CN-116836678-B - Salt spray corrosion resistant double-component silicone structural adhesive and preparation method thereof

CN116836678BCN 116836678 BCN116836678 BCN 116836678BCN-116836678-B

Abstract

The application discloses a salt spray corrosion resistant two-component silicone structural adhesive and a preparation method thereof, wherein the salt spray corrosion resistant two-component silicone structural adhesive comprises an A component and a B component, the A component comprises, by mass, 85-105 parts of 107 base adhesive, 90-120 parts of filler and 10-30 parts of dimethyl silicone oil, the B component comprises, by mass, 4-10 parts of fumed silica, 15-20 parts of carbon black, 25-32 parts of dimethyl silicone oil, 12-40 parts of a cross-linking agent, 20-46 parts of a coupling agent and 0.01-0.1 part of a catalyst, and the coupling agent comprises 9-26 parts of an acrylic acid modified epoxy silane oligomer. The epoxy groups and the alkyl groups contained in the acrylic acid belong to hydrophobic groups, the possibility that the water and chloride molecules contained in the water pass through the silicone structural adhesive is greatly reduced in a salt spray environment, and the salt spray corrosion resistance of the obtained structural adhesive is improved.

Inventors

NI JIANHUA
SHEN XIANG
LIU MING
HE YONGFU
GONG CHAOJIE
SHEN YONGFEI
NI HUANGWEI
LING JIANFENG
CHEN ZHIZHEN
Chen Hangming
WANG SHIZHAN
XU JUN

Assignees

杭州之江有机硅化工有限公司
杭州之江新材料有限公司

Dates

Publication Date: 20260512
Application Date: 20230721

Claims (9)

1. The salt spray corrosion resistant two-component silicone structural adhesive is characterized by comprising a component A and a component B, wherein the component A and the component B comprise the following raw materials in parts by weight: And (3) a component A: 85-105 parts of 107 base adhesive; 90-120 parts of filler; 10-30 parts of dimethyl silicone oil; And the component B comprises the following components: 4-10 parts of fumed silica; 15-20 parts of carbon black; 32-40 parts of dimethyl silicone oil; 12-40 parts of a cross-linking agent; 20-46 parts of a coupling agent; 0.01-0.1 part of a catalyst; The coupling agent comprises 9-26 parts by weight of acrylic acid modified epoxy silane oligomer; The acrylic acid modified epoxy silane oligomer is prepared by reacting an epoxy silane coupling agent oligomer with an acrylic acid compound, and the preparation raw materials comprise (by mass ratio) an epoxy silane coupling agent, a modified crosslinking agent, a catalyst and an acrylic acid compound, wherein the epoxy silane coupling agent, the modified crosslinking agent, the catalyst and the acrylic acid compound are 100 (45-50) (4-7) (10-13).
2. The salt spray corrosion resistant two-component silicone structural adhesive according to claim 1, wherein the epoxy silane coupling agent comprises one or a combination of a plurality of gamma- (2, 3-glycidoxy) propyl trimethoxy silane, 3- (glycidoxy) propyl methyl diethoxy silane and 3- (2, 3-glycidoxy) propyl methyl dimethoxy silane, the modified crosslinking agent comprises one or a combination of a plurality of tetraethoxysilane and tetramethylsilicate, and the catalyst is N, N-dimethylacetamide.
3. The salt spray corrosion resistant two-component silicone structural adhesive according to claim 1, wherein the acrylic compound comprises a mixture of methacrylic acid and propyl acrylic acid in a mass ratio of (0.8-1.2): 1.
4. The salt spray corrosion resistant two-component silicone structural adhesive of claim 1, wherein the acrylic acid modified epoxy silane oligomer is prepared by the following steps: s1, adding an epoxy silane coupling agent, a modified crosslinking agent and a catalyst into a solvent, regulating the pH value of the solution to 3-4, stirring and mixing at 45-60 ℃, adding deionized water, heating to 100-120 ℃, and stirring and reacting for 2-4 hours to obtain a pre-reactant; S2, adjusting the temperature of the pre-reactant to be 35-45 ℃, adding an acrylic acid compound, stirring and reacting for 3-6 hours, and performing reduced pressure distillation to obtain the acrylic acid modified epoxy silane oligomer.
5. The salt spray corrosion resistant two-component silicone structural adhesive according to claim 4, wherein a hydroxy acid compound with the mass of 3-5% of that of an epoxy silane coupling agent is further added in the step S2, and the hydroxy acid compound comprises one or a combination of more than one of alpha-hydroxy acid, beta-hydroxy acid, gamma-hydroxy acid and delta-hydroxy acid.
6. The salt spray corrosion resistant two-component silicone structural adhesive according to claim 1, wherein the coupling agent further comprises one or a combination of several of gamma-aminopropyl triethoxysilane, gamma-aminopropyl trimethoxysilane, N- (2-aminoethyl) -3-aminopropyl methyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyl methyldiethoxysilane, N- (2-aminoethyl) -3-aminopropyl methyldimethoxysilane, N-2-aminoethyl-3-aminopropyl triethoxysilane, triaminoplane N- (piperazinylethyl) -3-aminopropyl methyldimethoxysilane, and triaminoplane 3-diethylenetriaminopropyl methyldimethoxysilane.
7. The salt spray corrosion resistant two-component silicone structural adhesive according to claim 1, wherein the catalyst comprises one or a combination of a plurality of dibutyl tin dilaurate, dibutyl tin diacetate, dioctyl tin dilaurate and stannous octoate.
8. The salt spray corrosion resistant two-component silicone structural adhesive according to claim 1, wherein the cross-linking agent comprises one or a combination of several of methyl orthosilicate, ethyl orthosilicate, methyltrimethoxysilane, dimethyldimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, polyethyl silicate, polymethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, and cyclopentyltriethoxysilane.
9. The preparation method of the salt corrosion resistant two-component silicone structural adhesive according to any one of claims 1 to 8, which is characterized by comprising the following steps: the preparation of the component A comprises the steps of adding 107 base rubber, filler and dimethyl silicone oil into a reaction kettle, and stirring and mixing for 1-2 hours under the vacuum condition of 130-150 ℃ to obtain the component A; And (3) preparing the component B, namely premixing carbon black and dimethyl silicone oil, adding the mixture into a reaction kettle after mixing, stirring and mixing for 10-20 min under the vacuum condition of 140-160 ℃, sequentially adding a cross-linking agent and fumed silica after mixing, stirring and mixing for 20-40 min under the same condition, adding a coupling agent and a catalyst after mixing uniformly, and continuously stirring for 50-70 min to obtain the component B.

Description

Salt spray corrosion resistant double-component silicone structural adhesive and preparation method thereof Technical Field The application relates to the field of silicone structural adhesives, in particular to a salt spray corrosion resistant double-component silicone structural adhesive and a preparation method thereof. Background The two-component silicone structural adhesive has excellent adhesive property, weather resistance and ultraviolet aging resistance, is mainly used for structural adhesive assembly of glass curtain walls, and tightly combines metal components in building curtain walls with curtain wall glass. However, as the performance requirements of the structural adhesive of the building curtain wall are continuously improved, besides the conventional mechanical performance and the adhesive performance, the influence of the environment on the structural adhesive is also more and more concerned, wherein the structural adhesive is damaged by salt fog in the atmosphere in a salt fog environment, especially in a coastal city, so that corrosion is caused to metal components, and the structural adhesive subjected to salt fog resistance treatment has the capability of salt fog corrosion resistance to a certain extent at present, but the tensile retention rate is obviously reduced and cannot meet the standard requirements. Disclosure of Invention The application provides a salt spray corrosion resistant two-component silicone structural adhesive and a preparation method thereof, and aims to obtain the two-component structural adhesive with salt spray corrosion resistance and high performance. The application provides a salt spray corrosion resistant two-component silicone structural adhesive, which comprises an A component and a B component, wherein the A component and the B component comprise the following raw materials in parts by weight: And (3) a component A: 85-105 parts of 107 base adhesive; 90-120 parts of filler; 10-30 parts of dimethyl silicone oil; And the component B comprises the following components: 4-10 parts of fumed silica; 15-20 parts of carbon black; 32-40 parts of dimethyl silicone oil; 12-40 parts of a cross-linking agent; 20-46 parts of a coupling agent; 0.01-0.1 part of a catalyst; The coupling agent comprises 9-26 parts by weight of acrylic acid modified epoxy silane oligomer. Preferably, in the using process, the volume ratio of the component A to the component B is (8-12): 1. Preferably, the average polymerization degree of the acrylic modified epoxy silane oligomer is 5-10. Preferably, the 107-base adhesive is 20000-50000 cst. Preferably, the filler comprises one or a combination of a plurality of nano calcium carbonate, diatomite, kaolin and silica micropowder. More preferably, the filler is nano calcium carbonate, and the particle size of the nano calcium carbonate is 40-100 nm. Preferably, the viscosity of the simethicone is 50-1000 mm 2/s. Through adopting above-mentioned technical scheme, under salt fog environment, moisture and dissolve various chloride molecules in moisture and can diffuse to its inside through the hole in the structural adhesive, the hydrone can promote the swelling of silicone structural adhesive, and the entering of chloride solution makes the inside and outside of structural adhesive produce concentration difference, the hydrone in the air accelerates to the inside infiltration of silicone structural adhesive under the effect of osmotic pressure, the fracture reaction of phenol bond can take place between the molecules of silicone structural adhesive, the hydrone can destroy Van der Waals' force and hydrogen bonding effect between the macromolecular chain in the silicone structural adhesive simultaneously, lead to the interface to debond. The epoxy silane oligomer is added, so that the epoxy silane oligomer can carry out a crosslinking reaction with the silicone bond of the 107-base adhesive, on one hand, the compactness of the silicone structural adhesive can be improved, the erosion of water molecules and chloride molecules can be reduced, and on the other hand, the epoxy group is used as a hydrophobic group, so that the absorption of the silicone structural adhesive to moisture in the use process can be reduced, and the moisture is repelled outside the silicone structural adhesive, so that the silicone structural adhesive is not easy to swell. Meanwhile, the epoxy group is a functional group with strong reactivity, and can react with the functional group on the surface of the matrix material, so that the adhesion between the structural adhesive and the matrix is increased. But the epoxy silane oligomer has insufficient hydrophobicity, so that good waterproof and impervious effects cannot be realized, the hydrophobic alkyl group is introduced through the acrylic acid modified epoxy silane oligomer, the hydrophobic performance of the structural adhesive can be further improved, the possibility that water passes through the silicone structural