Sealing adhesive and preparation method thereof

Abstract

The invention discloses a sealing adhesive, which is characterized by being prepared from the following raw materials in parts by weight: 100 to 150 parts of carboxylated styrene butadiene rubber, 20 to 50 parts of styrene-isoprene-styrene block copolymer, 5 to 20 parts of succinic anhydride, 5 to 15 parts of polyamine compound, 1 to 5 parts of carboxyl activating agent, 20 to 60 parts of tackifying resin, 300 to 500 parts of solvent, 3 to 10 parts of anti-aging agent and 20 to 60 parts of inorganic filler. Therefore, the sealing adhesive provided by the invention has relatively high adhesion strength, mechanical strength and aging resistance.

Description

Technical Field

[0001] The present invention relates to the technical field of chemical engineering, and particularly relates to a carboxylated styrene-butadiene rubber-based sealant adhesive and a preparation method thereof. Background Art

[0002] Sealant adhesives are widely used in multiple industries such as construction, automotive, electronics, aerospace, etc. With the development of industrial technology, the requirements for sealant adhesives are getting higher and higher, requiring them to have excellent adhesive properties, good weather resistance, anti-aging properties, temperature resistance, and good processability. Among numerous sealant adhesives, rubber-based sealant adhesives are widely used in various industrial fields due to their excellent elasticity and chemical resistance. Especially in harsh environments such as high temperature, low temperature, humidity, and ultraviolet radiation, carboxylated styrene-butadiene rubber-based sealant adhesives exhibit adhesion and weather resistance. Styrene-butadiene rubber is a modified rubber material obtained by introducing carboxyl (-COOH) groups into the styrene-butadiene rubber chain, having excellent processing properties, adhesion properties, and heat resistance. Compared with ordinary styrene-butadiene rubber, carboxylated styrene-butadiene rubber can not only improve the adhesion to the substrate, but also improve the chemical resistance and ultraviolet resistance, becoming an ideal substrate for sealant adhesives.

[0003] Although carboxylated styrene-butadiene rubber has broad application prospects in sealant adhesives, the sealant adhesives of the prior art have poor performance in low-temperature environments. Especially under sub-zero temperature conditions, the elasticity and adhesion of the sealant significantly decrease, resulting in a reduced sealing effect. At the same time, under environmental conditions such as long-term ultraviolet radiation, rain erosion, and temperature difference changes, the existing sealant adhesives still have problems such as aging, cracking, and performance degradation. In practical applications, the adhesive properties of some sealant adhesives often cannot meet the application requirements of high strength and high requirements. Therefore, it is urgent to further improve the adhesion strength, mechanical strength, and anti-aging properties of sealant adhesives. Summary of the Invention

[0004] The present invention aims to solve at least one of the technical problems existing in the prior art to a certain extent. For this purpose, the present invention provides a sealant adhesive and a preparation method thereof. The sealant adhesive of the present invention has high adhesion strength, mechanical strength, and anti-aging properties.

[0005] In a first aspect of the present invention, the present invention provides a sealant adhesive, which comprises the following raw materials in parts by weight: 100 - 150 parts of carboxylated styrene-butadiene rubber, 20 - 50 parts of styrene-isoprene-styrene block copolymer, 5 - 20 parts of succinic anhydride, 5 - 15 parts of polyamine compound, and 1 - 5 parts of carboxyl activator.

[0006] In the sealant adhesive of the present invention, after succinic anhydride reacts with a polyamine compound, a functional monomer with carboxyl groups and amino groups is formed. This functional monomer undergoes an amide condensation reaction with the carboxyl groups of carboxylated styrene-butadiene rubber under the action of a carboxyl activator to form a macromolecular crosslinked network structure, effectively improving the adhesion strength and anti-aging property of the sealant adhesive. At the same time, styrene-isoprene-styrene block copolymer is added to form a crosslinked network as macromolecular chains, and together with the macromolecular structure based on carboxylated styrene-butadiene rubber, a double-network interpenetrating crosslinked structure is constructed, increasing the sealing performance and mechanical strength of the sealant adhesive.

[0007] In some embodiments, the polyamine compound includes at least one of ethylenediamine and diethylenetriamine.

[0008] In some embodiments, the carboxyl activator includes at least one of zinc oxide, magnesium oxide, and zinc stearate.

[0009] In some embodiments, the sealant adhesive further includes the following raw materials in parts by weight: 20 - 60 parts of tackifying resin, 300 - 500 parts of solvent, 3 - 10 parts of anti-aging agent, and 20 - 60 parts of inorganic filler.

[0010] In some embodiments, the sealant adhesive satisfies at least one of the following: (1) the tackifying resin includes at least one of octylphenol formaldehyde resin, TKM-modified alkylphenol formaldehyde resin, and silane-modified polyether; (2) the solvent includes toluene; (3) the anti-aging agent includes at least one of dibutyltin dilaurate, dilauryl thiodipropionate, and Tinuvin 326; (4) the inorganic filler includes at least one of aluminum hydroxide, titanium dioxide, silicon dioxide, and talc powder.

[0011] In a second aspect of the present invention, a method for preparing a carboxylated styrene-butadiene rubber-based sealant adhesive is proposed, including the following steps: mixing carboxylated styrene-butadiene rubber, styrene-isoprene-styrene block copolymer, and solvent to obtain a first solution; mixing succinic anhydride, polyamine compound, and solvent to obtain a second solution; mixing the first solution and the second solution, adding a carboxyl activator to obtain a third solution; mixing the third solution, tackifying resin, anti-aging agent, and inorganic filler to obtain the sealant adhesive. According to the preparation method provided by the embodiments of the present invention, the sealant adhesive of the present invention has high adhesion strength, mechanical strength, and anti-aging property.

[0012] In some embodiments, in the step of mixing carboxylated styrene-butadiene rubber, styrene-isoprene-styrene block copolymer, and solvent, the rotation speed during mixing is controlled to be 500 - 1000 r / min, and the temperature is 45 - 75 °C.

[0013] In some embodiments, in the step of mixing succinic anhydride, polyamine compound and solvent, the rotation speed during mixing is controlled to be 500-1000 r / min; and / or, after mixing succinic anhydride, polyamine compound and solvent, heat treatment is further included. The first temperature of the heat treatment is 40-60 °C, and the first reaction time is 20-60 min; the second temperature is 120-160 °C, and the second reaction time is 1-3 h.

[0014] In some embodiments, in the step of mixing the first solution and the second solution, it includes: dropping the second solution into the first solution, and controlling the dropping rate to be 8-12 parts / min; and / or, in the step of adding a carboxyl activator, controlling the reaction temperature to be 55-80 °C, the time to be 1-3 h, and the rotation speed to be 500-1000 r / min.

[0015] In some embodiments, the preparation method comprises the following raw materials in parts by weight: 100-150 parts of carboxylated styrene-butadiene rubber, 20-50 parts of styrene-isoprene-styrene block copolymer, 5-20 parts of succinic anhydride, 5-15 parts of polyamine compound, 20-60 parts of tackifying resin, 1-5 parts of carboxyl activator, 300-500 parts of solvent, 3-10 parts of anti-aging agent, and 20-60 parts of inorganic filler.

[0016] Compared with the prior art, the beneficial technical effects achieved by the present invention are as follows:

[0017] The present invention uses carboxylated styrene-butadiene rubber as a raw material, and by adding styrene-isoprene-styrene block copolymer, succinic anhydride and polyamine compound, an interpenetrating double cross-linked network structure is formed under the action of a carboxyl activator, so that the interaction between macromolecules is enhanced. Then, by adding tackifying resin, anti-aging agent and inorganic filler, the adhesion performance, anti-aging performance and adhesion strength of the sealant are improved. Due to the good adhesion strength and anti-aging performance, the sealant has a wide application in the field of sealing.

[0018] The additional aspects and advantages of the present invention will be partially given in the following description, partially become obvious from the following description, or be understood through the practice of the present invention. Detailed Embodiments

[0019] The embodiments of the present invention are described in detail below. The embodiments described below are exemplary and are only used to explain the present invention, and should not be construed as a limitation to the present invention.

[0020] It should be noted that the terms "first" and "second" are only used for descriptive purposes and should not be construed as indicating or implying relative importance or implicitly specifying the quantity of the indicated technical features. Thus, features defined with "first" and "second" may explicitly or implicitly include one or more of such features. Further, in the description of the present invention, unless otherwise specified, the meaning of "a plurality" is two or more.

[0021] The endpoints and any values in the ranges disclosed herein are not limited to the exact ranges or values, and these ranges or values should be understood to include values close to these ranges or values. For numerical ranges, the endpoint values of each range, between the endpoint values of each range, between the endpoint values of each range and individual point values, and between individual point values can be combined with each other to obtain one or more new numerical ranges, and these numerical ranges should be regarded as specifically disclosed herein.

[0022] In this document, the term "comprising" or "including" is an open-ended expression, that is, it includes the content specified in the present invention, but does not exclude other aspects of the content.

[0023] In the first aspect of the embodiments of the present invention, the present invention provides a sealing adhesive, and the sealing adhesive comprises the following raw materials in parts by weight: 100 - 150 parts of carboxylated styrene-butadiene rubber, 20 - 50 parts of styrene-isoprene-styrene block copolymer, 5 - 20 parts of succinic anhydride, 5 - 15 parts of polyamine compound, and 1 - 5 parts of carboxyl activator.

[0024] In the present invention, carboxylated styrene-butadiene rubber is used as the main raw material and is the basic substance for the reaction. The introduction of carboxyl (-COOH) makes the molecular chain of carboxylated styrene-butadiene rubber polar, and it can form stronger interaction forces with a variety of polar substrates (such as metals, glasses, ceramics, etc.), thereby improving the adhesion performance. Moreover, carboxylated styrene-butadiene rubber also has excellent adhesion performance, mechanical properties, and weather resistance. The inventors found that when its dosage is too high, the elasticity of the sealing adhesive will be too high and the adhesion strength will decrease, while when the dosage is too low, the viscosity of the sealing adhesive will be too high, the elasticity will be insufficient, and the mechanical properties will decrease.

[0025] After the reaction of succinic anhydride and polyamine compound, a functional monomer with carboxyl groups and amino groups is formed. This functional monomer then undergoes an acid amide condensation reaction with the carboxyl groups of carboxylated styrene-butadiene rubber to form a macromolecular cross-linked network structure, effectively improving the adhesion strength and anti-aging property of the sealing adhesive. The inventors found that when the dosage of succinic anhydride and polyamine compound is too high, it will lead to excessive cross-linking degree, resulting in gelation phenomenon, poor fluidity, and easy generation of cavities. When the dosage is too low, the cross-linking degree is low, and the interaction between molecular chains is small, resulting in poor mechanical properties of the sealing adhesive.

[0026] Styrene-isoprene-styrene block copolymer has excellent adhesion performance, good elasticity, aging resistance, and good compatibility with other materials. Adding it to the sealant adhesive can jointly build a double-network interpenetrating cross-linked structure with the carboxylated styrene-butadiene rubber-based macromolecular polymer, further increasing the adhesion strength and aging resistance.

[0027] The main function of the carboxyl activator is to activate the carboxyl groups of the carboxylated styrene-butadiene rubber, so as to further carry out an acid-amine condensation reaction with the functional monomer formed after reacting with succinic anhydride and polyamine compounds to form a macromolecular cross-linked network structure.

[0028] Therefore, the sealant adhesive of the present invention has high adhesion strength, mechanical strength, and aging resistance.

[0029] In some embodiments of the present invention, the polyamine compound includes at least one of ethylenediamine and diethylenetriamine. Thus, the adhesion strength, mechanical strength, and aging resistance of the sealant adhesive of the present invention can be further improved.

[0030] In some embodiments of the present invention, the carboxyl activator includes at least one of zinc oxide, magnesium oxide, and zinc stearate. Thus, the adhesion strength and mechanical strength of the sealant adhesive of the present invention can be further improved.

[0031] In some embodiments of the present invention, the sealant adhesive further includes the following raw materials in parts by weight: 20-60 parts of tackifying resin, 300-500 parts of solvent, 3-10 parts of anti-aging agent, and 20-60 parts of inorganic filler.

[0032] The tackifying resin provided in the embodiments of the present invention is mainly used to improve the adhesion performance of the sealant adhesive and improve the overall performance. The inventor found that when its dosage is too high, the viscosity of the sealant adhesive will increase, the elasticity will be insufficient, and the mechanical properties will decrease, while when the dosage is too low, the adhesion strength of the sealant adhesive will decrease. The solvent plays a role in dissolving the reaction raw materials and providing a reaction environment; the anti-aging agent mainly plays a role in preventing the sealant adhesive from aging and extending its service life; the inorganic filler mainly plays a role in enhancing the effect of shielding ultraviolet light of the sealant adhesive, thereby increasing the service life of the sealant adhesive. Therefore, the sealant adhesive of the present invention has high adhesion strength and excellent aging resistance.

[0033] In some embodiments of the present invention, the sealant adhesive satisfies at least one of the following: (1) the tackifying resin includes at least one of octylphenol formaldehyde resin, TKM-modified alkylphenol formaldehyde resin, and silane-modified polyether; (2) the solvent includes toluene; (3) the anti-aging agent includes at least one of dibutyltin dilaurate, dilauryl thiodipropionate, and Tinuvin 326; (4) the inorganic filler includes at least one of aluminum hydroxide, titanium dioxide, silica, and talc powder. Thus, the present invention can effectively improve the adhesion strength and anti-aging performance of the sealant adhesive.

[0034] In the second aspect of the embodiments of the present invention, the present invention provides a method for preparing a sealant adhesive, which includes the following steps: mixing carboxylated styrene-butadiene rubber, styrene-isoprene-styrene block copolymer, and a solvent to obtain a first solution; mixing succinic anhydride, polyamine compound, and a solvent to obtain a second solution; mixing the first solution and the second solution, and adding a carboxyl activator to obtain a third solution; mixing the third solution, tackifying resin, anti-aging agent, and inorganic filler to obtain the sealant adhesive.

[0035] In the method for preparing the sealant adhesive provided by the embodiments of the present invention, first, the carboxylated styrene-butadiene rubber and the styrene-isoprene-styrene block copolymer are completely dissolved in the solvent, and this step does not involve chemical reactions. In the process of obtaining the second solution, succinic anhydride reacts with the polyamine compound to generate a functional monomer. Taking the reaction of succinic anhydride and diethylenetriamine as an example, the reaction chemistry is shown in Formula I, and the functional monomer will participate in the subsequent polymerization reaction as a reactant. Therefore, in the process of obtaining the third solution, the carboxyl activator activates the carboxyl groups of the carboxylated styrene-butadiene rubber, enabling it to undergo an acid-amine polymerization reaction with the functional monomer of the second solution to generate a network macromolecular structure. At the same time, the network macromolecule based on carboxylated styrene-butadiene rubber and the styrene-isoprene-styrene block copolymer jointly build a double-network interpenetrating cross-linked structure, enhancing the performance of the sealant adhesive. Finally, adding the tackifying resin, anti-aging agent, and inorganic filler to the third solution will further improve the adhesion strength, mechanical strength, and anti-aging performance of the sealant adhesive. Thus, the sealant adhesive obtained by the preparation method of the present invention has high adhesion strength, mechanical strength, and anti-aging properties.

[0036]

[0037] In some embodiments of the present invention, in the step of mixing the carboxylated styrene-butadiene rubber, styrene-isoprene-styrene block copolymer, and the solvent, the rotation speed during mixing is controlled to be 500 - 1000 r / min, and the temperature is 45 - 75 °C.

[0038] The inventors found that heating and stirring at a temperature of 45-75°C and a rotation speed of 500-1000 r / min is beneficial to the full dissolution of raw materials for uniform mixing. Thus, the reaction efficiency can be improved.

[0039] As examples, the rotation speeds are 500 r / min, 600 r / min, 700 r / min, 800 r / min, 900 r / min, 1000 r / min, etc.

[0040] As examples, the temperatures are 45°C, 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, etc.

[0041] In some embodiments of the present invention, in the step of mixing succinic anhydride, polyamine compound and solvent, the rotation speed during mixing is controlled to be 500-1000 r / min; and / or, after mixing succinic anhydride, polyamine compound and solvent, heat treatment is further included. The first temperature of the heat treatment is 40-60°C, and the first reaction time is 20-60 min; the second temperature is 120-160°C, and the second reaction time is 1-3 h.

[0042] According to the embodiments provided by the present invention, the above steps are to open the ring of succinic anhydride and make it react with the polyamine compound to generate a functional monomer. The first temperature of the heat treatment is to completely dissolve succinic anhydride and polyamine compound in the solvent, and then raise the temperature to the second temperature to make succinic anhydride react with the polyamine compound.

[0043] As examples, the rotation speeds are 500 r / min, 600 r / min, 700 r / min, 800 r / min, 900 r / min, 1000 r / min, etc.

[0044] As examples, the first temperatures are 40°C, 45°C, 50°C, 55°C, 60°C, etc.

[0045] As examples, the first reaction times are 20 min, 30 min, 40 min, 50 min, 60 min, etc.

[0046] As examples, the second temperatures are 120°C, 130°C, 140°C, 150°C, 160°C, etc.

[0047] As examples, the second reaction times are 1 h, 1.5 h, 2 h, 2.5 h, 3 h, etc.

[0048] In some embodiments of the present invention, in the step of mixing the first solution and the second solution, it includes: dropping the second solution into the first solution, and controlling the dropping rate to be 8 - 12 parts / min; and / or, in the step of adding a carboxyl activator, controlling the reaction temperature to be 55 - 80 °C, the time to be 1 - 3 h, and the rotation speed to be 500 - 1000 r / min.

[0049] In the present invention, during the process of dropping the second solution into the first solution, it needs to be dropped slowly to better control the reaction rate and prevent the polymer from exploding and polymerizing, resulting in uneven molecular weight distribution and poor product performance. Then, a carboxyl activator is added, and it is heated and stirred to be mixed evenly to make the polymerization reaction more complete. Thus, a sealing adhesive with excellent performance can be obtained.

[0050] As an example, the dropping rate is 8 parts / min, 9 parts / min, 10 parts / min, 11 parts / min, 12 parts / min

[0051] As an example, the reaction temperature is 55 °C, 60 °C, 65 °C, 70 °C, 75 °C, 80 °C, etc.

[0052] As an example, the time is 1 h, 1.5 h, 2 h, 2.5 h, 3 h, etc.

[0053] As an example, the rotation speed is 500 r / min, 600 r / min, 700 r / min, 800 r / min, 900 r / min, 1000 r / min, etc.

[0054] In some embodiments of the present invention, the preparation method includes the following raw materials in parts by weight: 100 - 150 parts of carboxylated styrene - butadiene rubber,

[0055] 20 - 50 parts of styrene - isoprene - styrene block copolymer, 5 - 20 parts of succinic anhydride, 5 - 15 parts of polyamine compound, 20 - 60 parts of tackifying resin, 1 - 5 parts of carboxyl activator, 300 - 500 parts of solvent, 3 - 10 parts of anti - aging agent, 20 - 60 parts of inorganic filler.

[0056] Next, the solution of the present invention will be explained with reference to the examples. Those skilled in the art will understand that the following examples are only used to illustrate the present invention and should not be construed as limiting the scope of the present invention. For those not specified in the examples regarding specific techniques or conditions, they shall be carried out according to the techniques or conditions described in the literature in the art or according to the product specifications. For reagents or instruments not specified as to the manufacturer, they are all conventional products that can be obtained through commercial purchase.

[0057] Example 1:

[0058] (1) Heat and stir 110 parts of carboxylated styrene-butadiene rubber, 35 parts of styrene-isoprene-styrene block copolymer, and 250 parts of toluene until they are evenly mixed. The heating temperature is 55 °C, the stirring speed is 800 r / min, and stir until it is clear and transparent without visible solids to obtain the first solution;

[0059] (2) Stir 8 parts of succinic anhydride, 7 parts of diethylenetriamine (polyamine compound), and 100 parts of toluene at room temperature. The stirring speed is 600 r / min. After mixing evenly, heat to 55 °C and react for 40 min, then heat to 145 °C and react for 2 h to obtain the second solution;

[0060] (3) Slowly drip the second solution into the first solution at a dripping rate of 10 parts / min, then add 1 part of zinc oxide (carboxyl activator), heat and stir to mix evenly. The heating temperature is 70 °C, the stirring speed is 800 r / min, and the reaction time is 3 h;

[0061] (4) Add 29 parts of TKM-modified alkylphenolic resin (tackifying resin), 5 parts of dilauryl thiodipropionate (anti-aging agent), and 29 parts of titanium dioxide (inorganic filler) to the solution and mix evenly to obtain the carboxylated styrene-butadiene rubber-based sealant.

[0062] Example 2:

[0063] (1) Heat and stir 120 parts of carboxylated styrene-butadiene rubber, 40 parts of styrene-isoprene-styrene block copolymer, and 300 parts of toluene until they are evenly mixed. The heating temperature is 75 °C, the stirring speed is 1000 r / min, and stir until it is clear and transparent without visible solids to obtain the first solution;

[0064] (2) Stir 11 parts of succinic anhydride, 9 parts of ethylenediamine (polyamine compound), and 100 parts of toluene at room temperature. The stirring speed is 1000 r / min. After mixing evenly, heat to 50 °C and react for 60 min, then heat to 160 °C and react for 1 h to obtain the second solution;

[0065] (3) Slowly drip the second solution into the first solution at a dripping rate of 10 parts / min, add 2 parts of magnesium oxide (carboxyl activator), heat and stir to mix evenly. The heating temperature is 65 °C, the stirring speed is 1000 r / min, and the reaction time is 2 h;

[0066] (4) Add 38 parts of silane-modified polyether (tackifying resin), 6 parts of Tinuvin 326 (anti-aging agent), and 38 parts of talc (inorganic filler) to the solution and mix evenly to obtain the carboxylated styrene-butadiene rubber-based sealant.

[0067] Example 3:

[0068] (1) Heat and stir 130 parts of carboxylated styrene-butadiene rubber, 30 parts of styrene-isoprene-styrene block copolymer, and 300 parts of toluene until they are evenly mixed. The heating temperature is 70 °C, the stirring speed is 700 r / min, and stir until it is clear and transparent without visible solids to obtain the first solution;

[0069] (2) Stir 15 parts of succinic anhydride, 11 parts of diethylenetriamine (polyamine compound), and 150 parts of toluene at room temperature. The stirring speed is 900 r / min. After mixing evenly, heat to 60 °C and react for 50 min, then heat to 160 °C and react for 2 h to obtain the second solution;

[0070] (3) Slowly drip the second solution into the first solution at a dripping rate of 10 parts / min, then add 3 parts of zinc stearate (carboxyl activator), heat and stir to mix evenly. The heating temperature is 80 °C, the stirring speed is 1000 r / min, and the reaction time is 3 h;

[0071] (4) Add 50 parts of octylphenol formaldehyde resin (tackifying resin), 7 parts of dibutyltin dilaurate (anti-aging agent), and 50 parts of silica (inorganic filler) to the solution and mix evenly to obtain the carboxylated styrene-butadiene rubber-based sealant.

[0072] Example 4:

[0073] (1) Heat and stir 140 parts of carboxylated styrene-butadiene rubber, 45 parts of styrene-isoprene-styrene block copolymer, and 350 parts of toluene until they are evenly mixed. The heating temperature is 50 °C, the stirring speed is 550 r / min, and stir until it is clear and transparent without visible solids to obtain the first solution;

[0074] (2) Stir 18 parts of succinic anhydride, 13 parts of ethylenediamine (polyamine compound), and 120 parts of toluene at room temperature. The stirring speed is 650 r / min. After mixing evenly, heat to 50 °C and react for 45 min, then heat to 145 °C and react for 2 h to obtain the second solution;

[0075] (3) Slowly drip the second solution into the first solution at a dripping rate of 10 parts / min, then add 4 parts of zinc oxide (carboxyl activator), heat and stir to mix evenly. The heating temperature is 75 °C, the stirring speed is 1000 r / min, and the reaction time is 1 h;

[0076] (4) Add 60 parts of TKM-modified alkylphenol formaldehyde resin (tackifying resin), 9 parts of dilauryl thiodipropionate (anti-aging agent), and 45 parts of titanium dioxide (inorganic filler) to the solution and mix evenly to obtain the carboxylated styrene-butadiene rubber-based sealant.

[0077] Example 5:

[0078] (1) 150 parts of carboxylated styrene-butadiene rubber, 50 parts of styrene-isoprene-styrene block copolymer, and 380 parts of toluene are heated and stirred to mix them evenly. The heating temperature is 55 °C, the stirring speed is 800 r / min, and stirring is continued until it becomes clear and transparent without visible solids, obtaining a first solution;

[0079] (2) 20 parts of succinic anhydride, 15 parts of diethylenetriamine (polyamine compound), and 120 parts of toluene are stirred at room temperature. The stirring speed is 800 r / min. After mixing evenly, the temperature is raised to 50 °C, the reaction time is 50 min, then the temperature is raised to 150 °C, and the reaction is carried out for 3 h, obtaining a second solution;

[0080] (3) The second solution is slowly added dropwise into the first solution at a dropping rate of 10 parts / min. Then 5 parts of magnesium oxide (carboxyl activator) are added, and it is heated and stirred to mix evenly. The heating temperature is 70 °C, the stirring speed is 700 r / min, and the reaction time is 3 h;

[0081] (4) 60 parts of silane-modified polyether (tackifying resin), 10 parts of Tinuvin 326 (anti-aging agent), and 60 parts of talc (inorganic filler) are added to the solution and mixed evenly to obtain a carboxylated styrene-butadiene rubber-based sealant adhesive.

[0082] Comparative Example 1:

[0083] (1) 100 parts of carboxylated styrene-butadiene rubber, 20 parts of styrene-isoprene-styrene block copolymer, and toluene are heated and stirred to mix them evenly. The heating temperature is 45 °C, the stirring speed is 500 r / min, and stirring is continued until it becomes clear and transparent without visible solids, obtaining a first solution;

[0084] (2) 5 parts of succinic anhydride, 5 parts of ethylenediamine (polyamine compound), and toluene are stirred at room temperature. The stirring speed is 500 r / min. After mixing evenly, the temperature is raised to 40 °C, the reaction time is 20 min, then the temperature is raised to 120 °C, and the reaction is carried out for 3 h, obtaining a second solution;

[0085] (3) The second solution is slowly added dropwise into the first solution at a dropping rate of 10 parts / min. It is heated and stirred to mix evenly. The heating temperature is 55 °C, the stirring speed is 500 r / min, and the reaction time is 1 h;

[0086] (4) 20 parts of octylphenol formaldehyde resin (tackifying resin), 3 parts of dibutyltin dilaurate (anti-aging agent), and 20 parts of aluminum hydroxide (inorganic filler) are added to the solution and mixed evenly to obtain a carboxylated styrene-butadiene rubber-based sealant adhesive.

[0087] The formulations of the above examples and comparative examples are shown in Table 1.

[0088] Table 1 Formulation Table of Carboxylated Styrene-Butadiene Rubber-Based Sealant Adhesive for Examples and Comparative Examples

[0089]

[0090] After performance testing, the test results of the above-mentioned examples and comparative examples are shown in Table 2.

[0091] Table 2 Performance test results of carboxylated styrene-butadiene rubber-based sealant adhesives for examples and comparative examples

[0092]

[0093]

[0094] The above test results show that since the carboxyl activator is missing in Comparative Example 1, the functional monomers formed by the reaction of succinic anhydride and polyamine compounds cannot fully polymerize with carboxylated styrene-butadiene rubber, resulting in fewer macromolecular polymers in the carboxylated styrene-butadiene rubber-based sealant adhesive of Comparative Example 1. Therefore, the performance test results of Comparative Example 1 are worse than those of the examples. From the test results of the examples, in the preparation system of the present invention, due to the presence of the double-network crosslinked structure and inorganic fillers, it has excellent mechanical properties and thermal stability. At the same time, the addition of tackifying resin and anti-aging agent greatly increases the initial tack performance and adhesion strength of the carboxylated styrene-butadiene rubber-based sealant adhesive. Therefore, the sealant adhesive of the present invention can be widely used for sealing and bonding various materials such as wood, metal, and plastic, and can also be applied in the fields of sealing and bonding of automobiles, ships, etc.

[0095] In the description of this specification, the descriptions referring to terms such as "one embodiment", "some embodiments", "example", "specific example", or "some examples" mean that the specific features, structures, materials, or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials, or characteristics described can be combined in a suitable manner in any one or more embodiments or examples. In addition, without conflict, those skilled in the art can combine and combine the different embodiments or examples described in this specification and the features of different embodiments or examples.

[0096] Although the embodiments of the present invention have been shown and described above, it can be understood that the above embodiments are exemplary and should not be construed as limiting the present invention. Those of ordinary skill in the art can make changes, modifications, substitutions, and variations to the above embodiments within the scope of the present invention.

Claims

1. A sealing adhesive, characterized in that: The sealing adhesive comprises the following raw materials in parts by weight: 100-150 parts of carboxylated styrene-butadiene rubber, 20 to 50 parts of styrene-isoprene-styrene block copolymer, 5-20 parts of succinic anhydride, 5 to 15 parts of polyamine compounds, 1 to 5 parts of carboxyl activator.

2. The sealing adhesive according to claim 1, characterized in that: The polyamine compound includes at least one of ethylenediamine and diethylenetriamine.

3. The sealing adhesive according to claim 1 or 2, characterized in that: The carboxyl activator includes at least one of zinc oxide, magnesium oxide and zinc stearate.

4. The sealing adhesive according to any one of claims 1 to 3, characterized in that: The sealing adhesive further comprises the following raw materials in parts by weight: 20 to 60 parts of tackifying resin, 300-500 parts of solvent, 3 to 10 parts of anti-aging agent, 20 to 60 parts of inorganic filler.

5. The sealing adhesive according to claim 4, characterized in that: The sealing adhesive satisfies at least one of the following: (1) The tackifying resin includes at least one of octylphenol-formaldehyde resin, TKM-modified alkylphenol-formaldehyde resin, and silane-modified polyether; (2) The solvent includes toluene; (3) The antioxidant includes at least one of dibutyltin dilaurate, dilauryl thiodipropionate, and Tinuvin 326; (4) The inorganic filler includes at least one of aluminum hydroxide, titanium dioxide, silicon dioxide and talc.

6. A method for preparing a carboxylated styrene-butadiene rubber-based sealing adhesive, characterized in that: The following steps are involved: Mixing carboxylated styrene-butadiene rubber, styrene-isoprene-styrene block copolymer and solvent to obtain a first solution; Mixing dry succinic acid, a polyamine compound and a solvent to obtain a second solution; The first solution and the second solution are mixed, and a carboxyl activator is added to obtain a third solution; The third solution, tackifying resin, anti-aging agent and inorganic filler are mixed to obtain a sealing adhesive.

7. The preparation method according to claim 6, characterized in that: In the step of mixing the carboxylated styrene-butadiene rubber, the styrene-isoprene-styrene block copolymer and the solvent, the rotation speed during mixing is controlled to be 500-1000 r / min and the temperature is controlled to be 45-75° C.

8. The preparation method according to claim 6 or 7, characterized in that: In the step of mixing the dry succinic acid, the polyamine compound and the solvent, the rotation speed during mixing is controlled to be 500 to 1000 r / min; And / or, the step of mixing the dry succinic acid, the polyamine compound and the solvent further includes a heating treatment, wherein the first temperature of the heating treatment is 40-60° C., the first reaction time is 20-60 min; the second temperature is 120-160° C., and the second reaction time is 1-3 h.

9. The preparation method according to any one of claims 6 to 8, characterized in that: The step of mixing the first solution with the second solution includes: adding the second solution dropwise to the first solution at a rate of 8 to 12 parts / min; And / or, in the step of adding a carboxyl activator, the reaction temperature is controlled to be 55-80° C., the reaction time is 1-3 hours, and the rotation speed is 500-1000 r / min.

10. The preparation method according to any one of claims 6 to 9, characterized in that: The preparation method comprises the following raw materials in parts by weight: 100-150 parts of carboxylated styrene-butadiene rubber, 20 to 50 parts of styrene-isoprene-styrene block copolymer, 5-20 parts of succinic anhydride, 5 to 15 parts of polyamine compounds, 20 to 60 parts of tackifying resin, 1 to 5 parts of carboxyl activator, 300-500 parts of solvent, 3 to 10 parts of anti-aging agent, 20 to 60 parts of inorganic filler.

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