Polyacrylate copolymer emulsion with molecular weight in bimodal distribution and preparation method thereof

Abstract

The invention provides a polyacrylate copolymer emulsion with molecular weight in bimodal distribution and a preparation method thereof, and relates to the technical field of chemical engineering. Comprising the following components in parts by mass: 100 to 200 parts of radiation emulsion seeds, 200 to 300 parts of butyl acrylate, 100 to 20 parts of styrene, 5 to 10 parts of acrylic acid, 2 to 5 parts of N-hydroxymethyl acrylamide, 2 to 3 parts of acrylamide, 3 to 5 parts of peregal (O-25), 4 to 8 parts of sodium dodecyl sulfate (K12) and 584 to 469 parts of deionized water. The radiation emulsion obtained after radiation polymerization is used as a seed, persulfate is used for initiating emulsion polymerization under the high-temperature condition, different from a traditional single reaction system, polymerization reaction is carried out around radiation emulsion macromolecules, macromolecule nuclei are used as depends on the emulsion in the reaction, and polymer emulsion with the molecular weight in bimodal distribution is formed; and the advantages of the irradiation emulsion and the conventional emulsion are considered.

Description

Technical Field

[0001] The invention relates to the technical field of chemical industry, and in particular to a polyacrylate copolymer emulsion with bimodal molecular weight distribution and a preparation method thereof. Background Art

[0002] Emulsions for paint printing adhesives play a vital role in the paint printing process. Their main function is to firmly attach pigments or dyes to fabrics and form a uniform and continuous film. Emulsions for paint printing adhesives mainly include acrylic emulsions, polyurethane emulsions, ethylene-vinyl acetate copolymer emulsions (VAE emulsions), etc. These emulsions have different chemical structures and performance characteristics and are suitable for different printing processes and fabric materials. Acrylic emulsions are one of the most commonly used emulsions in paint printing adhesives. It can be compatible with a variety of pigments and dyes to form a stable printing slurry; polyurethane emulsions are suitable for printed fabrics that require high wear resistance and high elasticity, and VAE emulsions are suitable for a variety of fabric materials and printing processes;

[0003] The performance of the emulsion used in the paint printing adhesive has an important influence on the key indicators of the printing such as friction fastness, abrasion resistance and film-forming strength. In the traditional single reaction system emulsion polymerization method, when preparing paint printing adhesives such as acrylic emulsions, due to the control of the polymerization reaction and the limitations of process conditions, the molecular weight of the emulsion finally obtained is often small. This is mainly because side reactions such as chain transfer are prone to occur during the emulsion polymerization process, resulting in uneven molecular weight distribution of the product and low overall molecular weight, resulting in poor fastness, poor abrasion resistance and other problems. Therefore, the present invention proposes a polyacrylate copolymer emulsion with a bimodal molecular weight distribution and a preparation method thereof to solve the problems existing in the prior art. Summary of the invention

[0004] In view of the above problems, the present invention proposes a polyacrylate copolymer emulsion with a bimodal molecular weight distribution and a preparation method thereof. The polyacrylate copolymer emulsion with a bimodal molecular weight distribution takes into account the advantages of both irradiated emulsion and conventional emulsion, has a better effect on the color fixation performance of paint printing, and can effectively improve the friction fastness, abrasion resistance and film-forming strength and other properties.

[0005] To achieve the purpose of the present invention, the present invention is achieved through the following technical scheme: a polyacrylate copolymer emulsion with a bimodal molecular weight distribution, comprising the following components by weight: 100-200 parts of radiation emulsion seeds, 200-300 parts of butyl acrylate, 100-20 parts of styrene, 5-10 parts of acrylic acid, 2-5 parts of N-hydroxymethyl acrylamide, 2-3 parts of acrylamide, 3-5 parts of peregal (O-25), 4-8 parts of sodium dodecyl sulfonate (K12), and 584-469 parts of deionized water;

[0006] The radiated emulsion seed comprises the following components in mass ratio: 300-350 parts of butyl acrylate, 70-20 parts of styrene, 8-12 parts of acrylic acid, 5-10 parts of N-hydroxymethyl acrylamide, 2-5 parts of acrylamide, 5-15 parts of peregal (O-25), 4-8 parts of sodium dodecyl sulfonate (K12), and 603-580 parts of deionized water.

[0007] The further improvement is that it includes the following components in mass ratio: 150 parts of radiated emulsion seeds, 230 parts of butyl acrylate, 50 parts of styrene, 8 parts of acrylic acid, 3 parts of N-hydroxymethyl acrylamide, 2.5 parts of acrylamide, 4 parts of peregal (O-25), 6 parts of sodium dodecyl sulfonate (K12), and 500 parts of deionized water;

[0008] The radiated emulsion seed comprises the following components in mass ratio: 320 parts of butyl acrylate, 50 parts of styrene, 10 parts of acrylic acid, 7 parts of N-hydroxymethyl acrylamide, 3 parts of acrylamide, 12 parts of peregal (O-25), 6 parts of sodium dodecyl sulfonate (K12), and 595 parts of deionized water.

[0009] A method for preparing a polyacrylate copolymer emulsion with a bimodal molecular weight distribution comprises the following steps:

[0010] S1: putting the components of the irradiated emulsion seeds into an emulsifying tank and dispersing them to obtain a pre-emulsion;

[0011] S2: Take out the pre-emulsified liquid in the emulsification tank, put it into the reaction container, and put it into the radiation chamber for radiation reaction for 4 hours;

[0012] S3: After the irradiation is completed, the emulsion with the corresponding mass ratio is taken out as the irradiated emulsion seeds;

[0013] S4: Mix the irradiated emulsion seeds with other components and disperse them together for emulsification, and take them out after 20 minutes for use;

[0014] S5: Add deionized water and emulsifier into a four-necked flask and heat to 80°C;

[0015] S6: adding the reserved emulsion and ammonium persulfate solution dropwise into the flask to react for 3 hours;

[0016] S7: After the reaction is completed, keep the temperature for 1 hour, cool it down to below 40°C, and discharge the material.

[0017] A further improvement is that in S1, the rotation speed is controlled to 2800 r / min and the dispersion time is controlled to 20 min.

[0018] A further improvement is that in S2, the reaction container has a stirring function, and the stirring speed is controlled to be 200r / min.

[0019] A further improvement is that in S4, during dispersion and emulsification, the rotation speed is controlled to 2500-3000 r / min and the temperature is controlled to room temperature.

[0020] A further improvement is that in S6, during the dropwise addition, the stirring speed is controlled to be 100 r / min.

[0021] The beneficial effects of the present invention are:

[0022] 1. The present invention uses the radiation emulsion after radiation polymerization as a seed to carry out persulfate-initiated emulsion polymerization under high temperature conditions. Different from the traditional single reaction system, the polymerization reaction is carried out around the radiation emulsion macromolecule with a molecular weight of more than 1,000,000, so that the emulsion has a macromolecular core as a support in the reaction to form a polymer emulsion with a bimodal molecular weight distribution. The emulsion takes into account the advantages of the irradiated emulsion and the conventional emulsion, has a better effect on the color fixation performance of the coating printing, and can effectively improve the properties such as friction fastness, abrasion resistance and film-forming strength.

[0023] 2. The preparation method of the present invention is stable, has good repeatability, high efficiency, and high environmental protection. It can effectively improve the comprehensive performance of acrylic emulsion. The prepared acrylic emulsion is non-toxic, has the advantages of good fastness, wear resistance, good elasticity, and ecological protection, and can be applied to high-demand printing products. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 It is a flow chart of the present invention. DETAILED DESCRIPTION

[0025] In order to deepen the understanding of the present invention, the present invention will be further described in detail below in conjunction with examples. The examples are only used to explain the present invention and do not constitute a limitation on the protection scope of the present invention.

[0026] Embodiment 1

[0027] according to Figure 1 As shown, this embodiment proposes a polyacrylate copolymer emulsion with a bimodal molecular weight distribution, including the following components by weight: 50-100 parts of radiation emulsion seeds, 300 parts of butyl acrylate, 50 parts of styrene, 6 parts of acrylic acid, 2-5 parts of N-hydroxymethyl acrylamide, 2-3 parts of acrylamide, 5 parts of peregal (O-25), 5 parts of sodium dodecyl sulfonate (K12), and 550 parts of deionized water;

[0028] The radiated emulsion seeds include the following components in mass ratio: 320 parts of butyl acrylate, 50 parts of styrene, 10 parts of acrylic acid, 5-10 parts of N-hydroxymethyl acrylamide, 2-5 parts of acrylamide, 5 parts of peregal (O-25), 5 parts of sodium dodecyl sulfate (K12), and 600 parts of deionized water.

[0029] A method for preparing a polyacrylate copolymer emulsion with a bimodal molecular weight distribution comprises the following steps:

[0030] S1: Put the components of the irradiated emulsion seeds into an emulsifying tank and disperse them to obtain a pre-emulsified liquid; the speed is controlled at 2800r / min and the dispersion time is controlled at 20min;

[0031] S2: Take out the pre-emulsified liquid in the emulsifying tank and put it into the reaction container. The reaction container has a stirring function and the stirring speed is controlled at 200r / min. Then put it into the radiation chamber for radiation reaction for 4h;

[0032] S3: After the irradiation is completed, the emulsion with the corresponding mass ratio is taken out as the irradiated emulsion seeds;

[0033] S4: Mix the radiation emulsion seeds with other components and disperse them together, control the speed to 2500-3000r / min, control the temperature to room temperature, and take them out after 20 minutes for use;

[0034] S5: Add deionized water and emulsifier into a four-necked flask and heat to 80°C;

[0035] S6: dropwise add the reserved emulsion and ammonium persulfate solution into the flask to react for 3 hours; during the dropwise addition, control the stirring speed to be 100 r / min;

[0036] S7: After the reaction is completed, keep the temperature for 1 hour, cool it down to below 40°C, and discharge the material.

[0037] Embodiment 2

[0038] according to Figure 1 As shown, this embodiment proposes a polyacrylate copolymer emulsion with a bimodal molecular weight distribution, including the following components by weight: 50-100 parts of radiation emulsion seeds, 300 parts of butyl acrylate, 50 parts of styrene, 6 parts of acrylic acid, 2-10 parts of N-hydroxymethyl acrylamide, 2-5 parts of acrylamide, 5 parts of peregal (O-25), 5 parts of sodium dodecyl sulfonate (K12), and 550 parts of deionized water;

[0039] The radiated emulsion seeds include the following components in mass ratio: 320 parts of butyl acrylate, 50 parts of styrene, 10 parts of acrylic acid, 5-10 parts of N-hydroxymethyl acrylamide, 2-5 parts of acrylamide, 5 parts of peregal (O-25), 5 parts of sodium dodecyl sulfate (K12), and 600 parts of deionized water.

[0040] A method for preparing a polyacrylate copolymer emulsion with a bimodal molecular weight distribution comprises the following steps:

[0041] S1: Put the components of the irradiated emulsion seeds into an emulsifying tank and disperse them to obtain a pre-emulsified liquid; the speed is controlled at 2800r / min and the dispersion time is controlled at 20min;

[0042] S2: Take out the pre-emulsified liquid in the emulsifying tank and put it into the reaction container. The reaction container has a stirring function and the stirring speed is controlled at 200r / min. Then put it into the radiation chamber for radiation reaction for 4h;

[0043] S3: After the irradiation is completed, the emulsion with the corresponding mass ratio is taken out as the irradiated emulsion seeds;

[0044] S4: Mix the radiation emulsion seeds with other components and disperse them together, control the speed to 2500-3000r / min, control the temperature to room temperature, and take them out after 20 minutes for use;

[0045] S5: Add deionized water and emulsifier into a four-necked flask and heat to 80°C;

[0046] S6: dropwise add the reserved emulsion and ammonium persulfate solution into the flask to react for 3 hours; during the dropwise addition, control the stirring speed to be 100 r / min;

[0047] S7: After the reaction is completed, keep the temperature for 1 hour, cool it down to below 40°C, and discharge the material.

[0048] Embodiment 3

[0049] according to Figure 1 As shown, this embodiment proposes a polyacrylate copolymer emulsion with a bimodal molecular weight distribution, including the following components by weight: 200-300 parts of radiation emulsion seeds, 250 parts of butyl acrylate, 50 parts of styrene, 6 parts of acrylic acid, 2-5 parts of N-hydroxymethyl acrylamide, 2-3 parts of acrylamide, 5 parts of peregal (O-25), 5 parts of sodium dodecyl sulfonate (K12), and 480 parts of deionized water;

[0050] The radiated emulsion seeds include the following components in mass ratio: 320 parts of butyl acrylate, 50 parts of styrene, 10 parts of acrylic acid, 5-10 parts of N-hydroxymethyl acrylamide, 2-5 parts of acrylamide, 5 parts of peregal (O-25), 5 parts of sodium dodecyl sulfate (K12), and 600 parts of deionized water.

[0051] A method for preparing a polyacrylate copolymer emulsion with a bimodal molecular weight distribution comprises the following steps:

[0052] S1: Put the components of the irradiated emulsion seeds into an emulsifying tank and disperse them to obtain a pre-emulsified liquid; the speed is controlled at 2800r / min and the dispersion time is controlled at 20min;

[0053] S2: Take out the pre-emulsified liquid in the emulsifying tank and put it into the reaction container. The reaction container has a stirring function and the stirring speed is controlled at 200r / min. Then put it into the radiation chamber for radiation reaction for 4h;

[0054] S3: After the irradiation is completed, the emulsion with the corresponding mass ratio is taken out as the irradiated emulsion seeds;

[0055] S4: Mix the radiation emulsion seeds with other components and disperse them together, control the speed to 2500-3000r / min, control the temperature to room temperature, and take them out after 20 minutes for use;

[0056] S5: Add deionized water and emulsifier into a four-necked flask and heat to 80°C;

[0057] S6: dropwise add the reserved emulsion and ammonium persulfate solution into the flask to react for 3 hours; during the dropwise addition, control the stirring speed to be 100 r / min;

[0058] S7: After the reaction is completed, keep the temperature for 1 hour, cool it down to below 40°C, and discharge the material.

[0059] Embodiment 4

[0060] according to Figure 1 As shown, this embodiment proposes a polyacrylate copolymer emulsion with a bimodal molecular weight distribution, comprising the following components by weight: 50-100 parts of radiation emulsion seeds, 300 parts of butyl acrylate, 50 parts of styrene, 10-20 parts of acrylic acid, 2-5 parts of N-hydroxymethyl acrylamide, 2-3 parts of acrylamide, 5 parts of peregal (O-25), 5 parts of sodium dodecyl sulfonate (K12), and 550 parts of deionized water;

[0061] The radiated emulsion seeds include the following components in mass ratio: 320 parts of butyl acrylate, 50 parts of styrene, 10 parts of acrylic acid, 5-10 parts of N-hydroxymethyl acrylamide, 2-5 parts of acrylamide, 5 parts of peregal (O-25), 5 parts of sodium dodecyl sulfate (K12), and 600 parts of deionized water.

[0062] A method for preparing a polyacrylate copolymer emulsion with a bimodal molecular weight distribution comprises the following steps:

[0063] S1: Put the components of the irradiated emulsion seeds into an emulsifying tank and disperse them to obtain a pre-emulsified liquid; the speed is controlled at 2800r / min and the dispersion time is controlled at 20min;

[0064] S2: Take out the pre-emulsified liquid in the emulsifying tank and put it into the reaction container. The reaction container has a stirring function and the stirring speed is controlled at 200r / min. Then put it into the radiation chamber for radiation reaction for 4h;

[0065] S3: After the irradiation is completed, the emulsion with the corresponding mass ratio is taken out as the irradiated emulsion seeds;

[0066] S4: Mix the radiation emulsion seeds with other components and disperse them together, control the speed to 2500-3000r / min, control the temperature to room temperature, and take them out after 20 minutes for use;

[0067] S5: Add deionized water and emulsifier into a four-necked flask and heat to 80°C;

[0068] S6: dropwise add the reserved emulsion and ammonium persulfate solution into the flask to react for 3 hours; during the dropwise addition, control the stirring speed to be 100 r / min;

[0069] S7: After the reaction is completed, keep the temperature for 1 hour, cool it down to below 40°C, and discharge the material.

[0070] Embodiment 5

[0071] according to Figure 1 As shown, this embodiment proposes a polyacrylate copolymer emulsion with a bimodal molecular weight distribution, comprising the following components by weight: 300-500 parts of radiation emulsion seeds, 300 parts of butyl acrylate, 50 parts of styrene, 6 parts of acrylic acid, 2-5 parts of N-hydroxymethyl acrylamide, 2-3 parts of acrylamide, 5 parts of peregal (O-25), 5 parts of sodium dodecyl sulfonate (K12), and 300-450 parts of deionized water;

[0072] The radiated emulsion seeds include the following components in mass ratio: 320 parts of butyl acrylate, 50 parts of styrene, 10 parts of acrylic acid, 5-10 parts of N-hydroxymethyl acrylamide, 2-5 parts of acrylamide, 5 parts of peregal (O-25), 5 parts of sodium dodecyl sulfate (K12), and 600 parts of deionized water.

[0073] A method for preparing a polyacrylate copolymer emulsion with a bimodal molecular weight distribution comprises the following steps:

[0074] S1: Put the components of the irradiated emulsion seeds into an emulsifying tank and disperse them to obtain a pre-emulsified liquid; the speed is controlled at 2800r / min and the dispersion time is controlled at 20min;

[0075] S2: Take out the pre-emulsified liquid in the emulsifying tank and put it into the reaction container. The reaction container has a stirring function and the stirring speed is controlled at 200r / min. Then put it into the radiation chamber for radiation reaction for 4h;

[0076] S3: After the irradiation is completed, the emulsion with the corresponding mass ratio is taken out as the irradiated emulsion seeds;

[0077] S4: Mix the radiation emulsion seeds with other components and disperse them together, control the speed to 2500-3000r / min, control the temperature to room temperature, and take them out after 20 minutes for use;

[0078] S5: Add deionized water and emulsifier into a four-necked flask and heat to 80°C;

[0079] S6: dropwise add the reserved emulsion and ammonium persulfate solution into the flask to react for 3 hours; during the dropwise addition, control the stirring speed to be 100 r / min;

[0080] S7: After the reaction is completed, keep the temperature for 1 hour, cool it down to below 40°C, and discharge the material.

[0081] Verify data:

[0082] According to Example 1, Example 2, Example 3, Example 4 and Example 5, it can be concluded that the emulsion prepared by the present invention can be used as a pigment printing adhesive to effectively improve properties such as friction fastness, abrasion resistance and film-forming strength.

[0083]

[0084] The present invention uses radiation emulsion after radiation polymerization as a seed to carry out persulfate-initiated emulsion polymerization under high temperature conditions. Different from the traditional single reaction system, the polymerization reaction is carried out around the radiation emulsion macromolecule with a molecular weight of more than 1,000,000, so that the emulsion has a macromolecular core as a support in the reaction, and a polymer emulsion with a bimodal molecular weight distribution is formed. The emulsion takes into account the advantages of radiation emulsion and conventional emulsion, has a better effect on the color fixation performance of coating printing, and can effectively improve the friction fastness, wear resistance and film strength. The preparation method of the present invention is stable, has good repeatability, high efficiency, high environmental protection, can effectively improve the comprehensive performance of acrylic emulsion, and the prepared acrylic emulsion is non-toxic, has the advantages of good fastness, wear resistance, good elasticity, ecological environmental protection, etc., and can be applied to high-demand printing products.

[0085] The above shows and describes the basic principles, main features and advantages of the present invention. It should be understood by those skilled in the art that the present invention is not limited to the above embodiments. The above embodiments and descriptions are only for explaining the principles of the present invention. Without departing from the spirit and scope of the present invention, the present invention may have various changes and improvements, which fall within the scope of the present invention. The scope of protection of the present invention is defined by the attached claims and their equivalents.

Claims

1. A polyacrylate copolymer emulsion having a bimodal molecular weight distribution, characterized in that: The invention comprises the following components in weight ratio: 100-200 parts of radiation emulsion seeds, 200-300 parts of butyl acrylate, 100-20 parts of styrene, 5-10 parts of acrylic acid, 2-5 parts of N-hydroxymethyl acrylamide, 2-3 parts of acrylamide, 3-5 parts of peregal (O-25), 4-8 parts of sodium dodecyl sulfonate (K12), and 584-469 parts of deionized water; The radiated emulsion seed comprises the following components in mass ratio: 300-350 parts of butyl acrylate, 70-20 parts of styrene, 8-12 parts of acrylic acid, 5-10 parts of N-hydroxymethyl acrylamide, 2-5 parts of acrylamide, 5-15 parts of peregal (O-25), 4-8 parts of sodium dodecyl sulfonate (K12), and 603-580 parts of deionized water.

2. The polyacrylate copolymer emulsion with bimodal molecular weight distribution according to claim 1, characterized in that: The composition comprises the following components in mass ratio: 150 parts of radiation emulsion seeds, 230 parts of butyl acrylate, 50 parts of styrene, 8 parts of acrylic acid, 3 parts of N-hydroxymethyl acrylamide, 2.5 parts of acrylamide, 4 parts of peregal (O-25), 6 parts of sodium dodecyl sulfonate (K12), and 500 parts of deionized water; The radiated emulsion seed comprises the following components in mass ratio: 320 parts of butyl acrylate, 50 parts of styrene, 10 parts of acrylic acid, 7 parts of N-hydroxymethyl acrylamide, 3 parts of acrylamide, 12 parts of peregal (O-25), 6 parts of sodium dodecyl sulfonate (K12), and 595 parts of deionized water.

3. A method for preparing a polyacrylate copolymer emulsion with a bimodal molecular weight distribution, applied to the polyacrylate copolymer emulsion with a bimodal molecular weight distribution as claimed in any one of claims 1 to 2, characterized in that: The following steps are involved: S1: putting the components of the irradiated emulsion seeds into an emulsifying tank and dispersing them to obtain a pre-emulsion; S2: Take out the pre-emulsified liquid in the emulsification tank, put it into the reaction container, and put it into the radiation chamber for radiation reaction for 4 hours; S3: After the irradiation is completed, the emulsion with the corresponding mass ratio is taken out as the irradiated emulsion seeds; S4: Mix the irradiated emulsion seeds with other components and disperse them together for emulsification, and take them out after 20 minutes for use; S5: Add deionized water and emulsifier into a four-necked flask and heat to 80°C; S6: adding the reserved emulsion and ammonium persulfate solution dropwise into the flask to react for 3 hours; S7: After the reaction is completed, keep the temperature for 1 hour, cool it down to below 40°C, and discharge the material.

4. The method for preparing a polyacrylate copolymer emulsion having a bimodal molecular weight distribution according to claim 3, characterized in that: In S1, the rotation speed is controlled to 2800 r / min, and the dispersion time is controlled to 20 min.

5. The method for preparing a polyacrylate copolymer emulsion with a bimodal molecular weight distribution according to claim 3, characterized in that: In S2, the reaction container has a stirring function, and the stirring speed is controlled to be 200 r / min.

6. The method for preparing a polyacrylate copolymer emulsion having a bimodal molecular weight distribution according to claim 3, characterized in that: In the above S4, during dispersion and emulsification, the rotation speed is controlled to 2500-3000 r / min and the temperature is controlled to room temperature.

7. The method for preparing a polyacrylate copolymer emulsion with a bimodal molecular weight distribution according to claim 3, characterized in that: In S6, during the dropwise addition, the stirring speed was controlled to be 100 r / min. 。

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