A one-component silane-modified polyether sealant, its preparation method and application

Abstract

This invention provides a one-component silane-modified polyether sealant, its preparation method, and its application. The raw materials for preparing the one-component silane-modified polyether sealant include the following components by weight: 280-300 parts of silane-modified polyether resin, 100-130 parts of environmentally friendly plasticizer, 500-550 parts of nano-calcium carbonate, 10-30 parts of fumed silica, 3-5 parts of ultraviolet absorber, 3-5 parts of light stabilizer, 3-5 parts of antioxidant, 15-20 parts of dehydrating agent, 15-25 parts of silane coupling agent, and 3-5 parts of catalyst. The one-component silane-modified polyether sealant provided by this invention exhibits excellent adhesion to metal substrates, high hardness, high tensile strength, high elongation at break, and high shear strength, and has a moderate viscosity, which is beneficial for conventional construction processes, resulting in excellent overall performance.

Description

Technical Field

[0001] This invention belongs to the field of polyether sealant technology, specifically relating to a single-component silane-modified polyether sealant, its preparation method, and its application. Background Technology

[0002] Silane-modified polyether sealant is a new type of sealant, mainly composed of a base polymer, silane-modified polyether polymer, fillers, catalysts, and additives. Due to its excellent adhesion, good paintability, and stain resistance, it combines the advantages of both polyurethane and silicone sealants, and is widely used in various industrial fields such as construction, automotive, and electronics.

[0003] CN112980375A discloses a one-component silane-modified polyether sealant and its preparation method. The preparation of the one-component silane-modified polyether sealant includes the following components in parts by weight: 10-20 parts of silane-modified polyether resin A, 5-15 parts of silane-modified polyether resin B, 5-12 parts of plasticizer, 21-53 parts of reinforcing filler, 0.1-0.8 parts of antioxidant, 1-2 parts of dehydrating agent, 5-10 parts of coupling agent, and 0.1-0.5 parts of catalyst. This technical solution uses resins with different activities and novel aliphatic alkyl esters to work in combination with the remaining components, accelerating curing and crosslinking, improving the sealant's cohesiveness, tensile strength, and adhesive strength, but its hardness and tensile strength are relatively low.

[0004] CN105176470A discloses a silane-terminated polyether sealant and its preparation method. The silane-terminated polyether sealant, by weight percentage of the total raw materials, comprises the following: 30-50 parts silane-terminated polyether, 5-20 parts plasticizer, 25-45 parts reinforcing filler, 1-10 parts pigment, 1-2 parts ultraviolet absorber, 1-2 parts light stabilizer, 1-3 parts crosslinking agent, 1-3 parts tackifier, and 0.5-2 parts catalyst; the crosslinking agent is polyethyl silicate Si40. The silane-terminated polyether sealant provided by this technical solution exhibits high adhesion to the substrate after curing, and the adhesion does not significantly decrease after water immersion, but the adhesive strength is low and needs further improvement.

[0005] Therefore, there is a need to develop a single-component silane-modified polyether sealant with high hardness, good adhesion, and excellent overall performance. Summary of the Invention

[0006] To address the shortcomings of existing technologies, the present invention aims to provide a single-component silane-modified polyether sealant, its preparation method, and its application. The single-component silane-modified polyether sealant has a fast curing speed, short surface drying time, excellent adhesion to metal substrates, high tensile strength, shear strength, and elongation at break, and moderate viscosity, which is beneficial for conventional construction processes, resulting in excellent overall performance.

[0007] To achieve this objective, the present invention adopts the following technical solution:

[0008] In a first aspect, the present invention provides a one-component silane-modified polyether sealant, wherein the raw materials for preparing the one-component silane-modified polyether sealant include the following components by weight: 280-300 parts of silane-modified polyether resin (e.g., 282 parts, 284 parts, 286 parts, 288 parts, 290 parts, 292 parts, 294 parts, 296 parts, or 298 parts, etc.), and 100-130 parts of environmentally friendly plasticizer (e.g., 103 parts, 106 parts, 109 parts, etc.). 112 parts, 115 parts, 118 parts, 121 parts, 124 parts, or 127 parts, etc.), 500-550 parts of nano-calcium carbonate (e.g., 505 parts, 510 parts, 515 parts, 520 parts, 525 parts, 530 parts, 535 parts, 540 parts, or 545 parts, etc.), 10-30 parts of fumed silica (e.g., 12 parts, 14 parts, 16 parts, 18 parts, 20 parts, 22 parts, 24 parts, 26 parts, or 28 parts, etc.), 3-5 parts of ultraviolet absorber ( For example, 3.2 parts, 3.4 parts, 3.6 parts, 3.8 parts, 4.2 parts, 4.4 parts, 4.6 parts, or 4.8 parts, etc.); 3-5 parts of light stabilizer (for example, 3.2 parts, 3.4 parts, 3.6 parts, 3.8 parts, 4.2 parts, 4.4 parts, 4.6 parts, or 4.8 parts, etc.); 3-5 parts of antioxidant (for example, 3.2 parts, 3.4 parts, 3.6 parts, 3.8 parts, 4.2 parts, 4.4 parts, 4.6 parts, or 4.8 parts, etc.); 15-20 parts of water remover (…). For example, 15.5 parts, 16 parts, 16.5 parts, 17 parts, 17.5 parts, 18 parts, 18.5 parts, 19 parts or 19.5 parts, etc.), 15 to 25 parts of silane coupling agent (for example, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts, 21 parts, 22 parts, 23 parts or 24 parts, etc.), and 3 to 5 parts of catalyst (for example, 3.2 parts, 3.4 parts, 3.6 parts, 3.8 parts, 4.0 parts, 4.2 parts, 4.4 parts, 4.6 parts or 4.8 parts, etc.).

[0009] In this invention, nano-calcium carbonate is used as a reinforcing filler, and fumed silica is used as an auxiliary reinforcing filler. The two work synergistically to provide reinforcement. A reasonable ratio of silane coupling agent, silane-modified polyether resin, ultraviolet absorber, light stabilizer, antioxidant, dehydrating agent, and catalyst are also incorporated. Through the combined effect of these components, a single-component silane-modified polyether sealant is prepared with fast curing speed, short surface drying time, excellent adhesion to metal substrates, high tensile strength, shear strength, and elongation at break, and moderate viscosity, which is beneficial for conventional construction processes. Its overall performance is excellent. This single-component silane-modified polyether sealant solves the problems of low mechanical properties, low shear strength, low hardness, and poor adhesion of traditional silane-modified polyether sealants. It exhibits excellent adhesion to stainless steel and aluminum substrates under primerless application conditions and has excellent weather resistance, aging resistance, and excellent tensile and compressive recovery. The single-component silane-modified polyether sealant is solvent-free, isocyanate-free, and PVC-free. The product is non-toxic, odorless, pollution-free, and environmentally friendly. It cures upon contact with moisture in the air. The raw material composition is relatively simple, and the raw material cost is relatively moderate, enabling large-scale production.

[0010] Preferably, the silane-modified polyether resin is a dimethoxysilane-terminated polyether resin.

[0011] Preferably, the viscosity of the silane-modified polyether resin at 25°C is 10,000 to 80,000 mPa·s, such as 20,000 mPa·s, 30,000 mPa·s, 40,000 mPa·s, 50,000 mPa·s, 60,000 mPa·s, or 70,000 mPa·s.

[0012] Preferably, the modified silane polyether resin includes any one or a combination of at least two of Zhongyuan Chemical SAX400, Zhongyuan Chemical SAX750, Zhongyuan Chemical S303H, Zhongyuan Chemical S203H, Zhejiang Huangma Technology HMS-1063, Zhejiang Huangma Technology HMS-1107, Zhejiang Huangma Technology HMS-1167, or Zhejiang Huangma Technology HMS-1267.

[0013] Preferably, the environmentally friendly plasticizer includes any one or a combination of at least two of polyether polyols, di(2-propylheptyl) phthalate (DIDP), or diisononyl phthalate (DINP).

[0014] Preferably, the polyether polyol is polyether polyol C2020.

[0015] Preferably, the nano-calcium carbonate is active nano-calcium carbonate.

[0016] Preferably, the whiteness of the active nano-calcium carbonate is 95% to 99%, such as 95.5%, 96%, 96.5%, 97%, 97.5%, 98%, 98.5%, 99%, or 99.5%.

[0017] Preferably, the specific surface area of ​​the active nano-calcium carbonate is 15-20 m². 2 / g, for example, 15.5m 2 / g, 16m 2 / g, 16.5m 2 / g、17m 2 / g, 17.5m 2 / g、18m 2 / g, 18.5m 2 / g、19m 2 / g or 19.5m 2 / g etc.

[0018] Preferably, the oil absorption value of the active nano-calcium carbonate is 20-30 mL / 100g, such as 21 mL / 100g, 22 mL / 100g, 23 mL / 100g, 24 mL / 100g, 25 mL / 100g, 26 mL / 100g, 27 mL / 100g, 28 mL / 100g, or 29 mL / 100g.

[0019] In this invention, the active nano-calcium carbonate can be well and uniformly dispersed with environmentally friendly plasticizers and other raw materials, improving the strength and specific gravity of the single-component silane-modified polyether sealant. The specific surface area of ​​the active nano-calcium carbonate is preferably 15-20 m² / g. 2 / g, the small particle size of active nano-calcium carbonate results in better dispersibility, leading to a more uniform and delicate single-component silane-modified polyether sealant after dispersion and mixing. If the specific surface area is too small, the active nano-calcium carbonate particles will be large and have poor dispersibility, easily forming coarse particles in the single-component silane-modified polyether sealant. However, if the specific surface area is too high, the viscosity of the colloid will be high, the extrudability will be poor, and the elongation at break will be low.

[0020] Preferably, the active nano calcium carbonate includes any one or a combination of at least two of the following: Japanese Shiraishi CCR, Japanese Takegen SP, Guangxi Huana P150, OMY 2T, OMY 120, or OMY 160.

[0021] Preferably, the specific surface area of ​​the fumed silica is 140–200 m² / g. 2 / g, for example, 145m 2 / g, 150m 2 / g、155m 2 / g、160m 2 / g、165m2 / g、170m 2 / g、175m 2 / g、180m 2 / g、185m 2 / g、190m 2 / g or 195m 2 / g etc.

[0022] In this invention, the increased specific surface area of ​​the fumed silica can improve the tensile strength and elongation at break of the single-component silane-modified polyether sealant, resulting in a better reinforcing effect. However, the increased specific surface area also increases the viscosity of the single-component silane-modified polyether sealant, which is not conducive to construction.

[0023] In this invention, the fumed silica is a high specific surface area powdered fumed silica.

[0024] Preferably, the fumed silica includes any one or a combination of at least two of Cabot LM-150, Tokuyama QS-10, Tokuyama QS-102, Tokuyama QS-10LS, or Evonik R-974.

[0025] Preferably, the ultraviolet absorber comprises any one or a combination of at least two of 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-pentylphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, or 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole.

[0026] Preferably, the light stabilizer comprises any one or a combination of at least two of the following: bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, bis(1-octoxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, poly(1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidinyl) succinate, or poly{[6-[(1,1,3,3-tetramethylbutyl)amino]]-1,3,5-triazine-2,4-[(2,2,6,6-tetramethyl-piperidinyl)imino]-1,6-hexamethylene[(2,2,6,6-tetramethyl-4-piperidinyl)imino]}.

[0027] Preferably, the antioxidant comprises any one or a combination of at least two of the following: glycol bis-3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate, pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, diethylene thiobis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], or tris[2,4-di-tert-butylphenyl]phosphite.

[0028] Preferably, the dehydrating agent comprises vinyltrimethoxysilane and / or vinyltriethoxysilane.

[0029] Preferably, the silane coupling agent comprises any one or a combination of at least two of the following: γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, oligomeric bisaminosilane, multifunctional aminosilane oligomers, triaminotrimethoxysilane, or bis(trimethoxysilylpropyl)amine.

[0030] Preferably, the catalyst comprises any one or a combination of at least two of the reaction products of bis(acetylacetonate)dibutyltin, dibutyltin dilaurate, dibutylbis(2,4-glutarate-O,O')-(OC-6-11)-tin, or tetraethyl silicate with bis(acetoxy)dibutyltin alkyl.

[0031] Preferably, the raw materials for preparing the single-component silane-modified polyether sealant also include carbon black;

[0032] Preferably, the carbon black includes any one or a combination of at least two of the following: HZ6004 series carbon black, HZ630 series carbon black, HZ7100 series carbon black, or Euliron H30 carbon black.

[0033] Preferably, the carbon black content in the raw materials for preparing the single-component silane-modified polyether sealant is 0 to 20 parts by weight, such as 2 parts, 4 parts, 6 parts, 8 parts, 10 parts, 12 parts, 14 parts, 16 parts, or 18 parts.

[0034] Preferably, the raw materials for preparing the single-component silane-modified polyether sealant also include pigment colorants.

[0035] Preferably, the pigment colorant in the raw materials for preparing the single-component silane-modified polyether sealant is 10-30 parts by weight, such as 12 parts, 14 parts, 16 parts, 18 parts, 20 parts, 22 parts, 24 parts, 26 parts, or 28 parts, etc.

[0036] In this invention, the single-component silane-modified polyether sealant can be prepared into different colors such as black, white, and gray by adding pigment colorants, thus expanding its application range.

[0037] In a second aspect, the present invention provides a method for preparing a single-component silane-modified polyether sealant as described in the first aspect, wherein the single-component silane-modified polyether sealant comprises the following steps: mixing silane-modified polyether resin, environmentally friendly plasticizer, nano-calcium carbonate, fumed silica, ultraviolet absorber, light stabilizer, antioxidant, dehydrating agent, silane coupling agent and catalyst to obtain the single-component silane-modified polyether sealant.

[0038] Preferably, the single-component silane-modified polyether sealant specifically includes the following steps:

[0039] (1) Mix silane-modified polyether resin, nano-calcium carbonate, optional carbon black, optional pigment colorant, and fumed silica to obtain a first mixture.

[0040] (2) The first mixture obtained in step (1), the environmentally friendly plasticizer, the ultraviolet absorber, the light stabilizer and the antioxidant are mixed to obtain the second mixture.

[0041] (3) The second mixture obtained in step (2) is mixed with the dehydrating agent to obtain the third mixture.

[0042] (4) The third mixture obtained in step (3) is mixed with the silane coupling agent to obtain the fourth mixture.

[0043] (5) The fourth mixture obtained in step (4) is mixed with the catalyst to obtain the single-component silane-modified polyether sealant.

[0044] Preferably, the mixing in step (1) is carried out under a vacuum of -0.09 to 0.1 MPa (e.g., -0.08 MPa, -0.05 MPa, -0.02 MPa, 0.01 MPa, 0.04 MPa or 0.07 MPa).

[0045] Preferably, the mixing temperature in step (1) is 0 to 50°C, for example, 5°C, 10°C, 15°C, 20°C, 25°C, 30°C, 35°C, 40°C or 45°C.

[0046] Preferably, the mixing in step (1) is a stirring mixing, with a stirring speed of 900-1000 r / min (e.g., 910 r / min, 920 r / min, 930 r / min, 940 r / min, 950 r / min, 960 r / min, 970 r / min, 980 r / min or 990 r / min, etc.) and a stirring time of 30-40 min (e.g., 31 min, 32 min, 33 min, 34 min, 35 min, 36 min, 37 min, 38 min or 39 min, etc.).

[0047] Preferably, the mixing in step (2) includes stirring at 0–50°C (e.g., 5°C, 10°C, 15°C, 20°C, 25°C, 30°C, 35°C, 40°C, or 45°C, etc.) and a rotation speed of 900–1000 r / min (e.g., 910 r / min, 920 r / min, 930 r / min, 940 r / min, 950 r / min, 960 r / min, 970 r / min, 980 r / min, or 990 r / min, etc.) for 5–12 min (e.g., 6 min, 7 min, 8 min, 9 min, 10 min, or 11 min, etc.), and then heating to 110–130°C (e.g., 112°C, 114°C, 116°C, 118°C, 120°C, 122°C, etc.). The mixture is stirred and mixed for 2 to 3 hours (e.g., 2.1h, 2.2h, 2.3h, 2.4h, 2.5h, 2.6h, 2.7h, 2.8h, or 2.9h) at a vacuum of -0.09 to 0.1 MPa (e.g., -0.08 MPa, -0.05 MPa, -0.02 MPa, 0.01 MPa, 0.04 MPa, or 0.07 MPa) and a rotation speed of 150 to 250 r / min (e.g., 160 r / min, 170 r / min, 180 r / min, 190 r / min, 200 r / min, 210 r / min, 220 r / min, 230 r / min, or 240 r / min) at a speed of 150 to 250 r / min (e.g., 160 r / min, 170 r / min, 180 r / min, 190 r / min, 200 r / min, 210 r / min, 220 r / min, 230 r / min, or 240 r / min).

[0048] Preferably, the mixing described in steps (3), (4) and (5) is carried out independently under a vacuum of -0.09 to 0.1 MPa (e.g., -0.08 MPa, -0.05 MPa, -0.02 MPa, 0.01 MPa, 0.04 MPa or 0.07 MPa).

[0049] Preferably, the mixing temperatures in steps (3), (4), and (5) are each independently ≤45°C (e.g., 15°C, 20°C, 25°C, 30°C, or 35°C, etc.).

[0050] Preferably, the mixing in step (3) is a stirring mixing, with a stirring speed of 400-500 r / min (e.g., 410 r / min, 420 r / min, 430 r / min, 440 r / min, 450 r / min, 460 r / min, 470 r / min, 480 r / min or 490 r / min, etc.), and a stirring mixing time of 10-18 min, such as 11 min, 12 min, 13 min, 14 min, 15 min, 16 min or 17 min, etc.

[0051] Preferably, the mixing in step (4) is a stirring mixing, with a stirring speed of 400-500 r / min (e.g., 410 r / min, 420 r / min, 430 r / min, 440 r / min, 450 r / min, 460 r / min, 470 r / min, 480 r / min or 490 r / min, etc.), and a stirring mixing time of 10-18 min, such as 11 min, 12 min, 13 min, 14 min, 15 min, 16 min or 17 min, etc.

[0052] Preferably, the mixing in step (5) is a stirring mixing, with a stirring speed of 400-500 r / min (e.g., 410 r / min, 420 r / min, 430 r / min, 440 r / min, 450 r / min, 460 r / min, 470 r / min, 480 r / min or 490 r / min, etc.), and a stirring mixing time of 5-12 min, e.g., 6 min, 7 min, 8 min, 9 min, 10 min or 11 min, etc.

[0053] Thirdly, the present invention provides an application of the single-component silane-modified polyether sealant as described in the first aspect in the bonding and sealing of joints.

[0054] Compared with the prior art, the present invention has the following beneficial effects:

[0055] This invention uses nano-calcium carbonate as a reinforcing filler and fumed silica as an auxiliary reinforcing filler. The two work synergistically to provide reinforcement. A reasonable ratio of silane coupling agent, silane-modified polyether resin, UV absorber, light stabilizer, antioxidant, dehydrating agent, and catalyst is also incorporated. Through the combined effect of these components, a single-component silane-modified polyether sealant is prepared with fast curing speed, short surface drying time, and excellent adhesion to stainless steel, aluminum, and other metal substrates under primerless application conditions. It exhibits high hardness, high tensile strength, high elongation at break, and high shear strength, with moderate viscosity, facilitating conventional application processes and demonstrating excellent overall performance. The single-component silane-modified polyether sealant exhibits a shear strength of 3.0–4.2 MPa, a tensile strength of 2.7–3.5 MPa, an elongation at break of 330%–430%, a hardness of 50–68 HA, and a viscosity of 225,000–268,000 mPa·s for 304 stainless steel, demonstrating excellent overall performance. This invention solves the problems of low mechanical properties, low shear strength, low elongation at break, low hardness, and poor adhesion of traditional silane-modified polyether sealants. The single-component silane-modified polyether sealant has a moderate viscosity, can be applied using conventional sealant processes, enables primerless bonding, and has a simple application process. It is suitable for bonding and sealing joints in automobile bodies, elevator cars, containers, ships, metal structures, and machinery. It does not bubble under high temperature and humidity conditions and is safe and environmentally friendly. Detailed Implementation

[0056] The technical solution of the present invention will be further illustrated below through specific embodiments. Those skilled in the art should understand that the embodiments described are merely illustrative of the present invention and should not be construed as limiting the invention in any way.

[0057] The following are some of the raw materials used in the examples and comparative examples:

[0058] Activated nano-calcium carbonate: Guangxi Huana P150, whiteness ≥95%, specific surface area 17.5-19.5m² 2 / g, oil absorption value is 27.0±3mL / 100g;

[0059] Active nano calcium carbonate: OMY 160;

[0060] Active nano calcium carbonate: OMY 120;

[0061] Carbon black: HZ6004 series carbon black, manufactured by Tangyin Hangzhou New Materials Co., Ltd.

[0062] Fumed silica: Cabot LM-150, specific surface area 150±15m² 2 / g;

[0063] Fumed silica: Evonik R-974, specific surface area 150-190 m²2 / g, measured 175m 2 / g;

[0064] Fumed silica: Cabot LM-720, specific surface area 100±20m² 2 / g.

[0065] Example 1

[0066] This embodiment provides a one-component silane-modified polyether sealant and its preparation method. The one-component silane-modified polyether sealant comprises the following components by weight: 290 parts of silane-modified polyether resin (Zhongyuan Chemical SAX400), 120 parts of environmentally friendly plasticizer (polyether polyol C2020), 500 parts of activated nano calcium carbonate (Guangxi Huana P150), 20 parts of carbon black (HZ6004 series carbon black), 30 parts of fumed silica (Cabot LM-150), and an ultraviolet absorber. 3 parts of (2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole), 3 parts of light stabilizer (bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate), 4 parts of antioxidant (glycolic bis-3-(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate), 15 parts of dehydrating agent (vinyltrimethoxysilane), 20 parts of silane coupling agent (γ-glycidoxypropyltrimethoxysilane), and 4.5 parts of catalyst (dibutyltin dilaurate).

[0067] The preparation method of the single-component silane-modified polyether sealant is as follows:

[0068] (1) Add silane-modified polyether resin, active nano calcium carbonate, carbon black and fumed silica to a planetary stirred tank in sequence, evacuate, and mix at high speed for 35 min at 25℃ and vacuum degree of -0.09MPa. The stirring speed is 1000r / min. Take a sample and scrape it to check the appearance of the paste. The surface is fine and there are no particles. The first mixture is obtained.

[0069] (2) Add environmentally friendly plasticizer, ultraviolet absorber, light stabilizer and antioxidant to the first mixture obtained in step (1) in sequence. Stir at high speed for 10 min at 25°C with a stirring speed of 1000 r / min. Heat to 120°C and stir at low speed for 2.5 hours under a vacuum of -0.09 MPa with a stirring speed of 200 r / min to obtain the second mixture.

[0070] (3) Cool the second mixture obtained in step (2) to 40°C, purge with nitrogen to reduce pressure, add dehydrating agent, evacuate, and mix at medium speed for 15 minutes at 40°C and vacuum degree of -0.09MPa, with a stirring speed of 500r / min to obtain the third mixture.

[0071] (4) Nitrogen gas is introduced to reduce the pressure. Silane coupling agent is added to the third mixture obtained in step (3). Vacuum is drawn and the mixture is stirred at medium speed for 15 minutes at 40°C and a vacuum degree of -0.09MPa. The stirring speed is 500r / min to obtain the fourth mixture.

[0072] (5) Nitrogen gas is introduced to reduce the pressure. A catalyst is added to the fourth mixture obtained in step (4). Vacuum is drawn and the mixture is stirred at medium speed for 10 minutes at 40°C and a vacuum degree of -0.09MPa. The stirring speed is 500r / min. The resulting paste is uniform, fine, free of particles and gel, and the single-component silane-modified polyether sealant is obtained.

[0073] Example 2

[0074] This embodiment provides a one-component silane-modified polyether sealant and its preparation method. The one-component silane-modified polyether sealant comprises the following components by weight: 285 parts of silane-modified polyether resin (Zhejiang Huangma Technology HMS-1063), 110 parts of environmentally friendly plasticizer (di(2-propylheptyl) phthalate), and active nano-calcium carbonate (OMY). 500 parts of 160), 25 parts of pigment colorant (titanium dioxide R902), 30 parts of fumed silica (Cabot LM-150), 3 parts of ultraviolet absorber (2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole), 3 parts of light stabilizer (bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate), 4 parts of antioxidant (β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate), 15 parts of dehydrating agent (vinyltriethoxysilane), 20 parts of silane coupling agent (γ-glycidyl etheroxypropyltrimethoxysilane), and 4 parts of catalyst (dibutyltin dilaurate).

[0075] The preparation method of the single-component silane-modified polyether sealant is as follows:

[0076] (1) Add silane-modified polyether resin, active nano calcium carbonate, pigment colorant and fumed silica to a planetary stirred tank in sequence, evacuate, and mix at high speed for 40 min at 35℃ and vacuum degree of 0.01MPa. The stirring speed is 900r / min. Take a sample and scrape it to check the appearance of the paste. The surface is fine and there are no particles. The first mixture is obtained.

[0077] (2) Add environmentally friendly plasticizer, ultraviolet absorber, light stabilizer and antioxidant to the first mixture obtained in step (1) in sequence. Stir at high speed for 10 min at 35°C with a stirring speed of 900 r / min. Heat to 120°C and stir at low speed for 2 hours under a vacuum of 0.01 MPa with a stirring speed of 250 r / min to obtain the second mixture.

[0078] (3) Cool the second mixture obtained in step (2) to 35°C, purge with nitrogen to reduce pressure, add dehydrating agent, evacuate, and mix at medium speed for 15 minutes at 35°C and vacuum degree of 0.01MPa, with a stirring speed of 400r / min to obtain the third mixture.

[0079] (4) Nitrogen gas is introduced to reduce the pressure. Silane coupling agent is added to the third mixture obtained in step (3). Vacuum is drawn and the mixture is stirred at medium speed for 15 minutes at 35°C and a vacuum degree of 0.01MPa. The stirring speed is 450r / min to obtain the fourth mixture.

[0080] (5) Nitrogen gas is introduced to reduce the pressure. A catalyst is added to the fourth mixture obtained in step (4). Vacuum is drawn and the mixture is stirred at medium speed for 10 minutes at 35°C and a vacuum degree of 0.01MPa. The stirring speed is 450r / min. The resulting paste is uniform, fine, free of particles and gel, and the single-component silane-modified polyether sealant is obtained.

[0081] Example 3

[0082] This embodiment provides a one-component silane-modified polyether sealant and its preparation method. The one-component silane-modified polyether sealant comprises the following components by weight: 300 parts of silane-modified polyether resin (Zhejiang Huangma Technology HMS-1167), 100 parts of environmentally friendly plasticizer (diisononyl phthalate), 500 parts of activated nano-calcium carbonate (OMY120), 30 parts of fumed silica (Cabot LM-150), and 2- 3 parts of (2'-hydroxy-3',5'-di-tert-pentylphenyl)benzotriazole, 3 parts of light stabilizer (bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate), 4 parts of antioxidant (thiodiethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]), 15 parts of dehydrating agent (vinyltriethoxysilane), 20 parts of silane coupling agent (γ-glycidyl etheroxypropyltrimethoxysilane), and 4.5 parts of catalyst (dibutyltin dilaurate).

[0083] The preparation method of the single-component silane-modified polyether sealant is as follows:

[0084] (1) Add silane-modified polyether resin, active nano calcium carbonate and fumed silica sequentially to a planetary stirred tank, evacuate the vacuum, and mix at high speed for 35 min at 30℃ and vacuum degree of -0.09MPa. The stirring speed is 1000r / min. Take a sample and scrape it to check the appearance of the paste. The surface is fine and there are no particles. The first mixture is obtained.

[0085] (2) Add environmentally friendly plasticizer, ultraviolet absorber, light stabilizer and antioxidant to the first mixture obtained in step (1) in sequence. Stir at high speed for 10 min at 30°C with a stirring speed of 900 r / min. Heat to 120°C and stir at low speed for 2.5 hours under a vacuum of -0.09 MPa with a stirring speed of 150 r / min to obtain the second mixture.

[0086] (3) Cool the second mixture obtained in step (2) to 40°C, purge with nitrogen to reduce pressure, add dehydrating agent, evacuate, and mix at medium speed for 15 minutes at 40°C and vacuum degree of -0.09MPa, with a stirring speed of 500r / min to obtain the third mixture.

[0087] (4) Nitrogen gas is introduced to reduce the pressure. Silane coupling agent is added to the third mixture obtained in step (3). Vacuum is drawn and the mixture is stirred at medium speed for 15 minutes at 40°C and a vacuum degree of -0.09MPa. The stirring speed is 400r / min to obtain the fourth mixture.

[0088] (5) Nitrogen gas is introduced to reduce the pressure. A catalyst is added to the fourth mixture obtained in step (4). Vacuum is drawn and the mixture is stirred at medium speed for 10 minutes at 40°C and a vacuum degree of -0.09MPa. The stirring speed is 400r / min. The resulting paste is uniform, fine, free of particles and gel, and the single-component silane-modified polyether sealant is obtained.

[0089] Example 4

[0090] This embodiment provides a one-component silane-modified polyether sealant and its preparation method. The difference between this embodiment and Embodiment 1 is that the one-component silane-modified polyether sealant comprises the following components by weight: 290 parts of silane-modified polyether resin (Zhongyuan Chemical SAX400), 120 parts of environmentally friendly plasticizer (polyether polyol C2020), 500 parts of active nano-calcium carbonate (Guangxi Huana P150), 20 parts of carbon black (Eulion H30 carbon black), 30 parts of fumed silica (Evonik R-974), and ultraviolet absorber (…). The following ingredients were used: 5 parts of 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 5 parts of light stabilizer (bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, 3 parts of antioxidant (glycolic bis-3-(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate), 20 parts of dehydrating agent (vinyltrimethoxysilane), 20 parts of silane coupling agent (γ-glycidoxypropyltrimethoxysilane), and 3 parts of catalyst (dibutyltin dilaurate). Other conditions were the same as in Example 1.

[0091] Example 5

[0092] This embodiment provides a single-component silane-modified polyether sealant and its preparation method. The only difference between this embodiment and Example 1 is that the weight of carbon black (HZ6004 series carbon black) is adjusted to 10 parts, while other conditions are the same as in Example 1.

[0093] Example 6

[0094] This embodiment provides a single-component silane-modified polyether sealant and its preparation method. The only difference between this embodiment and Example 1 is that the weight of carbon black (HZ6004 series carbon black) is adjusted to 30 parts, while the other conditions are the same as in Example 1.

[0095] Example 7

[0096] This embodiment provides a single-component silane-modified polyether sealant and its preparation method. The only difference between this embodiment and Example 1 is that the weight of fumed silica (Cabot LM-150) is adjusted to 20 parts, while the other conditions are the same as in Example 1.

[0097] Example 8

[0098] This embodiment provides a single-component silane-modified polyether sealant and its preparation method. The only difference between this embodiment and Example 1 is that the weight of fumed silica (Cabot LM-150) is adjusted to 10 parts, while the other conditions are the same as in Example 1.

[0099] Example 9

[0100] This embodiment provides a single-component silane-modified polyether sealant and its preparation method. The only difference between this embodiment and Example 1 is that the weight of active nano-calcium carbonate (Guangxi Huana P150) is adjusted to 525 parts, while other conditions are the same as in Example 1.

[0101] Example 10

[0102] This embodiment provides a single-component silane-modified polyether sealant and its preparation method. The only difference between this embodiment and Example 1 is that the weight of active nano-calcium carbonate (Guangxi Huana P150) is adjusted to 550 parts, while the other conditions are the same as in Example 1.

[0103] Example 11

[0104] This embodiment provides a single-component silane-modified polyether sealant and its preparation method. The only difference between this embodiment and Example 1 is that the silane coupling agent (γ-glycidoxypropyltrimethoxysilane) is replaced with the same mass of silane coupling agent (γ-aminopropyltrimethoxysilane), while the other conditions are the same as in Example 1.

[0105] Example 12

[0106] This embodiment provides a single-component silane-modified polyether sealant and its preparation method. The only difference between this embodiment and Example 1 is that 15 parts of silane coupling agent (γ-glycidoxypropyltrimethoxysilane) are used, while other conditions are the same as in Example 1.

[0107] Example 13

[0108] This embodiment provides a single-component silane-modified polyether sealant and its preparation method. The only difference between this embodiment and Example 1 is that 25 parts of silane coupling agent (γ-glycidoxypropyltrimethoxysilane) are used, while other conditions are the same as in Example 1.

[0109] Example 14

[0110] This embodiment provides a single-component silane-modified polyether sealant and its preparation method. The only difference between this embodiment and Example 1 is that the fumed silica (Cabot LM-150) is replaced with the same mass of fumed silica (Cabot LM-720), while the other conditions are the same as in Example 1.

[0111] Comparative Example 1

[0112] This comparative example provides a one-component silane-modified polyether sealant and its preparation method. The only difference between this example and Example 1 is that the weight of the environmentally friendly plasticizer (polyether polyol C2020) is adjusted to 90 parts, while the other conditions are the same as in Example 1.

[0113] Comparative Example 2

[0114] This comparative example provides a one-component silane-modified polyether sealant and its preparation method. The only difference between this example and Example 1 is that the weight of the environmentally friendly plasticizer (polyether polyol C2020) is adjusted to 140 parts, while the other conditions are the same as in Example 1.

[0115] Comparative Example 3

[0116] This comparative example provides a single-component silane-modified polyether sealant and its preparation method. The only difference between this example and Example 1 is that the weight of active nano-calcium carbonate (Guangxi Huana P150) is adjusted to 600 parts, while other conditions are the same as in Example 1.

[0117] Comparative Example 4

[0118] This comparative example provides a single-component silane-modified polyether sealant and its preparation method. The only difference between this example and Example 1 is that fumed silica is not added, and the weight of active nano-calcium carbonate (Guangxi Huana P150) is adjusted to 530 parts. Other conditions are the same as in Example 1.

[0119] Comparative Example 5

[0120] This comparative example provides a one-component silane-modified polyether sealant and its preparation method. The only difference between this example and Example 1 is that active nano-calcium carbonate is not added, and the weight of fumed silica (Cabot LM-150) is adjusted to 530 parts. Other conditions are the same as in Example 1.

[0121] The following tests were conducted on the one-component silane-modified polyether sealants provided in Examples 1-14 and Comparative Examples 1-5:

[0122] (1) Surface drying time: Tested in accordance with GB / T 13477.5-2002 "Test methods for building sealing materials - Part 5: Determination of surface drying time";

[0123] (2) Curing speed: Tested according to GB / T 32369-2015 "Determination of curing degree of sealant";

[0124] (3) Viscosity: The viscosity of the single-component silane-modified polyether sealant was determined using a rotational rheometer in accordance with GB / T 2794-1995 "Standard for Determination of Viscosity of Adhesives".

[0125] (4) Hardness: The single-component silane-modified polyether sealant was cured for 168 hours at a temperature of 23℃ and a humidity of 50%, and then tested according to GB / T 531.1-1999 "Rust Pocket Hardness Tester Indentation Hardness Test Method";

[0126] (5) Density: The single-component silane-modified polyether sealant was cured at 23°C and 50% humidity for 168 hours and tested according to GB / T 533-2008 "Determination of density of vulcanized rubber or thermoplastic rubber".

[0127] (6) Adhesion without primer: According to GB / T 13477.18-2002 "Test methods for building sealing materials - Part 18: Determination of peel adhesion", the sealant layer formed by curing the single-component silane modified polyether sealant is cut and peeled from the test substrate with a blade. If the sealant adheres firmly to the test substrate, the bonding interface does not fall off and the cohesive failure is considered excellent.

[0128] (7) Tensile strength and elongation at break: The single-component silane-modified polyether sealant was cured at 23°C and 50% humidity for 168h and tested using type 2 dumbbell plates in accordance with GB / T 528-2009 "Determination of tensile stress-strain properties of vulcanized rubber or thermoplastic rubber".

[0129] (8) Shear strength: The shear strength of 304 stainless steel and aluminum was tested in accordance with GB / T 7124-2008 "Determination of tensile shear strength of adhesives (rigid material to rigid material)".

[0130] The test results are shown in Tables 1 and 2 below.

[0131] Table 1

[0132]

[0133] Table 2

[0134]

[0135]

[0136] As shown in Tables 1 and 2, the single-component silane-modified polyether sealant provided in Examples 1-14 has a tensile strength of 2.7–3.5 MPa, a shear strength of 3.0–4.2 MPa for 304 stainless steel, a shear plate test failure type of ≥90% cohesive failure, an elongation at break of 330%–430%, and a hardness of 50–68 HA. It exhibits excellent adhesion performance to both stainless steel and aluminum substrates without a primer.

[0137] Considering the overall product composition, raw material costs, cost control, manufacturing process requirements, and mechanical performance requirements for application scenarios, the single-component silane-modified polyether sealant prepared in Example 1 exhibits the best comprehensive performance. It has a surface drying time of 15 minutes, a hardness as high as 64HA, a tensile strength of 3.5MPa, an elongation at break of 365%, a shear strength of 3.9MPa against 304 stainless steel substrate, and a viscosity of 254000mpa·s. The viscosity is moderate, and the application is smooth.

[0138] A comparison of Examples 1, 5, and 6 shows that as the weight fraction of carbon black increases, the tensile strength and shear strength of the prepared single-component silane-modified polyether sealant increase, but the viscosity also increases and the elongation at break decreases.

[0139] A comparison of Examples 1, 12, and 13 shows that as the weight fraction of the silane coupling agent increases, the tensile strength and shear strength of the prepared single-component silane-modified polyether sealant increase, but the viscosity also increases and the elongation at break decreases.

[0140] Compared with Example 1, if the weight percentage of the environmentally friendly plasticizer is too low (Comparative Example 1), the viscosity of the prepared one-component silane-modified polyether sealant is too high, and the application is not smooth; if the weight percentage of the environmentally friendly plasticizer is too high (Comparative Example 2), the tensile strength and shear strength of the prepared one-component silane-modified polyether sealant are low.

[0141] Compared with Example 1, if the weight fraction of active nano-calcium carbonate is too high (Comparative Example 4), the viscosity of the prepared single-component silane-modified polyether sealant is too high, and the application is not smooth.

[0142] Compared to Example 1, the shear strength of the single-component silane-modified polyether sealant prepared without the addition of fumed silica (Comparative Example 5) is lower; the shear strength of the single-component silane-modified polyether sealant prepared without the addition of activated nano-calcium carbonate (Comparative Example 6) is also lower. Therefore, it can be concluded that the single-component silane-modified polyether sealant prepared by combining activated nano-calcium carbonate and fumed silica in this invention exhibits superior performance.

[0143] The applicant declares that this invention illustrates a single-component silane-modified polyether sealant, its preparation method, and its application through the above embodiments. However, this invention is not limited to the above embodiments, meaning that this invention does not necessarily rely on the above embodiments for implementation. Those skilled in the art should understand that any improvements to this invention, equivalent substitutions of raw materials, additions of auxiliary components, and selection of specific methods, etc., all fall within the protection and disclosure scope of this invention.

Claims

1. A one-component silane-modified polyether sealant, characterized in that, The raw materials for preparing the single-component silane-modified polyether sealant include the following components by weight: 280-300 parts of silane-modified polyether resin, 100-130 parts of environmentally friendly plasticizer, 500-550 parts of nano-calcium carbonate, 10-30 parts of fumed silica, 3-5 parts of ultraviolet absorber, 3-5 parts of light stabilizer, 3-5 parts of antioxidant, 15-20 parts of dehydrating agent, 15-25 parts of silane coupling agent, 3-5 parts of catalyst, and 10-20 parts of carbon black; The silane coupling agent is any one or a combination of at least two of γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, triaminotrimethoxysilane, or bis(trimethoxysilylpropyl)amine.

2. The single-component silane-modified polyether sealant according to claim 1, characterized in that, The silane-modified polyether resin is a dimethoxysilane-terminated polyether resin.

3. The single-component silane-modified polyether sealant according to claim 1, characterized in that, The viscosity of the silane-modified polyether resin at 25°C is 10,000~80,000 mPa·s.

4. The single-component silane-modified polyether sealant according to claim 1, characterized in that, The environmentally friendly plasticizer includes any one or a combination of at least two of polyether polyols, di(2-propylheptyl) phthalate or diisononyl phthalate.

5. The single-component silane-modified polyether sealant according to claim 1, characterized in that, The nano-calcium carbonate is active nano-calcium carbonate.

6. The single-component silane-modified polyether sealant according to claim 5, characterized in that, The whiteness of the active nano-calcium carbonate is 95%~99%.

7. The single-component silane-modified polyether sealant according to claim 5, characterized in that, The specific surface area of ​​the active nano-calcium carbonate is 15~20 m². 2 / g.

8. The single-component silane-modified polyether sealant according to claim 5, characterized in that, The oil absorption value of the active nano-calcium carbonate is 20~30 mL / 100g.

9. The single-component silane-modified polyether sealant according to claim 1, characterized in that, The specific surface area of ​​the fumed silica is 150~190 m². 2 / g.

10. The single-component silane-modified polyether sealant according to claim 1, characterized in that, The ultraviolet absorber includes any one or a combination of at least two of the following: 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-pentylphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, or 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole.

11. The single-component silane-modified polyether sealant according to claim 1, characterized in that, The light stabilizer comprises any one or a combination of at least two of the following: bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, bis(1-octoxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, poly(1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidinyl) succinate, or poly{[6-[(1,1,3,3-tetramethylbutyl)amino]]-1,3,5-triazine-2,4-[(2,2,6,6-tetramethyl-piperidinyl)imino]-1,6-hexamethylene[(2,2,6,6-tetramethyl-4-piperidinyl)imino]}.

12. The single-component silane-modified polyether sealant according to claim 1, characterized in that, The antioxidants include any one or a combination of at least two of the following: glycol bis-3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate, pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, diethylene thiobis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], or tris[2,4-di-tert-butylphenyl]phosphite.

13. The single-component silane-modified polyether sealant according to claim 1, characterized in that, The dehydrating agent includes vinyltrimethoxysilane and / or vinyltriethoxysilane.

14. The single-component silane-modified polyether sealant according to claim 1, characterized in that, The catalyst comprises any one or a combination of at least two of the reaction products of bis(acetylacetonate)dibutyltin, dibutyltin dilaurate, dibutylbis(2,4-glutarate-O,O')-(OC-6-11)-tin, or tetraethyl silicate with bis(acetoxy)dibutyltin alkyl.

15. The single-component silane-modified polyether sealant according to claim 1, characterized in that, The raw materials for preparing the single-component silane-modified polyether sealant also include pigment colorants.

16. The single-component silane-modified polyether sealant according to claim 15, characterized in that, The pigment colorant in the raw materials for preparing the single-component silane-modified polyether sealant is 10-30 parts by weight.

17. A method for preparing a single-component silane-modified polyether sealant as described in any one of claims 1-16, characterized in that, The single-component silane-modified polyether sealant comprises the following steps: mixing silane-modified polyether resin, environmentally friendly plasticizer, nano-calcium carbonate, fumed silica, carbon black, ultraviolet absorber, light stabilizer, antioxidant, dehydrating agent, silane coupling agent and catalyst to obtain the single-component silane-modified polyether sealant.

18. The preparation method according to claim 17, characterized in that, The single-component silane-modified polyether sealant specifically includes the following steps: (1) Mix silane-modified polyether resin, nano-calcium carbonate, carbon black, optional pigment colorant, and fumed silica to obtain a first mixture; (2) The first mixture obtained in step (1), the environmentally friendly plasticizer, the ultraviolet absorber, the light stabilizer and the antioxidant are mixed to obtain the second mixture; (3) Mix the second mixture obtained in step (2) with the dehydrating agent to obtain the third mixture; (4) Mix the third mixture obtained in step (3) with the silane coupling agent to obtain the fourth mixture; (5) The fourth mixture obtained in step (4) is mixed with the catalyst to obtain the single-component silane-modified polyether sealant.

19. The preparation method according to claim 18, characterized in that, The mixing in step (1) is carried out under a vacuum of -0.09 to 0.1 MPa.

20. The preparation method according to claim 18, characterized in that, The mixing temperature in step (1) is 0~50℃.

21. The preparation method according to claim 18, characterized in that, The mixing in step (1) is a stirring mixture, with a stirring speed of 900~1000 r / min and a stirring time of 30~40 min.

22. The preparation method according to claim 18, characterized in that, The mixing in step (2) includes stirring and mixing at 0~50℃ and 900~1000 r / min for 5~12 min, then heating to 100~120℃ and stirring and mixing at a vacuum of -0.09~0.1MPa and 150~250 r / min for 2~3 h.

23. The preparation method according to claim 18, characterized in that, The mixing described in steps (3), (4) and (5) is carried out independently under a vacuum of -0.09 to 0.1 MPa.

24. The preparation method according to claim 18, characterized in that, The mixing temperatures described in steps (3), (4) and (5) are each ≤45°C.

25. The preparation method according to claim 18, characterized in that, The mixing in step (3) is a stirring mixing, with a stirring speed of 400~500 r / min and a stirring time of 10~18 min.

26. The preparation method according to claim 18, characterized in that, The mixing in step (4) is a stirring mixing, with a stirring speed of 400~500 r / min and a stirring time of 10~18 min.

27. The preparation method according to claim 18, characterized in that, The mixing in step (5) is a stirring mixing, with a stirring speed of 400~500 r / min and a stirring time of 5~12 min.

28. The application of a single-component silane-modified polyether sealant as described in any one of claims 1-16 in the bonding and sealing of joints.

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