Multifunctional emulsion type silane treating agent as well as preparation and use methods thereof

Abstract

The invention provides a multifunctional emulsion type silane treating agent and a preparation method thereof, and belongs to the technical field of material surface functionalization treatment.The multifunctional emulsion type silane treating agent comprises a component A and a component B. The component A is prepared from, by weight, 15-28 parts of main materials, 50-70 parts of water, 1-10 parts of a catalyst, 0.1-10 parts of a pH regulator, 5-20 parts of an emulsifier, 0-10 parts of a dispersing agent and 2-10 parts of a modifier I; the component B comprises the following raw materials in parts by weight: 15-28 parts of a main material, 50-70 parts of water, 1-10 parts of a catalyst, 0.1-10 parts of a pH regulator, 5-20 parts of an emulsifier, 0-10 parts of a dispersant and 2-10 parts of a modifier II. The silane treating agent prepared by the invention can be used for functional treatment of surfaces of various substances such as powder, spare and accessory parts and ceramic tiles, including moisture-proof treatment, hydrophobic treatment, preservative treatment, heat-resistant treatment, oleophylic or oleophobic treatment and the like.

Description

TECHNICAL FIELD

[0001] The present application relates to a silane treatment agent, in particular to a multifunctional emulsion type silane treatment agent and a preparation method thereof, and belongs to the technical field of material surface functionalization treatment. BACKGROUND

[0002] Surface functionalization is a new technology that modifies the properties of materials at the surface level, thereby achieving performance improvement or new functions. It has been widely used in innovative materials and equipment, and has brought important influence to many industries, including mechanical manufacturing, electronic products, medical devices, energy and environmental protection.

[0003] Silanization treatment is a process of treating the surface of metal or non-metal materials with organic silane as the main raw material. Compared with traditional phosphating, silanization treatment has the following advantages: no harmful heavy metal ions, no phosphorus, no need for heating; silane treatment process does not produce sediment, the treatment time is short, and the control is simple; the treatment steps are less, the surface adjustment process can be omitted, and the bath can be reused; effectively improves the adhesion of paint to the substrate; can be co-linearly treated with various substrates such as iron plate, galvanized plate and aluminum plate. However, the traditional commonly used silane treatment agent has long synthesis process route and high cost, and volatile organic compounds such as alcohols are formed during the reaction process, which poses an environmental risk; the traditional siloxane ring body must use strong acids such as sulfuric acid and strong bases such as sodium hydroxide as catalysts, which can destroy the active modified groups such as amino and epoxy groups; and the traditional thickening agent such as sodium polyacrylate is only a thickening agent, dispersant or stabilizer, which must be added in the last mechanical emulsification process; the traditional catalysts such as strong acids and strong bases can destroy the active modified groups such as amino and epoxy groups due to their strong acidity and alkalinity. SUMMARY

[0004] In view of the above problems, the present application provides a multifunctional emulsion type silane treatment agent and a preparation method thereof.

[0005] To achieve the above purpose, the technical scheme of the present application is as follows: a multifunctional emulsion type silane treatment agent, comprising A component and B component, the A component comprises the following raw materials by weight: 15-28 parts of main material, 50-70 parts of water, 1-10 parts of catalyst, 0.1-10 parts of pH regulator, 5-20 parts of emulsifier, 0-10 parts of dispersant, 2-10 parts of modifier I, and the B component comprises the following raw materials by weight: 15-28 parts of main material, 50-70 parts of water, 1-10 parts of catalyst, 0.1-10 parts of pH regulator, 5-20 parts of emulsifier, 0-10 parts of dispersant, 2-10 parts of modifier II.

[0006] The main material in the A component and the B component comprises a hydroxyl-terminated organosiloxane with viscosity <200 cs, a graphene oxide modified hydroxyl-terminated organosiloxane, and an acryloxy-modified hydroxyl-terminated organosiloxane. The modifier I is an amino-containing silane, and the modifier II is an epoxy-containing silane.

[0007] Further, the main material in the A component and the B component comprises the following raw materials in terms of mass ratio of the main material: 20-90% of the hydroxyl-terminated organosiloxane with viscosity <200 cs, 0-30% of the graphene oxide modified hydroxyl-terminated organosiloxane, and 10-50% of the acryloxy-modified hydroxyl-terminated organosiloxane.

[0008] Further, the graphene oxide modified hydroxyl-terminated organosiloxane is prepared by the following method:

[0009] (1) Pretreatment: 100 parts by weight of the hydroxyl-terminated organosiloxane with viscosity <200 cs and 0.1-10 parts by weight of graphene oxide powder are mechanically stirred for 5-10 minutes, a high-speed shearing machine is continuously stirred for 20-40 minutes, and ultrasonic treatment is performed for 0.5-6 hours, and then the reaction kettle is added.

[0010] (2) Modification reaction: the reaction kettle is heated to 140-160℃, after the reaction in the reaction kettle is smooth and no obvious sound is heard, the reaction is continuously performed for 1-5 hours, and then the temperature is continuously increased to 170-200℃ and the reaction is performed for 10-60 minutes. The unreacted graphene oxide powder is removed by centrifugation to obtain the graphene oxide modified hydroxyl-terminated organosiloxane, and the temperature is decreased to room temperature for packaging.

[0011] Further, the acryloxy-modified hydroxyl-terminated organosiloxane is prepared by the following method:

[0012] (1) Pretreatment: one or more of KH570, KH571, and KH572 are mixed to obtain a mixture A; 100 parts by weight of the mixture A and 1-10 parts by weight of water are mixed, heated to 60-80℃, and reacted for 20-120 minutes, then the unreacted water and alcohol formed in the reaction are removed by vacuum to obtain an acryloxy-siloxane prepolymer, and the temperature is decreased to room temperature for packaging.

[0013] (2) Modification reaction: 100 parts by weight of the hydroxyl-terminated organosiloxane with viscosity <200 cs, 1-20 parts by weight of the acryloxy-siloxane prepolymer, and 0.01-0.5 parts by weight of KOH are mechanically stirred for 5-10 minutes, heated to 110-150℃ and reacted for 1-5 hours, then KOH with a mass of 140%-170% of the phosphoric acid is added for neutralization, and the water and small molecule siloxane are removed by vacuum to obtain the acryloxy-modified hydroxyl-terminated organosiloxane, and the temperature is decreased to room temperature for packaging.

[0014] Further, in the A component and the B component, the catalyst is one or more of polyacrylic acid, starch phosphate, alginic acid, etc., the pH regulator is sodium hydroxide aqueous solution or lithium hydroxide aqueous solution, the emulsifier is isomeric tridecanol ether series or Span-Tween series, and the dispersant is polyether silicone oil; the modifier I is KH602, KH550 or KH792, and the modifier II is KH560 or KH562.

[0015] Further, the multifunctional emulsion type silane treating agent further comprises the following adjusting agents as needed: hydrophobic adjusting agent, temperature resistant adjusting agent or oily adjusting agent.

[0016] The preparation method of the multifunctional emulsion type silane treating agent is as follows: the A component is prepared by the following method: (1) water, catalyst, emulsifier are added in proportion, stirred uniformly, then the pH regulator is added to adjust the pH value to 4-6; (2) the mixed solution is heated to 50-80℃, the main material and the modifier I and the adjusting agent added as needed are added in proportion; (3) after keeping constant temperature for 1-5 hours, the pH regulator is added to adjust the pH value to 6-8 and the product is discharged and packaged;

[0017] The B component is prepared by the following method: (1) water, catalyst, emulsifier are added in proportion, stirred uniformly, then the pH regulator is added to adjust the pH value to 4-6; (2) the mixed solution is heated to 50-80℃, the main material and the modifier II and the adjusting agent added as needed are added in proportion; (3) after keeping constant temperature for 1-5 hours, the pH regulator is added to adjust the pH value to 7±0.5 and the product is discharged and packaged.

[0018] The use method of the multifunctional emulsion type silane treating agent is as follows: the A component and the B component are configured and used in the molar ratio of epoxy value to ammonia value of 1-1.1:1.

[0019] Further, when used for powder treatment, the following method is used:

[0020] (1) the A component and the B component are mixed uniformly in proportion, then 10-20 times of water is added for dilution and then added into the production system;

[0021] (2) the powder is stirred and mixed for more than 30 minutes, and the temperature during stirring and mixing is normal temperature to 80℃;

[0022] (3) the powder is dried by A method or B method, and the treated powder is obtained;

[0023] The A method is: the supernatant is removed by filtration, a tumbling and drying device is added, and tumbling and drying are carried out at a temperature above 80℃ for 30-120 minutes to obtain qualified treated powder;

[0024] Method B: Add the mixed liquid into the spray drying pretreatment box, preheat to above 80℃ for 30-90 minutes, and spray dry to obtain qualified powder.

[0025] Furthermore, when used for surface functionalization of spare parts and tiles, the following method is used:

[0026] (1) After mixing components A and B in proportion, add 2-10 times water to dilute to a sprayable viscosity;

[0027] (2) Spray the diluted mixed solution evenly on the surface of the material to be treated;

[0028] (3) Drying and curing by method A, method B or method C can complete the surface functionalization treatment;

[0029] Method A: Dry in an environment above 80°C for at least 2 hours. After the water is completely evaporated, the surface functionalization treatment is completed.

[0030] Method B: Expose to UV light for 1-10 minutes or sunlight for 30-120 minutes. After drying, the surface functionalization treatment is completed.

[0031] Method C: After natural drying at room temperature in a lightless environment for 24-72 hours, the surface functionalization treatment can be completed.

[0032] The beneficial effects of the multifunctional emulsion-type silane treating agent and the preparation method thereof of the present invention are:

[0033] The silane treatment agent prepared by the present invention can be used for functional treatment of the surfaces of various materials such as powders, spare parts, tiles, etc., including moisture-proof treatment, hydrophobic treatment, anti-corrosion treatment, heat-resistant treatment, oleophilic or oleophobic treatment, etc.

[0034] The present invention selects hydroxyl-terminated organosiloxane, which has a wide source of raw materials and is low in price. No volatile organic compounds are produced during the reaction process, and the process is environmentally friendly and safe.

[0035] The present invention selects moderately acidic substances such as polyacrylic acid, starch phosphate, and alginic acid as catalysts, which can not only catalyze polymerization normally during the emulsion polymerization reaction and protect active modified groups such as amino and epoxy groups, but also be neutralized to become thickeners after the reaction is completed, without the need to add other thickeners. DETAILED DESCRIPTION

[0036] The technical solutions in the embodiments of the present invention are described clearly and completely below. Many specific details are set forth in the following description to facilitate a full understanding of the present invention. However, the present invention may also be implemented in other ways different from those described herein, and those skilled in the art may make similar generalizations without violating the scope of the present invention. Therefore, the present invention is not limited to the specific embodiments disclosed below.

[0037] A multifunctional emulsion type silane treating agent, comprising A component and B component, the specific composition is shown in the following table:

[0038] Table 1 A component formula

[0039]

[0040]

[0041] Table 2 B component formula

[0042]

[0043] The graphene oxide modified hydroxyl-terminated organosiloxane is prepared by the following method:

[0044] (1) Pretreatment: 100 parts by weight of hydroxyl-terminated organosiloxane with a viscosity of <200 cs and 0.1-10 parts by weight of graphene oxide powder are mechanically stirred for 5-10 minutes, a high-speed shearing machine is continuously stirred for 20-40 minutes, and ultrasonic treatment is performed for 0.5-6 hours, and then added to a reaction kettle;

[0045] (2) Modification reaction: the reaction kettle is heated to 140-160℃, and after the reaction in the reaction kettle is smooth and no obvious sound is heard, the reaction is continued for 1-5 hours, and then the temperature is further increased to 170-200℃ and reacted for 10-60 minutes. The unreacted graphene oxide powder is removed by centrifugation to obtain graphene oxide modified hydroxyl-terminated organosiloxane, and the temperature is lowered to room temperature for packaging.

[0046] The acryloxy-modified hydroxyl-terminated organosiloxane is prepared by the following method:

[0047] (1) Pretreatment: one or more of KH570, KH571 and KH572 are mixed to obtain a mixture A (there is no strict proportion limit between the above-mentioned substances when mixed and prepared, and the proportion affects the curing speed and emulsion viscosity, and the actual proportion is determined according to customer requirements); 100 parts by weight of the mixture A and 1-10 parts by weight of water are mixed, heated to 60-80℃, and reacted for 20-120 minutes, then the unreacted water and alcohol formed by the reaction are removed by vacuum, to obtain an acryloxy-siloxane prepolymer, which is cooled to room temperature for packaging;

[0048] (2) modification reaction: 100 parts by weight of hydroxyl-terminated organosiloxane with viscosity <200 cs, 1-20 parts by weight of acryloyloxy siloxane prepolymer and 0.01-0.5 parts by weight of KOH are mechanically stirred for 5-10 minutes, heated to 110-150°C for 1-5 hours, neutralized with phosphoric acid with 140%-170% of the mass of KOH, vacuumed to remove water and small molecule siloxane, to obtain acryloyloxy-modified hydroxyl-terminated organosiloxane, and cooled to room temperature for packaging.

[0049] The general names of isomeric tridecanol ether series products in Table 1 and Table 2 are: 1303, 1305, 1306, 1307, 1308, 1310, 1312, which are also written as 1330, 1350, 1360, 1370, 1380, 1310, 1312. Generally, two or three of them are selected for compounding. For example, the typical ratio is 1350 / 1380 1:1 mixture. The general names of Span products in the Span-Tween series are: S-20, S-40, S-60, S-80, S-85, and the general names of Tween products are: T-20, T-40, T-60, T-80, T-85. The typical ratio is S-80 / T-80 1:1 mixture.

[0050] Preparation method of A component and B component:

[0051] 1. Add water, catalyst and emulsifier in proportion, stir uniformly, add appropriate amount of pH adjuster, and adjust the pH value to 4-6;

[0052] 2. Heat the mixed solution to 50-80°C, add the main materials, modifiers and other adjusting agents in proportion, and other adjusting agents such as hydrophobic adjusting agent, temperature-resistant adjusting agent, oiliness adjusting agent, etc. (other adjusting agents are additives added as needed, and the specific proportion is determined according to customer demand in practice) ;

[0053] 3. After keeping constant temperature for 1-5 hours, add appropriate amount of pH adjuster, adjust the pH value to 6-8, and (B component is adjusted to 7±0.5 to ensure the stability of epoxy group) and discharge and package; A component and B component are prepared according to the above steps 1-3.

[0054] Method for using silane treatment agent:

[0055] 1. Compound scheme

[0056] The product A and B components are configured according to the molar ratio of epoxy value and amino value of 1-1.1:1. Meanwhile, according to the specific scene and comprehensive cost consideration, the A component can be replaced by an amino crosslinking agent with the same number of amino moles, and the B component can be replaced by an epoxy resin emulsion with the same number of epoxy moles (that is, when using the product of the present application, the A component or the B component can be selected alone, but when the A component is selected alone, it needs to be compounded with other epoxy resin emulsions with the same number of epoxy moles, and when the B component is selected alone, it needs to be compounded with other amino crosslinking agents with the same number of moles).

[0057] 2. Powder treatment process

[0058] (1) After the A and B components are uniformly mixed in proportion, 10-20 times water is added for dilution, and then added to the production system.

[0059] (2) Stir and mix with the powder for more than 30 minutes (room temperature to 80°C).

[0060] (3) Dry the powder by A method or B method to obtain the treated powder.

[0061] A method: remove the supernatant by filtration, add a tumbling and drying device, tumble at a temperature above 80°C for 30-120 minutes to obtain qualified treated powder.

[0062] B method: add the mixed solution to a spray drying pretreatment box, preheat to above 80°C for 30-90 minutes, and spray dry to obtain qualified treated powder.

[0063] 3. Surface functionalization treatment process of parts, tiles and other substances

[0064] (1) After the A and B components are uniformly mixed in proportion, 2-10 times water is added for dilution to a sprayable viscosity.

[0065] (2) The diluted mixed solution is uniformly sprayed on the surface of the material to be treated.

[0066] (3) Dry and cure by A method, B method or C method to complete the surface functionalization treatment.

[0067] A method: dry in an environment above 80°C for at least 2 hours, and after the water is completely volatilized, the surface functionalization treatment is completed.

[0068] B method: irradiate with ultraviolet light for 1-10 minutes or sunlight for 30-120 minutes, and after drying (at room temperature or with heating), the surface functionalization treatment is completed.

[0069] C method: after natural drying for 24-72 hours in a dark environment at room temperature, the surface functionalization treatment is completed.

[0070] The silane treatment agent prepared by the present application has the following characteristics or use precautions:

[0071] 1. It can be used for functional treatment of surfaces of various substances such as powder, spare parts, and ceramic tiles, including moisture-proof treatment, hydrophobic treatment, corrosion-proof treatment, heat-resistant treatment, lipophilic or oleophobic treatment, etc.

[0072] 2. The graphene oxide modified hydroxyl-terminated organosiloxane is only used in special scenarios where it is necessary to reduce the film resistance, and can not be used in scenarios where there is no requirement for resistance.

[0073] (1) The main material in the emulsion used in the powder treatment process must be graphene oxide modified hydroxyl-terminated organosiloxane.

[0074] (2) In the surface functionalization treatment process of substances such as spare parts and ceramic tiles, the graphene oxide modified hydroxyl-terminated organosiloxane used as the main material can be replaced by a mixture of one or more of graphene oxide, graphene, carbon nanotubes, and nano-carbon powder, which is pre-treated with hydroxyl-terminated organosiloxane, without the need for a modification reaction. The pre-treatment process can refer to the pre-treatment process for preparing the graphene oxide modified hydroxyl-terminated organosiloxane.

[0075] Preparation Example 1: Graphene oxide modified hydroxyl-terminated organosiloxane

[0076] Preparation Example 1-1

[0077] (1) Pre-treatment: 100 parts by weight of hydroxyl-terminated organosiloxane with a viscosity of <200 cs and 10 parts by weight of graphene oxide powder are mechanically stirred for 10 minutes, then stirred for 40 minutes with a high-speed shearing machine, and then treated with ultrasonic waves for 6 hours, and then added to a reaction kettle;

[0078] (2) Modification reaction: the reaction kettle is heated to 140℃, and after the reaction in the reaction kettle is smooth and there is no obvious sound, the reaction is continued for 5 hours, then the temperature is further increased to 200℃ and the reaction is continued for 10 minutes, then the unreacted graphene oxide powder is removed by centrifugation, and then the graphene oxide modified hydroxyl-terminated organosiloxane is obtained, and then the temperature is lowered to room temperature for packaging.

[0079] Preparation Example 1-2

[0080] (1) Pre-treatment: 100 parts by weight of hydroxyl-terminated organosiloxane with a viscosity of <200 cs and 5 parts by weight of graphene oxide powder are mechanically stirred for 8 minutes, then stirred for 30 minutes with a high-speed shearing machine, and then treated with ultrasonic waves for 3 hours, and then added to a reaction kettle;

[0081] (2) Modification reaction: the reaction kettle is heated to 150℃, and after the reaction in the reaction kettle is smooth and there is no obvious sound, the reaction is continued for 3 hours, then the temperature is further increased to 190℃ and the reaction is continued for 40 minutes, then the unreacted graphene oxide powder is removed by centrifugation, and then the graphene oxide modified hydroxyl-terminated organosiloxane is obtained, and then the temperature is lowered to room temperature for packaging.

[0082] Preparation Example 1-3

[0083] (1) Pretreatment: 100 parts by weight of hydroxyl-terminated organosiloxane with viscosity <200 cs and 0.1 parts by weight of graphene oxide powder were mechanically stirred for 5 minutes, a high-speed shearing machine was continuously stirred for 20 minutes, and ultrasonic treatment was performed for 0.5 hours, and then the reaction kettle was added;

[0084] (2) Modification reaction: the reaction kettle was heated to 140°C, after the reaction in the reaction kettle was smooth and no obvious sound, the reaction was continued for 1 hour, and then the temperature was continuously increased to 200°C and reacted for 10 minutes. The unreacted graphene oxide powder was removed by centrifugation to obtain graphene oxide modified hydroxyl-terminated organosiloxane, and then the temperature was decreased to room temperature for packaging.

[0085] Preparation Example 2: Acryloxy-modified hydroxyl-terminated organosiloxane

[0086] Preparation Example 2-1

[0087] (1) Pretreatment: KH570 and KH571 (in this example, the mass ratio is 1:1, and it can also be adjusted according to actual needs) were mixed to obtain a mixture A; 100 parts by weight of the mixture A and 10 parts by weight of water were mixed, heated to 80°C, and reacted for 20 minutes, then the unreacted water and alcohol formed by the reaction were removed by vacuum to obtain an acryloxy siloxane prepolymer, and then the temperature was decreased to room temperature for packaging.

[0088] (2) Modification reaction: 100 parts by weight of hydroxyl-terminated organosiloxane with viscosity <200 cs, 20 parts by weight of acryloxy siloxane prepolymer, and 0.5 parts by weight of KOH were mechanically stirred for 10 minutes, heated to 110°C and reacted for 5h, then neutralized with 140% of the mass of KOH in phosphoric acid, and then the water and small molecule siloxane were removed by vacuum to obtain acryloxy-modified hydroxyl-terminated organosiloxane, and then the temperature was decreased to room temperature for packaging.

[0089] Preparation Example 2-2

[0090] (1) Pretreatment: KH571 and KH572 (in this example, the mass ratio is 1:1, and it can also be adjusted according to actual needs) were mixed to obtain a mixture A; 100 parts by weight of the mixture A and 1 part by weight of water were mixed, heated to 60°C, and reacted for 20 minutes, then the unreacted water and alcohol formed by the reaction were removed by vacuum to obtain an acryloxy siloxane prepolymer, and then the temperature was decreased to room temperature for packaging.

[0091] (2) Modification reaction: 100 parts by weight of hydroxyl-terminated organosiloxane with viscosity <200 cs, 1 part by weight of acryloxy-siloxane prepolymer and 0.4 parts by weight of KOH were mechanically stirred for 5 minutes, heated to 120°C for 3 hours, neutralized with phosphoric acid with 150% of the mass of KOH, vacuumed to remove water and small molecule siloxane, to obtain acryloxy-modified hydroxyl-terminated organosiloxane, and cooled to room temperature for packaging.

[0092] Preparation Example 2-3

[0093] (1) Pretreatment: KH570 and KH572 (1:1 by mass in this example, which can also be adjusted according to actual needs) were mixed to obtain mixture A; 100 parts by weight of mixture A and 5 parts by weight of water were mixed, heated to 70°C, reacted for 70 minutes, vacuumed to remove unreacted water and alcohol formed by reaction, to obtain acryloxy-siloxane prepolymer, and cooled to room temperature for packaging.

[0094] (2) Modification reaction: 100 parts by weight of hydroxyl-terminated organosiloxane with viscosity <200 cs, 1 part by weight of acryloxy-siloxane prepolymer and 0.4 parts by weight of KOH were mechanically stirred for 5 minutes, heated to 120°C for 3 hours, neutralized with phosphoric acid with 150% of the mass of KOH, vacuumed to remove water and small molecule siloxane, to obtain acryloxy-modified hydroxyl-terminated organosiloxane, and cooled to room temperature for packaging.

[0095] Preparation Example 3: Preparation of A component and B component

[0096] Preparation Example 3-1

[0097] 1. 50 parts by weight of water, 10 parts by weight of catalyst (polyacrylic acid), 20 parts by weight of emulsifier (isotridecanol ether series, A component in this example selected 1350 / 1380 1:1 mixed, B component selected 1360), were added in proportion, stirred uniformly, then an appropriate amount of pH adjuster (aqueous sodium hydroxide solution) was added, and the pH value was adjusted to 4;

[0098] 2. The mixed solution was heated to 50°C, 28 parts by weight of main material (hydroxyl-terminated organosiloxane with viscosity <200 cs 85%, graphene oxide-modified hydroxyl-terminated organosiloxane prepared in preparation example 1-1 5%, acryloxy-modified hydroxyl-terminated organosiloxane prepared in preparation example 2-1 10%) and 10 parts by weight of modifier (A component added with modifier I KH602, B component added with modifier II KH560) and other adjusting agents as needed were added in proportion;

[0099] 3. After keeping constant temperature for 5 hours, add appropriate amount of pH regulator (sodium hydroxide aqueous solution) to adjust pH value to 8, (pH of B component is adjusted to 7±0.5 to ensure stability of epoxy group) and discharge for packaging; both A component and B component are prepared according to steps 1-3 above.

[0100] Preparation Example 3-2

[0101] 1. Add 70 parts by weight of water, 1 part by weight of catalyst (starch phosphate), 5 parts by weight of emulsifier (Span-Tween series, S-80 / T-80=1:2 is selected for A component and S-80 / T-80=1:1 is selected for B component in this example), and stir uniformly, then add appropriate amount of pH regulator (lithium hydroxide aqueous solution) to adjust pH value to 6;

[0102] 2. Heat the mixed solution to 80℃, add 15 parts by weight of main material (20% of hydroxyl-terminated organosiloxane with viscosity <200cs, 30% of graphene oxide modified hydroxyl-terminated organosiloxane prepared in Preparation Example 1-2, 50% of acryloxy-modified hydroxyl-terminated organosiloxane prepared in Preparation Example 2-2) and modifier (KH550 is added as modifier I for A component and KH562 is added as modifier II for B component), and other adjusting agents as needed;

[0103] 3. After keeping constant temperature for 1 hour, add appropriate amount of pH regulator (lithium hydroxide aqueous solution) to adjust pH value to 6, (pH of B component is adjusted to 7±0.5 to ensure stability of epoxy group) and discharge for packaging; both A component and B component are prepared according to steps 1-3 above.

[0104] Preparation Example 3-3

[0105] 1. Add 60 parts by weight of water, 5 parts by weight of catalyst (alginic acid), 10 parts by weight of emulsifier (isotridecanol ether series, 1350 / 1310 1:1 mixture is selected for A component and 1360 is selected for B component in this example), and stir uniformly, then add appropriate amount of pH regulator (sodium hydroxide aqueous solution) to adjust pH value to 5;

[0106] 2. Heat the mixed solution to 60℃, add 20 parts by weight of main material (80% of hydroxyl-terminated organosiloxane with viscosity <200cs, 10% of graphene oxide modified hydroxyl-terminated organosiloxane prepared in Preparation Example 1-3, 10% of acryloxy-modified hydroxyl-terminated organosiloxane prepared in Preparation Example 2-2) and modifier (KH792 is added as modifier I for A component and KH560 is added as modifier II for B component), and other adjusting agents as needed;

[0107] 3. After keeping the temperature constant for 3 hours, add an appropriate amount of pH adjuster to adjust the pH value to 7 (the B component is adjusted to 7±0.5 to ensure the stability of the epoxy group), and discharge and package; both the A component and the B component are prepared according to the above steps 1-3.

[0108] Preparation Example 3-4 Non-oxidized graphene modified organosiloxane

[0109] 1. Add 60 parts by weight of water, 8 parts by weight of catalyst (polyacrylic acid and starch phosphate in a mass ratio of 1:1), and 15 parts by weight of emulsifier (isomeric tridecanol ether series, in this embodiment, the A component is selected to be 1350 / 1380 in a mass ratio of 1:1, and the B component is selected to be 1330 / 1360 in a mass ratio of 1:1), stir uniformly, and then add an appropriate amount of pH adjuster (lithium hydroxide aqueous solution) to adjust the pH value to 4;

[0110] 2. Heat the mixed solution to 60°C, add 15 parts by weight of main material (80% of hydroxyl-terminated organosiloxane with a viscosity of less than 200 cs and 20% of acryloxy-modified hydroxyl-terminated organosiloxane prepared in Preparation Example 2-1) and modifier (KH602 is added as modifier I for the A component, and KH562 is added as modifier II for the B component), and other adjusters as needed;

[0111] 3. After keeping the temperature constant for 2 hours, add an appropriate amount of pH adjuster (lithium hydroxide aqueous solution) to adjust the pH value to 8 (the B component is adjusted to 7±0.5 to ensure the stability of the epoxy group), and discharge and package; both the A component and the B component are prepared according to the above steps 1-3.

[0112] Preparation Example 3-5 Non-oxidized graphene modified organosiloxane

[0113] 1. Add 65 parts by weight of water, 3 parts by weight of catalyst (polyacrylic acid, starch phosphate, and alginic acid in a mass ratio of 1:1:1), and 15 parts by weight of emulsifier (span-tween series, in this embodiment, the A component is selected to be S-80 / T-80 in a mass ratio of 3:7, and the B component is selected to be S-80 / T-80 in a mass ratio of 4:6), stir uniformly, and then add an appropriate amount of pH adjuster (sodium hydroxide aqueous solution) to adjust the pH value to 5;

[0114] 2. Heat the mixed solution to 50°C, add 25 parts by weight of main material (60% of hydroxyl-terminated organosiloxane with a viscosity of less than 200 cs and 40% of acryloxy-modified hydroxyl-terminated organosiloxane prepared in Preparation Example 2-1) and modifier, and other adjusters as needed;

[0115] 3. After keeping the temperature constant for 4 hours, add an appropriate amount of pH adjuster (aqueous sodium hydroxide solution) to adjust the pH value to 7 (the B component is adjusted to 7±0.5 to ensure the stability of the epoxy group) and discharge for packaging; the A component and the B component are prepared according to steps 1-3 above.

[0116] Example 1

[0117] The A component and the B component prepared in Preparation Example 3-1 are configured according to a molar ratio of 1:1 of the epoxy value and the ammonia value, and the configured mixture is added to a battery negative carbon powder treatment aqueous solution at a ratio of 5%-10% of the weight of the battery negative carbon powder treatment aqueous solution. After the treatment process is completed, the treated carbon powder is obtained by centrifugal dewatering and drying. The silane treatment agent prepared in this example does not contain other additives.

[0118] Moisture-proof performance test method: 10±0.5g of carbon powder is evenly spread on a 60mm diameter surface dish, and placed in a constant humidity device at room temperature and 50% humidity. The weight is measured every 1h to calculate the water content.

[0119] Resistivity test method: dry powder is loaded into an insulating mold, pressed into a tablet, and the thickness and diameter are accurately measured. The resistance is measured by a resistance meter, and the resistivity is calculated by combining the size and pressure value.

[0120] Resistivity = resistance value * tablet cross-sectional area / tablet thickness

[0121] Table 3

[0122]

[0123] Example 2

[0124] The A component and the B component prepared in Preparation Example 3-4 are configured according to a molar ratio of 1.1:1 of the epoxy value and the ammonia value, and are used for carbon powder treatment. In this example, the silane treatment agent contains other additives. Specifically, 3 parts by weight of hydrophobic modifier, dodecyl triethoxysilane, is added to the A component and the B component (another part without the hydrophobic modifier is prepared as a comparison). The specific steps are as follows:

[0125] (1) The A component and the B component are mixed uniformly according to the ratio, diluted with 10-20 times water, and then added to the production system.

[0126] (2) Stir and mix with the powder for more than 30 minutes (room temperature to 80°C).

[0127] (3) Dry the powder by A method or B method to obtain the treated powder.

[0128] A method: filter the clear liquid, add a tumbling and drying device, tumble at a temperature above 80°C for 30-120 minutes, and obtain the qualified treated powder.

[0129] B method: the mixed solution is added into a spray drying pretreatment box, preheated to 80°C or above for 30-90 minutes, and spray dried to obtain a qualified powder.

[0130] The contact angle test method is performed according to ASTM D7334 (sessile drop method), and the contact angle < 90° is hydrophilic, 90-110° is hydrophobic, and ≥ 110° is superhydrophobic.

[0131] Table 4

[0132]

[0133] From the above results, (1) the contact angle of the epoxy resin treated is between 80-90, which cannot reach above 90;

[0134] (2) the contact angle of the active silicone oil emulsion treated is between 90-100, but due to insufficient film forming effect on the powder surface, the water droplets can quickly penetrate;

[0135] (3) the addition of hydrophobic modifier is to strengthen the hydrophobic effect, and without the addition of hydrophobic treatment agent, the powder surface can also be well wrapped and formed into a film, with a hydrophobic non-penetration effect.

[0136] Example 3

[0137] The A component and the B component prepared in Preparation Example 3-4 are configured according to the molar ratio of epoxy value to ammonia value 1:1, and are used for surface functionalization treatment of PVC toy accessories, pipe materials and pipe fittings, and non-wear accessories of automotive interior decoration. In this embodiment, other modifiers are added to the silane treatment agent during preparation. Specifically, 3 parts by weight of oil-repellent modifier trifluoromethyl triethoxysilane + di(trifluoromethyl) diethoxysilane are added to the A component and the B component, and the details are as follows:

[0138] (1) After the A and B components are uniformly mixed according to the proportion, 2-10 times water is added for dilution to a sprayable viscosity.

[0139] (2) The mixed solution after dilution is uniformly sprayed on the surface of the material to be treated.

[0140] (3) The A method, the B method or the C method is used for drying and curing, and the surface functionalization treatment is completed.

[0141] A method: drying at 80°C or above for at least 2 hours, and after the water is completely volatilized, the surface functionalization treatment is completed.

[0142] B method: UV light irradiation for 1-10 minutes or sunlight irradiation for 30-120 minutes, and after drying (at room temperature or with heating), the surface functionalization treatment is completed.

[0143] C method: The surface functionalization treatment can be completed after 24-72 hours of natural drying at room temperature in a light-free environment.

[0144] The contact angle test method is performed according to ASTM D7334 (sessile drop method), and the contact angle < 90° is hydrophilic, 90-110° is hydrophobic, and ≥ 110° is super-hydrophobic.

[0145] Table 5

[0146]

[0147] Example 4

[0148] The A component and the B component prepared in Preparation Example 3-5 are configured according to a molar ratio of 1.1:1 of the epoxy value and the ammonia value, and are used for the surface functionalization treatment of ceramic tiles. In this embodiment, other modifiers are added to the silane treatment agent during preparation. Specifically, 5 parts by weight of trifluoromethyltrimethoxysilane, an oil-repellent modifier, is added to each of the A component and the B component, and the details are as follows:

[0149] (1) After the A component and the B component are uniformly mixed according to the proportions, 2-10 times water is added to dilute the mixture to a sprayable viscosity.

[0150] (2) The diluted mixture is uniformly sprayed on the surface of the material to be treated.

[0151] (3) The A method, the B method, or the C method is used for drying and curing, and the surface functionalization treatment can be completed.

[0152] A method: The surface functionalization treatment can be completed after at least 2 hours of drying at 80°C or above.

[0153] B method: The surface functionalization treatment can be completed after 1-10 minutes of UV light irradiation or 30-120 minutes of sunlight irradiation, followed by drying (at room temperature or with heating).

[0154] C method: The surface functionalization treatment can be completed after 24-72 hours of natural drying at room temperature in a light-free environment.

[0155] The contact angle test method is performed according to ASTM D7334 (sessile drop method), and the contact angle < 90° is hydrophilic, 90-110° is hydrophobic, and ≥ 110° is super-hydrophobic.

[0156] Table 6

[0157]

[0158] Example 5

[0159] The A component and B component prepared from Preparation Example 3-5 were configured according to the molar ratio of epoxy value, ammonia value 1.1:1, and were also used for the antifouling treatment of building, highway railings, signs, and automobile glass surfaces. In this embodiment, other modifiers were added during the preparation of the silane treatment agent. In one specific case, no oleophobic modifier was added to the A component and the B component as a comparison. In another specific case, the A component and the B component were both added with 2 parts by weight of trifluoromethyl triethoxysilane + 3 parts by weight of bis(trifluoromethyl)diethoxysilane as an oleophobic modifier. The details are as follows:

[0160] (1) The A component and the B component were mixed uniformly according to the proportions, and then diluted with 2-10 times water to a sprayable viscosity.

[0161] (2) The diluted mixture was uniformly sprayed on the surface of the material to be treated.

[0162] (3) The A method, the B method, or the C method was used for drying and curing, and the surface functionalization treatment was completed.

[0163] A method: drying at an environment above 80°C for at least 2 hours, and after the water was completely volatilized, the surface functionalization treatment was completed.

[0164] B method: ultraviolet light irradiation for 1-10 minutes or sunlight irradiation for 30-120 minutes, and after drying (at room temperature or with heating), the surface functionalization treatment was completed.

[0165] C method: natural drying at room temperature in a dark environment for 24-72 hours, and the surface functionalization treatment was completed.

[0166] The contact angle test method was performed according to ASTM D7334 (sessile drop method). A contact angle < 90° was hydrophilic, a contact angle of 90-110° was hydrophobic, and a contact angle ≥ 110° was superhydrophobic.

[0167] Table 7

[0168]

[0169]

[0170] The above results of Examples 3-5 show that (1) the antifouling effect of the epoxy resin treatment is poor: it is difficult to erase the marker writing;

[0171] (2) the antifouling effect of the active silicone oil emulsion treatment is general and not durable, and the antifouling effect is lost after repeated wiping 3-5 times;

[0172] (3) the addition of the oleophobic modifier is to strengthen the antifouling effect, and the treatment agent without the addition of the oleophobic modifier also has a certain antifouling effect and is durable (the antifouling effect is still present after repeated wiping more than 10 times).

[0173] Obviously, the embodiments described are only some of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

Claims

1. A multifunctional emulsion silane treatment agent, characterized in that: The invention comprises component A and component B, wherein component A comprises the following raw materials in parts by weight: 15-28 parts of main material, 50-70 parts of water, 1-10 parts of catalyst, 0.1-10 parts of pH regulator, 5-20 parts of emulsifier, 0-10 parts of dispersant, and 2-10 parts of modifier I; and component B comprises the following raw materials in parts by weight: 15-28 parts of main material, 50-70 parts of water, 1-10 parts of catalyst, 0.1-10 parts of pH regulator, 5-20 parts of emulsifier, 0-10 parts of dispersant, and 2-10 parts of modifier II; The main ingredients in component A and component B include hydroxyl-terminated organic siloxane with a viscosity of less than 200 cs, graphene oxide-modified hydroxyl-terminated organic siloxane, and acryloxy-modified hydroxyl-terminated organic siloxane. The modifier I contains amino silane, and the modifier II contains epoxy silane.

2. A multifunctional emulsion silane treating agent according to claim 1, characterized in that, The main ingredients in component A and component B both include the following raw materials in the following mass ratios: 20-90% of hydroxyl-terminated organic siloxane with a viscosity of less than 200 cs, 0-30% of graphene oxide-modified hydroxyl-terminated organic siloxane, and 10-50% of acryloxy-modified hydroxyl-terminated organic siloxane.

3. A multifunctional emulsion silane treating agent according to claim 1, characterized in that: The graphene oxide modified hydroxyl-terminated organosiloxane is prepared by the following method: (1) Pretreatment: 100 parts by weight of hydroxyl-terminated organosiloxane with a viscosity of less than 200 cs and 0.1-10 parts by weight of graphene oxide powder were mechanically stirred for 5-10 minutes, stirred for 20-40 minutes using a high-speed shearing machine, and ultrasonically treated for 0.5-6 hours before being added to a reactor; (2) Modification reaction: The reactor is heated to 140-160°C, and the reaction is continued for 1-5 hours after the materials in the reactor react smoothly without obvious sound. The temperature is then raised to 170-200°C and the reaction is continued for 10-60 minutes. The unreacted graphene oxide powder is removed by centrifugation to obtain graphene oxide modified hydroxyl-terminated organosiloxane, which is then cooled to room temperature and packaged for later use.

4. A multifunctional emulsion silane treating agent according to claim 1, characterized in that: Acryloyloxy-modified hydroxyl-terminated organosiloxane is prepared by the following method: (1) Pretreatment: Mix one or more of KH570, KH571, and KH572 to obtain a mixture A; mix 100 parts by weight of the mixture A with 1-10 parts by weight of water, heat to 60-80° C., react for 20-120 minutes, remove unreacted water and alcohol formed by the reaction under vacuum to obtain an acryloxysiloxane prepolymer, cool to room temperature, and package for later use; (2) Modification reaction: 100 parts by weight of a hydroxyl-terminated organosiloxane with a viscosity of less than 200 cs, 1-20 parts by weight of an acryloxysiloxane prepolymer, and 0.01-0.5 parts by weight of KOH are mechanically stirred for 5-10 minutes, heated to 110-150° C., reacted for 1-5 hours, and neutralized by adding phosphoric acid with a mass ratio of 140% to 170% of the KOH. The water and small molecular weight siloxane are removed in vacuo to obtain an acryloxy-modified hydroxyl-terminated organosiloxane. The mixture is cooled to room temperature and packaged for later use.

5. A multifunctional emulsion silane treating agent according to any one of claims 1 to 4, characterized in that: In component A and component B, the catalyst is one or more of polyacrylic acid, starch phosphate, alginic acid, etc., the pH adjuster is a sodium hydroxide aqueous solution or a lithium hydroxide aqueous solution, the emulsifier is an isomeric tridecyl alcohol ether series or a Span-Tween series, and the dispersant is a polyether silicone oil; the modifier I is KH602, KH550 or KH792, and the modifier II is KH560 or KH562.

6. A multifunctional emulsion silane treating agent according to claim 5, characterized in that: The multifunctional emulsion-type silane treatment agent further comprises the following regulators as needed: a hydrophobic regulator, a temperature-resistant regulator or an oiliness regulator.

7. The method for preparing a multifunctional emulsion silane treating agent according to claim 6, characterized in that: Component A is prepared as follows: (1) adding water, catalyst, and emulsifier in proportion, stirring evenly, and then adding a pH regulator to adjust the pH value to 4-6; (2) heating the mixed solution to 50-80°C, adding the main ingredient and modifier I in proportion, and adding a regulator as needed; (3) maintaining a constant temperature for 1-5 hours, adding a pH regulator to adjust the pH value to 6-8, and then discharging and packaging; Component B is prepared as follows: (1) water, catalyst, and emulsifier are added in proportion, stirred evenly, and then a pH regulator is added to adjust the pH value to 4-6; (2) the mixture is heated to 50-80°C, and the main ingredients and modifier II, as well as regulators as needed, are added in proportion; (3) the reaction is maintained at a constant temperature for 1-5 hours, and then a pH regulator is added to adjust the pH value to 7±0.5 and the material is discharged and packaged.

8. The multifunctional emulsion silane treatment agent according to any one of claims 1 to 6 and the method for using the multifunctional emulsion silane treatment agent prepared by the method according to claim 7, characterized in that: Component A and component B are configured and used according to the epoxy value and ammonia value molar ratio of 1-1.1:

1.

9. The method of use according to claim 8, characterized in that: When used for powder processing, proceed as follows: (1) After mixing components A and B evenly in proportion, add 10-20 times water to dilute and then add to the production system; (2) Stirring and mixing with the powder for more than 30 minutes at a temperature ranging from room temperature to 80°C; (3) Drying the powder using method A or method B to obtain the treated powder; Method A: Filter to remove the clear liquid, add the powder into the stir-fry drying equipment, stir-fry at a temperature above 80°C for 30-120 minutes to obtain qualified powder; Method B: Add the mixed liquid into the spray drying pretreatment box, preheat to above 80℃ for 30-90 minutes, and spray dry to obtain qualified powder.

10. The method of use according to claim 8, characterized in that: When used for surface functionalization of spare parts and tiles, proceed as follows: (1) After mixing components A and B in proportion, add 2-10 times water to dilute to a sprayable viscosity; (2) Spray the diluted mixed solution evenly on the surface of the material to be treated; (3) Drying and curing by method A, method B or method C can complete the surface functionalization treatment; Method A: Dry in an environment above 80°C for at least 2 hours. After the water is completely evaporated, the surface functionalization treatment is completed. Method B: Expose to UV light for 1-10 minutes or sunlight for 30-120 minutes. After drying, the surface functionalization treatment is completed. Method C: After natural drying at room temperature in a lightless environment for 24-72 hours, the surface functionalization treatment can be completed.

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