CN113072660A - Preparation method of large-particle-size polybutadiene latex - Google Patents
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Abstract
The invention belongs to the technical field of high polymer materials, and discloses a preparation method of large-particle-size polybutadiene latex.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a preparation method of polybutadiene latex with large particle size.
Background
The polybutadiene latex with large particle size and the copolymer latex thereof such as styrene-butadiene latex, butyronitrile latex and the like have important application values in the fields of synthetic rubber, synthetic resin, adhesive and the like. In the process of preparing synthetic resin such as ABS resin, the particle size and the particle size distribution of polybutadiene latex with large particle size are key factors for determining the mechanical property of the final ABS resin, and research shows that the ABS resin can have good mechanical property only when the average particle size of the polybutadiene latex is more than 250nm, so that the preparation of the polybutadiene latex with large particle size is the core technology of synthesizing the ABS resin.
The existing process technology for synthesizing the polybutadiene latex with large particle size can be divided into two processes, namely a one-step process and a two-step process. For example, the one-step method for preparing polybutadiene latex with large particle size reported in the synthetic rubber industry (1987, 5: 328-331) utilizes the batch emulsion polymerization technology, adopts the process of step temperature rise and batch emulsifier addition, and finally prepares the polybutadiene latex with the particle size of 250nm for 55-60 h. The polybutadiene latex prepared by the one-step method has the advantages of narrow particle size distribution, good latex stability, long storage time and the disadvantages of long polymerization period and low production efficiency. In recent years, many studies have been reported on the preparation of large-particle-size polybutadiene latex by two-step process, for example, large-particle-size styrene-isoprene-butadiene latex reported in patent CN108250519A and a preparation method thereof, the first step is to synthesize small-particle-size latex with particle size of 60-85 nm, add an agglomerating agent composed of acetic acid and acrylic latex to the small-particle-size latex, reduce the pH value of the emulsion system by using the agglomerating agent, reduce the stability of the small-particle-size emulsion, promote the agglomeration of the small-particle-size latex, and the final agglomerated latex has particle size of 200-500 nm. Patent CN102050889A reports a method for preparing polybutadiene latex with ultra-large particle size by using polymer agglomerant, which comprises the first step of synthesizing polybutadiene latex with small particle size, then synthesizing polymer agglomerant by using monomers such as styrene, acrylate and acrylic acid, and finally adding the synthesized polymer agglomerant into the polybutadiene latex with small particle size to agglomerate to prepare polybutadiene latex with ultra-large particle size (400-1000 nm). Patent CN103848942A reports a method for preparing a large-particle size polybutadiene latex by using a pressure agglomeration method, in which a small-particle size butadiene latex is subjected to high-pressure homogenization, and the small-particle size latex is agglomerated into a large-particle size latex by using high pressure. Compared with the method for preparing the latex with the large particle size by the same step, the method for preparing the polybutadiene latex with the large particle size by the two-step method has the advantages that the preparation period is shorter, the time from the preparation of the latex with the small particle size to the completion of agglomeration is generally within 12-18 h, the production efficiency is higher, the defects are that the particle size distribution of the agglomerated latex is wider, the stability of the latex is poor, and the solid content of the agglomerated latex is about 30 wt%.
Whether the two-step agglomeration technology and the one-step method for preparing the large-particle-size polybutadiene latex can be combined into a whole or not, and the defects among the two can be overcome by utilizing the advantages of the two processes, which is a key problem in the process of improving the large-particle-size polybutadiene and is also a core problem in improving the product quality. The core of the two-step method for preparing the large-particle-size polybutadiene latex is an agglomeration process, wherein the agglomeration process is substantially that the adsorption mode of the emulsifier on the particle surface of the latex particles is changed under external stimulation (such as conditions of pH change, pressure change, ionic strength change and the like), so that the interface energy between the latex particles and a continuous phase is increased, the stability of the latex particles is promoted to be poor thermodynamically, the particles are aggregated to reduce the interface area, the stability is enhanced, and finally the particles are aggregated to be small-particle aggregates, namely the large-particle-size polybutadiene latex particles are obtained. If the agglomeration process of the latex particles is transplanted to the polymerization process of the one-step method, the agglomeration among the particles occurs in the early process of the one-step method synthesis, so that the size of the particles can be greatly increased, and the later-stage monomer polymerization can also promote the fusion of molecular chain segments in the agglomerates to change the agglomerates into truly large particles, thereby increasing the particle size and improving the product quality. The reaction rate can be increased by a large number of particles in the early stage of agglomeration, the polymerization time of the butadiene latex is shortened, the two technologies are completely fused into one technology, the purpose of preparing the latex with large particle size in a one-step method and a short period is achieved, and the production efficiency of the latex with large particle size is improved.
Therefore, how to provide a preparation method for efficiently preparing polybutadiene latex with large particle size in a short period is a problem to be solved by those skilled in the art.
Disclosure of Invention
In view of the above, the invention provides a preparation method of polybutadiene latex with large particle size, which can effectively improve the polymerization reaction rate, shorten the reaction period, significantly improve the production efficiency of polybutadiene latex, and reduce the production cost. The key point is that in the process of butadiene emulsion polymerization, the electrolyte and the emulsifier are utilized to induce butadiene monomer to rapidly nucleate and generate coalescence among particles, thereby accelerating the polymerization reaction rate and increasing the particle size. The aggregation process of the particles is a process which is initiated by thermodynamics and is controlled by kinetics, the specific surface area of polybutadiene latex particles with smaller sizes is large under the condition of high concentration, and further the specific surface energy is large, the aggregation of the polybutadiene latex particles with small particle sizes is promoted to be changed into aggregates so as to increase the size, and the polybutadiene particles with large particle sizes are realized.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of large-particle size polybutadiene latex comprises the following steps:
(1) adding 2-7 parts of emulsifier, 0.1-0.5 part of initiator, 0.5-5 parts of electrolyte, 0.1-1 part of chain transfer agent and 30-45 parts of deionized water into a polymerization reaction kettle, and stirring at room temperature until the emulsifier, the initiator and the deionized water are completely dissolved;
(2) introducing nitrogen into the reaction kettle to replace air in the reaction kettle, then adding 55-70 parts of butadiene monomer and 0.1-5 parts of comonomer, and stirring at the speed of 120-200 rpm;
(3) heating the reaction kettle to 60-69 ℃, and keeping the temperature for 6-12 h to obtain a first-stage polymerization reaction; after the first-stage polymerization reaction, 0.03-0.1 part of initiator is added, and the temperature is raised to 70-72 ℃ for constant-temperature reaction for 6-10 h, namely a second-stage polymerization reaction; and after the second-stage polymerization reaction, adding 0.03-0.1 part of initiator, heating to 73-75 ℃, reacting at a constant temperature for 6-10 h to obtain a third-stage polymerization reaction, and cooling and discharging after the third-stage polymerization reaction is finished to obtain the polybutadiene latex with the large particle size.
Preferably, in the above preparation method of the large-particle size polybutadiene latex, the emulsifier is a mixture of any several of disproportionated potassium rosinate soap, potassium fatty acid soap, potassium oleate soap, potassium stearate soap, alkyl naphthalene sulfonate, sodium dodecyl benzene sulfonate and potassium ricinoleate.
Preferably, in the above method for preparing large-particle size polybutadiene latex, the initiator is one or a mixture of ammonium persulfate, potassium persulfate and sodium persulfate.
Preferably, in the above preparation method of the large-particle size polybutadiene latex, the electrolyte is one or a mixture of potassium carbonate, potassium bicarbonate, sodium carbonate, sodium bicarbonate, potassium hydroxide, potassium chloride and sodium chloride.
Preferably, in one of the above-mentioned methods for preparing a large-particle size polybutadiene latex, the chain transfer agent is dodecyl mercaptan.
Preferably, in the above method for preparing large-particle size polybutadiene latex, the comonomer is one or a mixture of several of styrene, methyl methacrylate, acrylonitrile, acrylate and methacrylate monomers.
According to the technical scheme, compared with the prior art, the invention discloses the preparation method of the polybutadiene latex with the large particle size, the composite emulsifier is used in a high-concentration butadiene emulsion polymerization system based on the emulsion polymerization principle, the using amount of the emulsifier is increased, a trace amount of comonomer is introduced, the nucleation of latex particles is promoted under the high-temperature condition, the number of the formed latex particles is greatly increased, and the polymerization reaction rate is accelerated; the usage amount of electrolyte is greatly increased in the formula, the ionic strength in a continuous phase is improved, the thickness of a double electric layer on the surface of newly formed emulsion particles is compressed, the generated small particles are promoted to agglomerate after the particle nucleation period is finished, and the particle size is increased; and finally, the number of free radicals in the system is guaranteed by adopting a mode of gradually raising the temperature at constant temperature in stages and a mode of replenishing an initiator, so that the polymerization reaction is further accelerated, the polymerization reaction period is shortened, and the production efficiency of the latex with large particle size is improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is a graph showing a distribution of particle diameters of polybutadiene latex according to example 1 of the present invention;
FIG. 2 is a graph showing a distribution of particle diameters of polybutadiene latex according to example 2 of the present invention;
FIG. 3 is a graph showing a distribution of particle diameters of polybutadiene latex according to example 3 of the present invention;
FIG. 4 is a graph showing a distribution of particle diameters of polybutadiene latex of comparative example 1 according to the present invention;
FIG. 5 is a graph showing a distribution of particle diameters of a polybutadiene latex of comparative example 2 according to the present invention;
FIG. 6 is a graph showing a distribution of particle diameters of the polybutadiene latex of comparative example 3 according to the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention relates to a novel one-step method technology for preparing polybutadiene latex with high solid content, which is developed by combining two process technologies of a one-step method and an agglomeration method for preparing polybutadiene latex, and the polybutadiene latex with the highest solid content of more than 60 wt% and the average particle size of more than 300nm can be prepared within 30 hours by using the method. According to the method, the composite high-concentration emulsifier is used for inducing a polymerization system to rapidly nucleate at a high initial temperature to generate smaller latex particles, the generated small particles agglomerate in the polymerization process under high ionic strength, so that the size of the particles is increased, the number of free radicals in the system is guaranteed by adopting a mode of dropwise adding the initiator in sections and raising the temperature at constant temperature in stages, the polymerization reaction rate is increased, the reaction period is shortened, the rapid preparation of the butadiene latex with large particle size and high solid content is finally realized, the production efficiency is remarkably improved, and the production cost is reduced.
Example 1
1.5 parts of emulsifier disproportionated potassium abietate soap, 1 part of fatty acid, 0.5 part of potassium oleate, 0.1 part of alkyl sodium naphthalene sulfonate, 0.2 part of initiator ammonium persulfate, 2 parts of electrolyte potassium carbonate, 0.3 part of chain transfer agent dodecyl mercaptan and 40 parts of deionized water are placed in a reaction kettle, and a stirring paddle is started to completely dissolve the materials.
After nitrogen gas is introduced to remove air in the reaction kettle, 60 parts of butadiene monomer and 0.5 part of comonomer butyl acrylate are added, and the stirring speed is constant at 150 rpm.
Heating the reaction kettle to 65 ℃, and polymerizing for 10 hours to finish the first stage reaction; adding 0.05 part of initiator potassium persulfate, heating to 70 ℃ and reacting for 10 hours to complete the second stage reaction; and (3) supplementing 0.03 part of initiator sodium persulfate, heating to 75 ℃, reacting for 8 hours to finish the third stage of reaction, and cooling and discharging after the third stage of reaction is finished to obtain the large-particle-size polybutadiene latex.
The average particle size of the particles is 312nm and the polydispersity index is 0.009 as tested by a Malvern dynamic light scattering instrument (NanoZS90), and the solid content is 60.5 wt% as tested by a solid content tester (CSY-G1, Shenzhen Analyzer Co., Ltd.).
Example 2
1 part of emulsifier potassium stearate soap, 1.5 parts of fatty acid potassium soap, 0.5 part of potassium ricinoleate, 0.2 part of sodium dodecyl sulfate, 0.3 part of initiator ammonium persulfate, 2 parts of electrolyte sodium carbonate, 0.5 part of potassium chloride, 0.3 part of chain transfer agent dodecyl mercaptan and 45 parts of deionized water are placed in a reaction kettle, and a stirring paddle is started to be completely dissolved.
After nitrogen gas was introduced to remove air in the reaction vessel, 55 parts of butadiene monomer and 0.5 part of styrene as a comonomer were added, and the stirring speed was constant at 150 rpm.
Heating the reaction kettle to 60 ℃, and polymerizing for 8 hours to finish the first stage reaction; adding 0.05 part of initiator potassium persulfate, heating to 70 ℃ and reacting for 12 hours to complete the second stage reaction; and (3) supplementing 0.03 part of initiator sodium persulfate, heating to 75 ℃, reacting for 6 hours to finish the third stage of reaction, and cooling and discharging after the third stage of reaction is finished to obtain the large-particle-size polybutadiene latex.
The average particle size of the particles is 278nm and the polydispersity index is 0.005 as tested by a Malvern dynamic light scattering instrument (NanoZS90), and the solid content is 54.5 wt% as tested by a solid content tester (CSY-G1, Shenzhen Analyzer Co., Ltd.).
Example 3
1 part of emulsifier disproportionated potassium rosinate soap, 2 parts of fatty acid potassium soap, 0.5 part of potassium ricinoleate, 0.2 part of lauryl sodium sulfate, 0.3 part of initiator potassium persulfate, 2 parts of electrolyte sodium bicarbonate, 0.5 part of sodium chloride, 0.4 part of chain transfer agent dodecyl mercaptan and 35 parts of deionized water are placed in a reaction kettle, and a stirring paddle is started to completely dissolve the materials.
Introducing nitrogen to remove air in the reaction kettle, adding 65 parts of butadiene monomer and 1 part of comonomer acrylonitrile, and keeping the stirring speed constant at 120 rpm.
Heating the reaction kettle to 60 ℃, and polymerizing for 12 hours to finish the first stage reaction; adding 0.08 part of initiator potassium persulfate, heating to 70 ℃ and reacting for 12 hours to complete the second stage reaction; and (3) supplementing 0.03 part of initiator sodium persulfate, heating to 75 ℃, reacting for 10 hours to finish the third stage of reaction, and cooling and discharging after the third stage of reaction is finished to obtain the large-particle-size polybutadiene latex.
The average particle size of the particles is 338nm and the polydispersity index is 0.005 as tested by a Malvern dynamic light scattering instrument (NanoZS90), and the solid content is 63.3 wt% as tested by a solid content tester (CSY-G1, Shenzhen Analyzer Co., Ltd.).
Comparative example 1
Compared with example 1, in comparative example 1, 60 parts of butadiene and 0.5 part of comonomer butyl acrylate are added to be continuously fed at a constant speed, the total feeding time is set to be 28 hours, and the use amount of other auxiliary agents and the process conditions are not changed. After the polymerization reaction time is reached, the average particle size of the particles is 186nm and the polydispersity index is 0.147 as tested by a Malvern dynamic light scattering instrument (nano ZS90), and the solid content is 48.91 wt% as tested by a solid content detector (CSY-G1, Shenzhen Analyzer Limited, Inc.) as shown in the attached figure 4.
Comparative example 2
In comparison with example 1, in comparative example 2, no electrolyte potassium carbonate was added, and other formulation composition and process conditions were the same as in example 1. After the polymerization reaction time is reached, the average particle size of particles is 206nm and the polydispersity index is 0.027 as tested by a Malvern dynamic light scattering instrument (nano ZS90), and the solid content is 58.91 wt% as tested by a solid content tester (CSY-G1, Shenzhen Analyzer Co., Ltd., Shenzhen, see FIG. 5 for details). It is noted that the latex prepared in comparative example 2 is relatively viscous and has substantially no fluidity.
Comparative example 3
In comparison with example 1, in comparative example 3, 40 parts of butadiene monomer was added, and the rest of the formulation and process conditions were the same as in example 1. After the polymerization time is reached, the average particle size of the particles is 166nm and the polydispersity index is 0.047 as tested by a Malvern dynamic light scattering instrument (nano ZS90), in detail as shown in FIG. 6, and the solid content is 40.91 wt% as tested by a solid content tester (CSY-G1, Shenzhen Analyzer Co., Ltd.).
Summarizing comparative examples 1 to 3 and comparative examples 1 to 3, it can be shown that a method for preparing a large-particle-size polybutadiene latex according to the present invention is centered on inducing aggregation of latex particles to some extent at the initial stage of polymerization, i.e., in-situ agglomeration. High monomer feed concentration, high electrolyte concentration, high emulsifier concentration are key factors in determining whether the invention can be carried out.
TABLE 1 results of performance test of latexes prepared in examples 1 to 3 and comparative examples 1 to 3
| Solid content (%) | Average particle diameter (nm) | Index of dispersion | |
| Example 1 | 60.5 | 312 | 0.009 |
| Example 2 | 54.5 | 253 | 0.005 |
| Example 3 | 63.3 | 338 | 0.005 |
| Comparative example 1 | 48.91 | 186 | 0.147 |
| Comparative example 2 | 58.91 | 206 | 0.027 |
| Comparative example 3 | 40.91 | 166 | 0.047 |
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other. For the scheme disclosed by the embodiment, the scheme corresponds to the method disclosed by the embodiment, so that the description is simple, and the relevant points can be referred to the method part for description.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (6)
1. A preparation method of large-particle size polybutadiene latex is characterized by comprising the following steps:
(1) adding 2-7 parts of emulsifier, 0.1-0.5 part of initiator, 0.5-5 parts of electrolyte, 0.1-1 part of chain transfer agent and 30-45 parts of deionized water into a polymerization reaction kettle, and stirring at room temperature until the emulsifier, the initiator and the deionized water are completely dissolved;
(2) introducing nitrogen into the reaction kettle to replace air in the reaction kettle, then adding 55-70 parts of butadiene monomer and 0-5 parts of comonomer, and stirring at the speed of 120-200 rpm;
(3) heating the reaction kettle to 60-69 ℃, and keeping the temperature for 6-12 h to obtain a first-stage polymerization reaction; after the first-stage polymerization reaction, 0.03-0.1 part of initiator is added, and the temperature is raised to 70-72 ℃ for constant-temperature reaction for 6-10 h, namely a second-stage polymerization reaction; and after the second-stage polymerization reaction, adding 0.03-0.1 part of initiator, heating to 73-75 ℃, reacting at a constant temperature for 6-10 h to obtain a third-stage polymerization reaction, and cooling and discharging after the third-stage polymerization reaction is finished to obtain the polybutadiene latex with the large particle size.
2. The method of claim 1, wherein the emulsifier is a mixture of any of disproportionated potassium rosinate soap, potassium fatty acid soap, potassium oleate soap, potassium stearate soap, alkyl naphthalene sulfonate, sodium dodecyl benzene sulfonate, and potassium ricinoleate.
3. The method for preparing polybutadiene latex with large particle size according to claim 1, wherein the initiator is one or more of ammonium persulfate, potassium persulfate and sodium persulfate.
4. The method of claim 1, wherein the electrolyte is one or more selected from potassium carbonate, potassium bicarbonate, sodium carbonate, sodium bicarbonate, potassium hydroxide, potassium chloride, and sodium chloride.
5. The method of preparing a large-particle size polybutadiene latex according to claim 1, wherein said chain transfer agent is dodecyl mercaptan.
6. The method for preparing polybutadiene latex with large particle size according to claim 1, wherein the comonomer is one or more of styrene, methyl methacrylate, acrylonitrile, acrylate and methacrylate monomers.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115947884A (en) * | 2022-12-20 | 2023-04-11 | 山东万达化工有限公司 | Synthesis method of large-particle-size polybutadiene latex |
| CN118652379A (en) * | 2024-08-21 | 2024-09-17 | 潍坊蓝励新材料有限公司 | Large-particle-size low-temperature stable styrene-butadiene latex and preparation method thereof |
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| WO2024130825A1 (en) * | 2022-12-20 | 2024-06-27 | 山东万达化工有限公司 | Synthetic method for large-particle-size polybutadiene latex |
| CN118652379A (en) * | 2024-08-21 | 2024-09-17 | 潍坊蓝励新材料有限公司 | Large-particle-size low-temperature stable styrene-butadiene latex and preparation method thereof |
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