Acrylic resin glue and preparation method thereof

Abstract

The invention relates to the field of acrylic resin, in particular to acrylic resin glue and a preparation method thereof. Comprising 17 to 34 parts of an acrylic monomer, 2 to 7 parts of a propylene modified monomer, 0.5 to 2.5 parts of vinyl acetate, 1 to 5 parts of nano-silica, 0.6 to 1.8 parts of an emulsifier, 0.1 to 0.5 part of a thickening agent, 0.1 to 0.5 part of a leveling agent, 0.1 to 0.3 part of an initiator, 0.4 to 1.2 parts of a neutralizer and 35 to 55 parts of deionized water. In the water-based glue prepared by the invention, besides the acrylic acid monomer, the propylene modified monomer is also added as a reinforcing modifier, so that the brittleness problem of the water-based glue is well improved, and the problem that the water-based glue is easy to crack and fall off after being used for a long time is solved. In addition, the addition of the propylene modified monomer can accelerate the drying speed of the water-based acrylic glue under the conditions of low temperature and high humidity to a certain extent.

Description

Technical Field

[0001] The invention relates to the field of acrylic resins, and in particular to acrylic resin glue and a preparation method thereof. Background Art

[0002] Traditional solvent-based glues contain too many volatile organic compounds due to the use of organic solvents, which is not only a waste of resources, but also has great damage to human health and the environment. Water-based glues do not contain VOCs or their content is extremely low, and have excellent environmental performance. With the requirements for environmental protection at home and abroad, the research and application of water-based glues have received widespread attention. Water-based acrylic glue is an environmentally friendly adhesive with water as the dispersion medium, which is widely used in the bonding of materials such as paper, plastics, and textiles.

[0003] Water-based glue can be mainly divided into water-based acrylic glue, water-based epoxy glue, water-based alkyd glue and water-based polyurethane glue according to the type of resin. Water-based acrylic glue is widely used in packaging, construction, automobile manufacturing and electronics industries due to its advantages such as low cost, simple construction and good performance. Water-based acrylic glue is mainly made of acrylate monomers (such as n-butyl acrylate and isooctyl acrylate) through emulsion polymerization. In addition, the formula may also contain cross-linking agents, emulsifiers, initiators and other additives to optimize performance.

[0004] Water-based acrylic glue has excellent properties such as easy cleaning, high adhesion, and rich color selection. However, it is sensitive to temperature and humidity, has high requirements for construction conditions, and dries slowly under low temperature and high humidity conditions. It also has brittleness problems, and is easy to soften and debond in humid or long-term water-immersion environments, and is prone to cracking and falling off. Summary of the invention

[0005] In view of the problems existing in the prior art, the object of the present invention is to provide an acrylic resin glue and a preparation method thereof.

[0006] The purpose of the present invention is achieved by the following technical solutions:

[0007] In a first aspect, the present invention provides an acrylic resin glue, calculated by weight, comprising:

[0008] 17-34 parts of acrylic monomer, 2-7 parts of propylene modified monomer, 0.5-2.5 parts of vinyl acetate, 1-5 parts of nano-silicon dioxide, 0.6-1.8 parts of emulsifier, 0.1-0.5 parts of thickener, 0.1-0.5 parts of leveling agent, 0.1-0.3 parts of initiator, 0.4-1.2 parts of neutralizer and 35-55 parts of deionized water.

[0009] Preferably, the acrylic monomer is at least one of acrylic acid, methacrylic acid, methyl acrylate, butyl acrylate, methyl methacrylate, and diethylaminoethyl methacrylate.

[0010] More preferably, the acrylic monomer is a mixture of acrylic acid, butyl acrylate, methyl methacrylate, and diethylaminoethyl methacrylate in a mass ratio of 1:0.2 - 0.4:0.3 - 0.8:0.8 - 1.2.

[0011] Preferably, the emulsifier is at least one of sodium dodecyl sulfate (SDS), polysorbate - 20 (Tween - 20), and polysorbate - 80 (Tween - 80).

[0012] Preferably, the thickener is at least one of methyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, and hydroxypropyl methyl cellulose.

[0013] Preferably, the leveling agent is at least one of BYK - 333, BYK - 381, and BYK - 349.

[0014] Preferably, the initiator is at least one of sodium persulfate, ammonium persulfate, and tert - butyl hydroperoxide.

[0015] Preferably, the neutralizing agent is at least one of triethylamine, ammonia water, and dimethylethanolamine.

[0016] Preferably, the preparation method of the propylene - modified monomer includes:

[0017] S1. Weigh 2 - methylacrolein and 2 - aminocyclohexanol, add them into an organic solvent, introduce an inert gas as a protective gas, and stir magnetically until uniform to obtain a mixed reaction solution;

[0018] S2. Place the mixed reaction solution in a water bath, dropwise add an acidic catalyst, and reflux and stir the reaction at 55 - 75 °C for 10 - 20 h, continuously separating water during this period. After the reaction ends, rotary evaporate to remove the solvent, perform recrystallization treatment, and then dry to obtain the propylene - modified monomer.

[0019] Preferably, in S1, the mass - to - volume ratio of 2 - methylacrolein, 2 - aminocyclohexanol, and the organic solvent is (0.7 - 1.4) g:(1.2 - 2.4) g:(5 - 15) mL.

[0020] Preferably, in S1, the inert gas is one of helium, argon, neon, and xenon.

[0021] Preferably, in S1, the organic solvent is one of methanol, ethanol, dimethyl sulfoxide, and N,N - dimethylformamide.

[0022] Preferably, in the step S2, the acidic catalyst is glacial acetic acid or concentrated hydrochloric acid, and the addition amount is 2%-8% of the mass of 2-methylacrolein.

[0023] Preferably, in the step S2, the solvent for recrystallization treatment is a mixed solution of ethanol and n-hexane in a ratio of 1:1-3.

[0024] In a second aspect, the present invention provides a method for preparing an acrylic resin glue, comprising the following steps:

[0025] Step 1, weigh acrylic monomers, propylene-modified monomers, vinyl acetate and an emulsifier, add them to deionized water, and shear and stir at a speed of 4000-8000 rpm until uniform to obtain a mixed emulsion;

[0026] Step 2, add an initiator to the mixed emulsion, heat it to 45-55°C under the protection of nitrogen, and stir for 1.2-2 h to obtain a polymerized emulsion;

[0027] Step 3, add nano-silica to the polymerized emulsion cooled to room temperature, mix well, and then sequentially add a thickener, a leveling agent and a neutralizing agent, and stir well to obtain the acrylic resin glue.

[0028] The beneficial effects of the present invention are as follows:

[0029] 1. The present invention prepares an aqueous acrylic resin glue, the main components of which include acrylic monomers, propylene-modified monomers and vinyl acetate. Among them, the acrylic monomers are used as the basic monomers, the propylene-modified monomers are used as the modified and enhanced monomers, and vinyl acetate can enhance the viscosity and film-forming property of the emulsion. In addition, the present invention also adds nano-silica to improve the system viscosity and thixotropy.

[0030] 2. In the aqueous glue prepared by the present invention, in addition to acrylic monomers, a propylene-modified monomer is added as an enhancing modifier, which can better improve the brittleness problem of the aqueous glue and solve the problem of cracking and peeling that easily occurs during long-term use. In addition, the addition of the propylene-modified monomer can accelerate the drying speed of the aqueous acrylic glue under low-temperature and high-humidity conditions to a certain extent.

[0031] 3. The propylene-modified monomer is prepared from 2-methylacrolein and 2-aminocyclohexanol as raw materials through an aldehyde-amine condensation reaction. The prepared propylene-modified monomer contains not only olefin bonds but also amide groups and cyclohexyl groups. Through detection, it is found that the introduction of the propylene-modified monomer into the aqueous glue has a certain enhancing effect on the drying speed, strength, brittleness and weather resistance of the glue. Description of the Drawings

[0032] The present invention is further described using the accompanying drawings, but the embodiments in the accompanying drawings do not constitute any limitation to the present invention. A person skilled in the art can obtain other drawings based on the following drawings without creative work.

[0033] Figure 1 is a schematic diagram of the acrylic resin glue prepared in Example 1 of the present invention being coated on a non-woven fabric and dried;

[0034] Figure 2 It is a schematic diagram of the acrylic resin glue prepared in Example 1 of the present invention after being coated on a cement floor and dried. DETAILED DESCRIPTION

[0035] The technical solution of the present invention is described below through specific examples. It should be understood that the one or more method steps mentioned in the present invention do not exclude the existence of other method steps before and after the combination step or the insertion of other method steps between these explicitly mentioned steps; it should also be understood that these embodiments are only used to illustrate the present invention and are not used to limit the scope of the present invention. Moreover, unless otherwise specified, the numbering of each method step is only a convenient tool for identifying each method step, and is not intended to limit the order of arrangement of each method step or to limit the scope of the present invention. The change or adjustment of the relative relationship thereof shall also be regarded as the scope of the present invention without substantially changing the technical content.

[0036] In order to better understand the above technical scheme, the exemplary embodiments of the present invention are described in more detail below. Although exemplary embodiments of the present invention are shown, it should be understood that the present invention can be implemented in various forms and should not be limited by the embodiments set forth herein. On the contrary, these embodiments are provided in order to enable a more thorough understanding of the present invention and to enable the scope of the present invention to be fully communicated to those skilled in the art.

[0037] The present invention will be further described below in conjunction with the following examples.

[0038] Example 1

[0039] An acrylic resin glue, calculated by weight, comprising:

[0040] 25 parts of acrylic monomer, 5 parts of propylene modified monomer, 1.5 parts of vinyl acetate, 3 parts of nano-silicon dioxide, 1.2 parts of emulsifier, 0.3 parts of thickener, 0.2 parts of leveling agent, 0.2 parts of initiator, 0.8 parts of neutralizer and 45 parts of deionized water.

[0041] The acrylic monomer is a mixture of acrylic acid, butyl acrylate, methyl methacrylate and diethylaminoethyl methacrylate in a mass ratio of 1:0.3:0.5:1.

[0042] Among them, the emulsifier is sodium dodecyl sulfate (SDS); the thickener is hydroxyethyl cellulose; the leveling agent is BYK-333; the initiator is sodium persulfate; and the neutralizer is triethylamine.

[0043] Wherein, the preparation method of propylene modified monomer comprises:

[0044] S1. Weigh 1.1 g of 2-methylacrolein and 1.8 g of 2-aminocyclohexanol and add them to 10 mL of ethanol, introduce argon as a protective gas, and stir magnetically until uniform to obtain a mixed reaction solution;

[0045] S2. Place the mixed reaction liquid in a water bath, build a condensation reflux device, add glacial acetic acid dropwise in an amount of 5% of the mass of 2-methylacrolein, reflux and stir the reaction at 65°C for 15 hours, during which the generated water is continuously removed from the reaction system using a water separator. After the reaction is completed, remove the solvent by rotary evaporation, and dry after recrystallization with n-hexane / ethanol in a volume ratio of 1:2 to obtain a propylene modified monomer.

[0046] The preparation method of the acrylic resin glue comprises the following steps:

[0047] Step 1, weighing acrylic monomer, propylene modified monomer, vinyl acetate and emulsifier, adding them into deionized water, and shearing and stirring at a speed of 6000 rpm until uniform, to obtain a mixed emulsion;

[0048] Step 2, adding an initiator to the mixed emulsion, heating to 50° C. under the protection of nitrogen, and stirring for 1.6 hours to obtain a polymer emulsion;

[0049] Step 3, adding nano-silicon dioxide to the polymer emulsion cooled to room temperature, mixing thoroughly and evenly, and then sequentially adding a thickener, a leveling agent and a neutralizer, stirring thoroughly and evenly to obtain acrylic resin glue.

[0050] Example 2

[0051] An acrylic resin glue, calculated by weight, comprising:

[0052] 17 parts of acrylic monomer, 2 parts of propylene modified monomer, 0.5 parts of vinyl acetate, 1 part of nano-silicon dioxide, 0.6 parts of emulsifier, 0.1 parts of thickener, 0.1 parts of leveling agent, 0.1 parts of initiator, 0.4 parts of neutralizer and 35 parts of deionized water.

[0053] The acrylic monomer is a mixture of acrylic acid, butyl acrylate, methyl methacrylate and diethylaminoethyl methacrylate in a mass ratio of 1:0.2:0.3:0.8.

[0054] Among them, the emulsifier is polysorbate-20 (Tween-20); the thickener is methyl cellulose; the leveling agent is BYK-381; the initiator is ammonium persulfate; and the neutralizer is ammonia water.

[0055] Wherein, the preparation method of propylene modified monomer comprises:

[0056] S1. Weigh 0.7 g of 2-methylacrolein and 1.2 g of 2-aminocyclohexanol and add them to 5 mL of ethanol, introduce argon as a protective gas, and stir magnetically until uniform to obtain a mixed reaction solution;

[0057] S2. Place the mixed reaction liquid in a water bath, build a condensation reflux device, add glacial acetic acid dropwise in an amount of 2% of the mass of 2-methylacrolein, reflux and stir the reaction at 55°C for 10 hours, during which the generated water is continuously removed from the reaction system using a water separator. After the reaction is completed, remove the solvent by rotary evaporation, and dry after recrystallization with n-hexane / ethanol in a volume ratio of 1:1 to obtain a propylene modified monomer.

[0058] The preparation method of the acrylic resin glue comprises the following steps:

[0059] Step 1, weighing acrylic monomer, propylene modified monomer, vinyl acetate and emulsifier, adding them into deionized water, and shearing and stirring at a speed of 4000 rpm until uniform, to obtain a mixed emulsion;

[0060] Step 2, adding an initiator to the mixed emulsion, heating to 45° C. under the protection of nitrogen, and stirring for 1.2 hours to obtain a polymer emulsion;

[0061] Step 3, adding nano-silicon dioxide to the polymer emulsion cooled to room temperature, mixing thoroughly and evenly, and then sequentially adding a thickener, a leveling agent and a neutralizer, stirring thoroughly and evenly to obtain acrylic resin glue.

[0062] Example 3

[0063] An acrylic resin glue, calculated by weight, comprising:

[0064] 34 parts of acrylic monomer, 7 parts of propylene modified monomer, 2.5 parts of vinyl acetate, 5 parts of nano silicon dioxide, 1.8 parts of emulsifier, 0.5 parts of thickener, 0.5 parts of leveling agent, 0.3 parts of initiator, 1.2 parts of neutralizer and 55 parts of deionized water.

[0065] The acrylic monomer is a mixture of acrylic acid, butyl acrylate, methyl methacrylate and diethylaminoethyl methacrylate in a mass ratio of 1:0.4:0.8:1.2.

[0066] Among them, the emulsifier is polysorbate-80 (Tween-80); the thickener is hydroxypropyl methylcellulose; the leveling agent is BYK-349; the initiator is tert-butyl hydroperoxide; and the neutralizer is dimethylethanolamine.

[0067] Wherein, the preparation method of propylene modified monomer comprises:

[0068] S1. Weigh 1.4 g of 2-methylacrolein and 2.4 g of 2-aminocyclohexanol and add them to 15 mL of ethanol, introduce argon as a protective gas, and stir magnetically until uniform to obtain a mixed reaction solution;

[0069] S2. Place the mixed reaction liquid in a water bath, build a condensation reflux device, add glacial acetic acid dropwise in an amount of 8% of the mass of 2-methylacrolein, reflux and stir the reaction at 75°C for 20 hours, during which the generated water is continuously removed from the reaction system using a water separator. After the reaction is completed, remove the solvent by rotary evaporation, and dry after recrystallization with n-hexane / ethanol in a volume ratio of 1:3 to obtain a propylene modified monomer.

[0070] The preparation method of the acrylic resin glue comprises the following steps:

[0071] Step 1, weighing acrylic monomer, propylene modified monomer, vinyl acetate and emulsifier, adding them into deionized water, and shearing and stirring at a speed of 8000 rpm until uniform, to obtain a mixed emulsion;

[0072] Step 2, adding an initiator to the mixed emulsion, heating to 55° C. under the protection of nitrogen, and stirring for 2 hours to obtain a polymer emulsion;

[0073] Step 3, adding nano-silicon dioxide to the polymer emulsion cooled to room temperature, mixing thoroughly and evenly, and then sequentially adding a thickener, a leveling agent and a neutralizer, stirring thoroughly and evenly to obtain acrylic resin glue.

[0074] Comparative Example 1

[0075] An acrylic resin glue, which differs from Example 1 in that the propylene-modified monomer is replaced by an acrylic monomer of equal mass, and the other components and preparation method are the same as those of Example 1. Calculated by weight, it includes:

[0076] 30 parts of acrylic monomer, 1.5 parts of vinyl acetate, 3 parts of nano-silicon dioxide, 1.2 parts of emulsifier, 0.3 parts of thickener, 0.2 parts of leveling agent, 0.2 parts of initiator, 0.8 parts of neutralizer and 45 parts of deionized water.

[0077] Comparative Example 2

[0078] An acrylic resin glue, which differs from Example 1 in that the propylene-modified monomer is replaced by an equal amount of 2-methylacrolein, and the other components and preparation method are the same as those of Example 1. Calculated by weight, it includes:

[0079] 25 parts of acrylic monomer, 5 parts of 2-methylacrolein, 1.5 parts of vinyl acetate, 3 parts of nano-silicon dioxide, 1.2 parts of emulsifier, 0.3 parts of thickener, 0.2 parts of leveling agent, 0.2 parts of initiator, 0.8 parts of neutralizer and 45 parts of deionized water.

[0080] Comparative Example 3

[0081] An acrylic resin glue, which is different from Example 1 in that the propylene modified monomer is prepared by using 2-methylacrolein and ethylenediamine, and the other components and preparation methods after conversion are the same as those of Example 1. Calculated by weight, it includes:

[0082] 25 parts of acrylic monomer, 5 parts of propylene modified monomer, 1.5 parts of vinyl acetate, 3 parts of nano-silicon dioxide, 1.2 parts of emulsifier, 0.3 parts of thickener, 0.2 parts of leveling agent, 0.2 parts of initiator, 0.8 parts of neutralizer and 45 parts of deionized water.

[0083] Wherein, the preparation method of propylene modified monomer comprises:

[0084] S1. Weigh 1.1 g of 2-methylacrolein and 0.9 g of ethylenediamine and add them to 10 mL of ethanol, introduce argon as a protective gas, and stir magnetically until uniform to obtain a mixed reaction solution;

[0085] S2. Place the mixed reaction liquid in a water bath, build a condensation reflux device, add glacial acetic acid dropwise in an amount of 5% of the mass of 2-methylacrolein, reflux and stir the reaction at 65°C for 15 hours, during which the generated water is continuously removed from the reaction system using a water separator. After the reaction is completed, remove the solvent by rotary evaporation, and dry after recrystallization with n-hexane / ethanol in a volume ratio of 1:2 to obtain a propylene modified monomer.

[0086] Experimental testing

[0087] The performance of the acrylic resin glue prepared in Example 1 and Comparative Examples 1-3 was tested. The testing standard of drying time (coating thickness 50 μm, room temperature: 25°C, 55RH%; low temperature: 5°C, 75RH%) was based on GB / T 1728-1979 method B, the testing standard of hardness was based on GB / T 6739-2022, the testing standard of adhesion was based on GB / T 9286-2021, and the testing standard of flexibility was based on GB / T 1731-2020. The water resistance was tested by immersing in tap water at room temperature for 120 hours to observe whether blistering or shedding occurred.

[0088] The test results are shown in Table 1 as follows:

[0089] Table 1 Performance Tests of Different Glues

[0090]

[0091] As can be seen from Table 1, regarding the surface drying time, by comparing Example 1 (the technology of the present invention) and Comparative Example 1 (the prior art), it can be seen that the surface drying time of Example 1 is faster than that of Comparative Example 1, and it is significantly superior to Comparative Example 1 in terms of hardness, adhesion, flexibility, and water resistance; while although the surface drying time of Comparative Example 2 and Comparative Example 3 is slightly faster than that of Example 1, their performances in other aspects are inferior to Example 1, especially in terms of hardness and water resistance. In summary, it can be shown that the waterborne acrylic glue prepared in Example 1 of the present invention has a relatively fast drying speed, especially with better performance at low temperatures. In addition, it also has the best comprehensive performance in terms of mechanical strength and water resistance.

[0092] In the description of this specification, the description referring to terms such as "one embodiment", "some embodiments", "example", "specific example", or "some examples", etc. means 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 descriptions of the above terms should not be understood as necessarily referring 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, those skilled in the art can combine and combine the different embodiments or examples described in this specification.

[0093] 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. An acrylic resin glue, characterized in that, Calculated by weight parts, it includes: 17 - 34 parts of acrylic monomers, 2 - 7 parts of propylene - modified monomers, 0.5 - 2.5 parts of vinyl acetate, 1 - 5 parts of nano - silica, 0.6 - 1.8 parts of emulsifier, 0.1 - 0.5 parts of thickener, 0.1 - 0.5 parts of leveling agent, 0.1 - 0.3 parts of initiator, 0.4 - 1.2 parts of neutralizer and 35 - 55 parts of deionized water.

2. The acrylic resin glue according to claim 1, characterized in that, The acrylic monomers are at least one of acrylic acid, methacrylic acid, methyl acrylate, butyl acrylate, methyl methacrylate, and diethylaminoethyl methacrylate.

3. An acrylic resin glue according to claim 2, characterized in that, The acrylic monomers are a mixture of acrylic acid, butyl acrylate, methyl methacrylate, and diethylaminoethyl methacrylate in a mass ratio of 1:0.2 - 0.4:0.3 - 0.8:0.8 - 1.

2.

4. An acrylic resin glue according to claim 1, wherein The emulsifier is at least one of sodium dodecyl sulfate, polysorbate - 20, and polysorbate - 80.

5. An acrylic resin glue according to claim 1, characterized in that, The thickener is at least one of methyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, and hydroxypropyl methyl cellulose.

6. The acrylic resin glue according to claim 1, characterized in that, The leveling agent is at least one of BYK - 333, BYK - 381, and BYK - 349.

7. An acrylic resin glue according to claim 1, characterized in that, The initiator is at least one of sodium persulfate, ammonium persulfate, and tert - butyl hydroperoxide; the neutralizer is at least one of triethylamine, ammonia water, and dimethylethanolamine.

8. An acrylic resin glue according to claim 1, characterized in that, The preparation method of the propylene - modified monomer includes: S1. Weigh 2 - methylacrolein and 2 - aminocyclohexanol and add them into an organic solvent. Pass an inert gas as a protective gas. After magnetic stirring until uniform, a mixed reaction solution is obtained. S2. Place the mixed reaction solution in a water - bath kettle, dropwise add an acidic catalyst, and carry out reflux stirring reaction at 55 - 75 °C for 10 - 20 h. During this period, water is continuously separated. After the reaction ends, rotate and evaporate to remove the solvent, and after recrystallization treatment and drying, the propylene - modified monomer is obtained.

9. An acrylic resin glue according to claim 8, characterized in that, In the above S1, the mass - to - volume ratio of 2 - methylacrolein, 2 - aminocyclohexanol, and the organic solvent is (0.7 - 1.4) g:(1.2 - 2.4) g:(5 - 15) mL; in the above S2, the acidic catalyst is glacial acetic acid or concentrated hydrochloric acid, and the addition amount is 2% - 8% of the mass of 2 - methylacrolein.

10. A method for preparing the acrylic resin glue according to claim 1, characterized in that, It includes the following steps: Step 1, weigh acrylic monomers, propylene - modified monomers, vinyl acetate, and emulsifier and add them into deionized water. Shear - stir at a speed of 4000 - 8000 rpm until uniform to obtain a mixed emulsion. Step 2, add an initiator to the mixed emulsion, heat up to 45 - 55 °C under the protection of nitrogen, and stir for 1.2 - 2 h to obtain a polymerization emulsion. Step 3, add nano - silica to the polymerization emulsion cooled to room temperature, mix well, and then add a thickener, a leveling agent, and a neutralizer in sequence, and stir well to obtain the acrylic resin glue.

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