CN115651114A - Method for controlling polymerization particle size of acrylic emulsion - Google Patents
Method for controlling polymerization particle size of acrylic emulsion Download PDFInfo
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- CN115651114A CN115651114A CN202211359835.7A CN202211359835A CN115651114A CN 115651114 A CN115651114 A CN 115651114A CN 202211359835 A CN202211359835 A CN 202211359835A CN 115651114 A CN115651114 A CN 115651114A
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Abstract
The invention discloses a particle size control process of acrylic emulsion, which is characterized in that the preparation raw materials mainly comprise the following components in parts by mass: the composition comprises monomers (5-15 parts of acrylamide, 300-400 parts of butyl acrylate, 300-400 parts of methyl methacrylate and 8-14 parts of acrylic acid), 700-800 parts of water, 3-5 parts of an initiator, 10-15 parts of an emulsifier, redox additives (0.2-1 part of an oxidant and 0.1-0.8 part of a reducing agent), and aftertreatment additives (4-8 parts of a neutralizer, 0.1-1 part of a defoaming agent and 5-15 parts of a preservative). The method comprises the steps of firstly preparing a pre-emulsion, then adding the pre-emulsion into a kettle bottom solution, and finally adding an oxidation reducing agent and a post-treatment additive to obtain the acrylic emulsion. The particle size of the emulsion is controlled by strictly controlling the adding time of the pre-emulsion, and the method is simple and efficient.
Description
Technical Field
The invention belongs to the field of emulsion processing and preparation, and particularly relates to a method for controlling the polymerization particle size of an acrylic emulsion.
Background
In the practical application of acrylic emulsion, the particle size and the particle size distribution of the emulsion directly affect the appearance and the water resistance of the emulsion. In actual production, besides the raw material formula, the particle size of the finished acrylic emulsion is also related to the preparation process, the reaction temperature, the stirring speed and other human factors.
CN102234351A adopts a semi-continuous seed emulsion polymerization process to increase the particle size of the emulsion and prepare the vinyl acetate emulsion with large particle size. The method can effectively control the diameter and the distribution of emulsion particles by adopting a seeded emulsion polymerization method, and can reduce the amount of seeded emulsion under the premise of not changing the amount of monomers, so that the particle size of the emulsion can be increased to about 25 micrometers.
The production process adopted by CN110330587B is a seed emulsion polymerization and circulation dropping method, the polymerized seed emulsion is continuously returned to a pre-emulsion tank and continuously dropped into a reaction tank together with a pre-emulsified monomer, the particle size of the seed emulsion is adjusted to obtain the acrylic emulsion, the particle size distribution of the acrylic emulsion is wide, the preparation of the acrylic emulsion with high solid content and low viscosity can be realized, and the transportation, storage and use of the acrylic emulsion are convenient.
CN108997519A discloses a preparation method of a water-resistant acrylic ester emulsion with ultra-fine particle size, which comprises three steps of (1) dissolving an emulsifier in water to form a micelle/water phase mixture, (2) mixing a monomer with a cosurfactant to form an oil phase mixture, and (3) emulsion polymerization for micro-nucleation. The prepared water-resistant ultrafine-particle-size acrylate emulsion product has the particle size of 20-50nm, the solid content of more than or equal to 30 percent, and has the advantages of high solid content, nanoscale particle size and good water resistance.
CN102070730B relates to a method for effectively controlling latex particle components, particle size and distribution in emulsion polymerization, thereby controlling the solid content and viscosity of the emulsion, which is characterized in that a composite emulsifier is injected into a system stage by stage at one time within a proper temperature range during monomer dropping, then the monomer is dropped for nucleating again, and N times of injection can form N + 1-element particle size distribution emulsion by controlling the size and distribution of the latex particles of the system through the times and concentration of injecting the composite emulsifier at one time, wherein N can be a natural number larger than 2. The method is an effective way for preparing the composite emulsion in situ and realizing the design of latex particles, and can be used as a general method for industrially preparing the multi-element composite emulsion with high solid content and low viscosity in particle size distribution due to simple process and high control efficiency.
CN107793518A relates to the use of a neutralizing agent in controlling the emulsion particle size of EVA elastomer emulsion, comprising: and (2) in a single reactor, adding an emulsifier and vinyl acetate into deionized water serving as a water phase, then adding a neutralizer, and carrying out copolymerization reaction on the vinyl acetate and ethylene under the action of an initiator to obtain the EVA elastomer emulsion. The neutralizing agent can control the particle size of the emulsion, reduce the particle size of the emulsion, prevent adhesion and improve the stability and the dispersibility of the system.
CN110627590B controls the size of the aqueous phase liquid drops of the ammonium dinitramide through adjusting parameters such as oil/water volume ratio, ammonium dinitramide aqueous solution concentration, template dispersion solution concentration, template/ammonium dinitramide mass ratio and the like, and finally realizes the regulation and control of the particle size of the spherical ammonium dinitramide powder.
In the research on the influence factors of the particle size of the acrylate emulsion, the influence of factors such as the content of an emulsifier, the amount of seed emulsion, the glass transition temperature Tg of the emulsion and the like on the particle size of the emulsion is investigated.
In the article "emulsion polymerization of butyl acrylate and particle size control", the influence of monomer feed concentration, copolymerization composition and emulsifier type on the particle size of the emulsion was examined.
As can be seen from the above, the general means for controlling the particle size of the emulsion mainly comprises raw materials (neutralizer, emulsifier, monomer types) and preparation processes (seed emulsion, cyclic multiple addition of seed emulsion, feeding concentration) and the like. If the emulsion with the target particle size is required to be obtained, the raw material formula needs to be changed, and the change is large; if the process is changed, it means that the existing operation may need to be changed or even the equipment needs to be added.
Therefore, it is very important to obtain an acrylic emulsion with controllable particle size by changing and adjusting process parameters without changing the current preparation raw materials and preparation process.
Disclosure of Invention
In order to solve the above problems, the present invention provides the following technical solutions.
A method for controlling the polymerization particle size of acrylic emulsion comprises the following raw materials in parts by mass: monomers (5-15 parts of acrylamide, 300-400 parts of butyl acrylate, 300-400 parts of methyl methacrylate and 8-14 parts of acrylic acid), 700-800 parts of water, 3-5 parts of an initiator, 10-15 parts of an emulsifier, a redox additive (0.2-1 part of an oxidant and 0.1-0.8 part of a reducing agent), and a post-treatment additive (4-8 parts of a neutralizer, 0.1-1 part of a defoaming agent and 5-15 parts of a preservative);
the preparation method mainly comprises the following steps:
(1) Weighing all monomers, part of emulsifier, part of initiator and 400-450 parts by mass of water, and mixing to prepare a pre-emulsion;
(2) Weighing the residual emulsifier, adding the residual emulsifier and 300-350 parts by mass of water into a reaction kettle, and preparing reaction kettle liquid; heating to 85-88 ℃, adding the rest initiator, beginning to dropwise add the pre-emulsion after X minutes, dropwise adding the pre-emulsion at a constant speed for 180-270 minutes, and then continuously preserving the temperature for 50-90 minutes;
(3) Cooling to 70-74 ℃, and dropwise adding a redox additive;
(4) Cooling to 40-50 ℃, and dropwise adding an after-treatment additive to prepare the acrylic emulsion.
Preferably, the initiator is ammonium persulfate.
Preferably, the emulsifier is a anionic nonionic emulsifier.
Preferably, the oxidizing agent in the redox additive is a hydroperoxide, more preferably t-butyl hydroperoxide; the reducing agent in the redox additive is sodium bisulfite.
Preferably, the neutralizing agent in the post-treatment additive is ammonia; the defoaming agent is mineral oil; the preservative is cason.
Preferably, in the step (1), the addition amount of the emulsifier is 92-95% of the total emulsifier amount, and the addition amount of the initiator is 75-85% of the total initiator amount.
Preferably, in the step (2), the time X for starting the dropwise addition of the pre-emulsion is 0 to 7 minutes.
In the invention, the pre-emulsion is dripped after the initiator is initially added for 3 minutes, and the particle size of the emulsion is increased. The main reason is that the initiator is thermally decomposed to generate free radicals, and the generation rates of the free radicals at different time are different, so that 3 minutes is the critical point of the change of the emulsion particle size, and the pre-emulsion is added dropwise after 3-7 minutes from the initial addition of the initiator, so that the emulsion particle size is obviously increased.
The invention has the beneficial effects that:
(1) In the emulsion production process, the time for dripping the pre-emulsion is strictly controlled, so that the increase of the particle size fluctuation can be effectively avoided.
(2) The present invention can be used to increase the particle size of the emulsion in a simulation of a race emulsion to fit the performance data of the race emulsion.
(3) The process can lead each acrylic emulsion engineer to have a direction in designing the formula, namely how to increase the particle size of the emulsion in a limited condition, and can also avoid the abnormality of the particle size value of the emulsion in production.
Detailed Description
Example 1:
the specific mass of the raw materials for preparing the acrylic emulsion polymer is shown in Table 1.
TABLE 1
A method for controlling the polymerization particle diameter of acrylic emulsion mainly comprises the following steps:
(1) Weighing the pre-emulsion raw materials as shown in the table 1, and mixing to prepare a pre-emulsion;
(2) Weighing the reaction kettle liquid raw materials as shown in the table 1, and adding water and an emulsifier in the reaction kettle to prepare reaction kettle liquid; raising the temperature to 87 ℃, adding an initiator, beginning to dropwise add the pre-emulsion after X = 0min (namely, immediately starting), dropwise adding at a uniform speed for 240 min, and then continuing to preserve heat for 60 min;
(3) Cooling to 70 ℃, and dripping an oxidation and reduction additive;
(4) Cooling to below 50 ℃, and dropwise adding a post-treatment additive to prepare the acrylic emulsion.
Examples 2 to 8:
the starting materials were prepared and the specific procedure was the same as in example 1 except that in the step (2), the time X for starting the dropwise addition of the pre-emulsion was 1 to 7 minutes, respectively. Detailed Description
The results described in examples 1-8 are as follows.
TABLE 1
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. It is specifically intended herein that the examples are for the purpose of describing and further illustrating preferred additive formulation levels of the present invention and are not to be construed as limiting the scope of the present invention, as numerous modifications will be apparent to those skilled in the art to which the examples pertain, and that non-essential modifications and adaptations of the present invention in light of the above teachings are intended to be covered thereby, and that the present invention is not to be limited to the examples illustrated herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (7)
1. The method for controlling the polymerization particle size of the acrylic emulsion is characterized in that the preparation raw materials mainly comprise the following components in parts by mass: monomers (5-15 parts of acrylamide, 300-400 parts of butyl acrylate, 300-400 parts of methyl methacrylate and 8-14 parts of acrylic acid), 700-800 parts of water, 3-5 parts of an initiator, 10-15 parts of an emulsifier, a redox additive (0.2-1 part of an oxidant and 0.1-0.8 part of a reducing agent), and a post-treatment additive (4-8 parts of a neutralizer, 0.1-1 part of a defoaming agent and 5-15 parts of a preservative);
the preparation method mainly comprises the following steps:
(1) Weighing all monomers, part of emulsifier, part of initiator and 400-450 parts by mass of water, and mixing to prepare a pre-emulsion;
(2) Weighing the residual emulsifier, adding the residual emulsifier and 300-350 parts by mass of water into a reaction kettle, and preparing reaction kettle liquid; heating to 85-88 ℃, adding the rest initiator, dropwise adding the pre-emulsion after X minutes, uniformly dropwise adding the pre-emulsion for 180-270min, and then continuously preserving the heat for 50-90min;
(3) Cooling to 70-74 ℃, and dripping redox additive;
(4) Cooling to 40-50 ℃, and dropwise adding an after-treatment additive to prepare the acrylic emulsion.
2. The method of claim 1, wherein the initiator is ammonium persulfate.
3. The method for controlling the polymer particle size of acrylic emulsion according to claim 1 wherein said emulsifier is a negative nonionic emulsifier.
4. The method for controlling the particle size of acrylic emulsion polymerization according to claim 1 wherein said oxidizing agent is a hydroperoxide species, more preferably t-butyl hydroperoxide; the reducing agent is sodium bisulfite.
5. The method of claim 1, wherein the neutralizing agent is ammonia; the defoaming agent is mineral oil; the preservative is cason.
6. The method for controlling the polymerized particle size of acrylic emulsion according to claim 1, wherein in step (1), the emulsifier is added in an amount of 92 to 95% of the total emulsifier amount, and the initiator is added in an amount of 75 to 85% of the total initiator amount.
7. The method for controlling the polymer particle size of acrylic emulsion as claimed in claim 1, wherein the time X for starting the addition of the pre-emulsion in the step (2) is 0 to 7 minutes.
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| CN202211359835.7A CN115651114A (en) | 2022-11-02 | 2022-11-02 | Method for controlling polymerization particle size of acrylic emulsion |
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| CN202211359835.7A CN115651114A (en) | 2022-11-02 | 2022-11-02 | Method for controlling polymerization particle size of acrylic emulsion |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103193917A (en) * | 2013-04-03 | 2013-07-10 | 衡水新光化工有限责任公司 | Method for preparing pure acrylate copolymer coating emulsion for building external wall elastic coating |
| CN111205400A (en) * | 2020-03-12 | 2020-05-29 | 广东巴德富新材料有限公司 | Low-internal-stress acrylic emulsion and preparation method thereof |
| CN111363081A (en) * | 2020-04-29 | 2020-07-03 | 广东巴德富新材料有限公司 | Acrylate emulsion for stain-resistant water-based finish varnish and preparation method thereof |
| CN114929756A (en) * | 2019-12-20 | 2022-08-19 | 巴斯夫欧洲公司 | Seed resin stabilized high solids emulsion polymers |
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- 2022-11-02 CN CN202211359835.7A patent/CN115651114A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103193917A (en) * | 2013-04-03 | 2013-07-10 | 衡水新光化工有限责任公司 | Method for preparing pure acrylate copolymer coating emulsion for building external wall elastic coating |
| CN114929756A (en) * | 2019-12-20 | 2022-08-19 | 巴斯夫欧洲公司 | Seed resin stabilized high solids emulsion polymers |
| CN111205400A (en) * | 2020-03-12 | 2020-05-29 | 广东巴德富新材料有限公司 | Low-internal-stress acrylic emulsion and preparation method thereof |
| CN111363081A (en) * | 2020-04-29 | 2020-07-03 | 广东巴德富新材料有限公司 | Acrylate emulsion for stain-resistant water-based finish varnish and preparation method thereof |
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