshes, and drying the crushed flame retardant body for 15 hours at the temperature of 75 ℃ and under the air pressure of 5kPa to obtain the flame retardant.
The coupling agent is a mixture of trifluoropropylmethyl cyclotrisiloxane and dimethyl diacetoxysilane in a mass ratio of 2: 1.
The inorganic modifier is a mixture of aluminum silicate and zinc borate according to the mass ratio of 2: 3.
The organic modifier is a mixture of polycarbonate resin and polyoxyethylene sorbitan trioleate in a mass ratio of 1: 1.
Test example 4
And (3) testing the flame retardance: the flame retardancy of the vulcanized silicone rubber obtained in each example of the present invention was tested according to the vertical burning method of method B in GB/T10707-. The test piece had a length of 130mm, a width of 13mm and a thickness of 3 mm. Five samples were taken for each of the vulcanized silicone rubbers obtained in the examples, and the test results were averaged. The test results are shown in table 4.
TABLE 4 vertical burning behavior of vulcanized Silicone rubber
Figure BDA0003194045390000191
Figure BDA0003194045390000201
Test example 5
Tensile strength: the tensile strength of the vulcanized silicone rubber obtained in each example of the present invention was tested according to GB/T528-2009 determination of tensile stress strain Properties of vulcanized rubber or thermoplastic rubber. The sample type is 1 type; the moving speed of the clamper is 500 mm/min; for each of the vulcanized silicone rubbers obtained in the examples, 4 specimens were taken and the test results were averaged. The test results are shown in table 5.
TABLE 5 tensile Strength of the vulcanized Silicone rubber
Tensile Strength (MPa)
Example 2 4.4
Example 3 4.1
Example 4 3.9
Example 5 3.4
Example 6 3.6
Example 7 4.0
Example 8 4.1
Example 9 4.3
According to the invention, methyltrimethoxysilane is used as a modifier to modify alpha, omega-dihydroxy polysiloxane, so that the polyalkoxysilane terminated polydimethylsiloxane with good compatibility with active nano calcium carbonate and active heavy calcium carbonate is obtained, and the polyalkoxysilane terminated polydimethylsiloxane is used as the component A and is mixed with the component B to obtain the high-efficiency bonding bi-component room temperature vulcanized silicone rubber with high hardness, good bonding effect and high bonding strength. The number of hydrogen bond acceptors and the number of rotatable chemical bonds in the dibutyl phosphate can promote the modification of the alpha, omega-dihydroxy polysiloxane by the methyltrimethoxysilane to a sufficient degree; the reaction activity of the nitrogen-hydrogen bond in the triethylamine is beneficial to the end-capping reaction of the alpha, omega-dihydroxy polysiloxane, so that the sufficient degree and the reaction rate of the end-capping reaction can be further enhanced when the dibutyl phosphate and the triethylamine are used as synergists for the silane end-capping treatment of the alpha, omega-dihydroxy polysiloxane, and the efficient bonding bi-component room-temperature vulcanized silicone rubber with high hardness, good bonding effect and high bonding strength can be obtained subsequently. The invention prepares the modified silane with good wettability with the active nano calcium carbonate and the active heavy calcium carbonate by reacting N- (2-aminoethyl) -3-aminopropyl trimethoxy silane and 3-methacryloxypropyl methyl dimethoxy silane in advance, improves the service reliability of the poly-alkoxy silane end-capped polydimethylsiloxane, and prepares the component A together with bis (trimethoxysilylpropyl) amine and di-N-butyl ethyl diacetylacetate tin to obtain the high-efficiency bonding bi-component room temperature vulcanized silicone rubber with high hardness, good bonding effect and high bonding strength.
The invention firstly reacts N- (2-aminoethyl) -3-aminopropyltrimethoxysilane and 3-methacryloxypropylmethyldimethoxysilane to prepare the modified silane with good wettability with the active nano calcium carbonate, the active heavy calcium carbonate and the anhydrous calcium chloride, and the component A is prepared together with bis (trimethoxysilylpropyl) amine and di-N-butyl diacetyl ethyl acetate tin, so that the high-efficiency bonding bi-component room temperature vulcanized silicone rubber with high hardness, good bonding effect and high bonding strength is obtained.
Corn starch and tapioca starch have complex spatial three-dimensional structures and abundant amylopectin groups, wherein tapioca starch can be used as a "binder" between an inorganic filler and an organic matrix due to its unique peak viscosity. According to the invention, after the spatial structures of corn starch and cassava starch are broken through a steam explosion mode, the corn starch and the cassava starch are recombined in a reducing atmosphere of sulfur dioxide, and modified starch with higher wettability is obtained under the promotion action of ultraviolet specific wavelength energy, wherein the modified starch can effectively and durably combine inorganic flame retardants, namely aluminum silicate and zinc borate, with an organic silicon sulfide rubber system taking alkoxy silane terminated polydimethylsiloxane as a main body, so that the silicon sulfide rubber with extremely high service reliability and flame retardant capability is obtained.
The fluorine-silicon atom ratio in the trifluoropropylmethyl cyclotrisiloxane and the relative orientation of the silicon atom in the dimethyldiacetoxysilane and an ester bond can ensure that the aluminum silicate and the zinc borate can be firmly locked in the space network structure of the modified starch due to electric negative attraction, improve the service reliability, and can also cooperate with an organic modifier to further enhance the mechanical toughness of the space network structure of the modified starch, thereby improving the macroscopic mechanical properties of the vulcanized silicone rubber including tensile strength.
The polycarbonate resin has good flame retardance and oxidation resistance, high mechanical strength, high elastic coefficient and high impact strength, and can effectively enhance the mechanical strength of a space network structure of the modified starch when being compounded with polyoxyethylene sorbitan trioleate to be used as an organic modifier for preparing the flame retardant, and meanwhile, the polycarbonate resin has good compatibility with the inorganic modifier, so that good flame retardant property is obtained.

Claims (10)

1. The high-efficiency bonding bi-component room temperature vulcanized silicone rubber is characterized in that: consists of a component A and a component B;
the component A comprises the following raw materials: the composite material comprises polyalkoxysilane terminated polydimethylsiloxane, filler, a stabilizer, a tackifier and a catalyst;
the component B comprises the following raw materials in parts by weight: hydroxyl/methyl terminated polydimethylsiloxane, filler, cross-linking agent and deep-layer curing accelerator.
2. A highly efficient adhesive two-component room temperature vulcanizing silicone rubber as defined in claim 1, wherein:
the component A comprises the following raw materials in parts by weight: 95-105 parts of poly-alkoxy silane end-capped polydimethylsiloxane, 70-120 parts of filler, 0.5-3 parts of stabilizer, 3-6 parts of tackifier and 0.1-1 part of catalyst;
the component B comprises the following raw materials in parts by weight: 95-105 parts of hydroxyl/methyl terminated polydimethylsiloxane, 70-120 parts of filler, 3-10 parts of cross-linking agent and 3-15 parts of deep curing accelerator.
3. The high-adhesion two-component room temperature vulcanizing silicone rubber as claimed in claim 2, wherein:
the polyalkoxy silane end-capped polydimethylsiloxane is a modified polymer which is prepared by taking hydroxyl-terminated polydimethylsiloxane as a basic adhesive and performing end-capping modification and combination on the hydroxyl-terminated polydimethylsiloxane by using one or a mixture of more of tetramethoxy silane, tetraethoxy silane, methyltrimethoxy silane, methyltriethoxy silane, methyldimethoxy silane and methyldiethoxy silane as a modifier.
4. The high-adhesion two-component room temperature vulcanizing silicone rubber as claimed in claim 2, wherein:
the stabilizer is one or a mixture of hexamethyldisilazane, hexamethylcyclotrisilazane, divinyl tetramethyl disilazane, p-toluenesulfonyl isocyanate, isocyanatopropyl triethoxysilane, a molecular sieve and anhydrous calcium chloride;
the filler is one or a mixture of more of active nano calcium carbonate, active heavy calcium carbonate, light calcium carbonate, heavy calcium carbonate, fumed silica, precipitated silica, surface-treated hydrophobic silica and active silica micropowder.
5. The high-adhesion two-component room temperature vulcanizing silicone rubber as claimed in claim 2, wherein:
the tackifier can be one or more of gamma-aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, bis (trimethoxysilylpropyl) amine, bis (triethoxysilylpropyl) amine or hydrolyzed oligomers thereof; or epoxy silane or acyl silane, such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3- (methacryloyloxy) propyltrimethoxysilane, 3- (methacryloyloxy) propyltriethoxysilane, 3- (acryloyloxy) propyltrimethoxysilane, or hydrolyzed oligomer thereof; the silane coupling agent can also be prepared by compounding and modifying the silane coupling agent.
6. The high-adhesion two-component room temperature vulcanizing silicone rubber as claimed in claim 2, wherein:
the catalyst is one or more of dibutyl tin dilaurate, dibutyl tin diacetate, dioctyl tin dilaurate, stannous octoate, dimethyl tin dineodecanoate, triisobutyl tin octanoate, methyl tin mercaptide, butyl tin mercaptide, octyl tin mercaptide, monobutyl tin maleate, mono octyl butyl tin maleate, octyl tin maleate, di-neodecanoate tin dilaurate and dodecyl tin mercaptide; or one or more of chelate compounds of organotin such as di-n-butyl tin bis (ethylacetoacetate), di-n-butyl tin bis (acetylacetonate) and the like.
7. The high-adhesion two-component room temperature vulcanizing silicone rubber as claimed in claim 2, wherein:
the hydroxyl/methyl-terminated polydimethylsiloxane is one or a mixture of alpha, omega-dihydroxyl polysiloxane, single-end alkoxy modified polydimethylsiloxane and dimethyl polysiloxane.
8. The high-adhesion two-component room temperature vulcanizing silicone rubber as claimed in claim 2, wherein:
the cross-linking agent is one or a mixture of more of polyethyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane or hydrolyzed oligomer thereof, polymethyltriethoxysilane, tetraethoxysilane or oligomer thereof, propyl orthosilicate or oligomer thereof, tetramethoxysilane or oligomer thereof.
9. The high-adhesion two-component room temperature vulcanizing silicone rubber as claimed in claim 2, wherein: the deep curing accelerator is a mixture of water, hydroxyl silicone oil, precipitated white carbon black and acid-base salt.
10. The process for preparing the high-efficiency adhesive two-component room temperature vulcanizing silicone rubber as claimed in any one of claims 1 to 9, wherein: mixing the component A and the component B to obtain the composition.
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CN118146637A (en) * 2023-09-20 2024-06-07 山东元开电气有限公司 Wide-temperature-range salt-spray-corrosion-resistant silicon rubber insulating sheath and preparation method thereof

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