阅读说明：本技术 一种高分子附聚胶乳的制备方法及其应用技术 (Preparation method and application technology of polymer agglomerated latex ) 是由 张东梅 李永华 邵维彧 魏丽娟 唐明 肖大君 李秉荣 武天希 韩丽君 范铁军 于 2021-08-27 设计创作，主要内容包括：本发明提供一种高分子附聚胶乳的制备方法及其应用。其中高分子附聚剂是以丙烯酸乙酯和甲基丙烯酸甲酯的为原料,按一定配比量配制成混合单体,在反应初期,加入部分混合单体、乳化剂和去离子水于反应釜中,并充分搅拌混匀,升温至50-70℃,在该温度稳定后,连续加入剩余的丙烯酸乙酯和甲基丙烯酸甲酯的混合单体及乳化剂、引发剂溶液,在该温度反应3-5小时后得到乳白色乳液即为附聚剂。再将高分子附聚剂和乳化剂、去离子水配成均匀的乳液,然后加入到待附聚胶乳中搅拌混合,半小时后可使待附胶乳的有效粒径由80-110nm增大至280-330nm。(The invention provides a preparation method and application of polymer agglomerated latex. The polymer agglomerant is prepared by using ethyl acrylate and methyl methacrylate as raw materials, preparing a mixed monomer according to a certain proportion, adding part of the mixed monomer, an emulsifier and deionized water into a reaction kettle at the initial stage of reaction, fully stirring and uniformly mixing, heating to 50-70 ℃, continuously adding the rest of the mixed monomer of ethyl acrylate and methyl methacrylate, the emulsifier and an initiator solution after the temperature is stable, and reacting at the temperature for 3-5 hours to obtain a milky emulsion, namely the agglomerant. Then the polymer agglomerant, the emulsifier and the deionized water are prepared into uniform emulsion, and then the uniform emulsion is added into the latex to be agglomerated to be stirred and mixed, and after half an hour, the effective particle size of the latex to be attached can be increased from 80-110nm to 280-330 nm.)

1. The polymer agglomerant emulsion is characterized by comprising the following raw materials in percentage by weight:

100 percent of deionized water

0.5 to 2 percent of emulsifier

1-20% of polymer agglomerant.

2. The polymer agglomerant emulsion of claim 1 wherein the polymer agglomerant is comprised of the following raw materials in weight percent:

3. the polymer agglomerant emulsion of claim 1 or 2, wherein the emulsifier is sodium dodecylbenzene sulfonate or potassium oleate or potassium disproportionate rosin acid.

4. The polymer agglomerant emulsion of claim 2 wherein the initiator is potassium persulfate or sodium persulfate.

5. The application of the polymer agglomerant emulsion of claim 1, wherein the polymer agglomerant emulsion and the latex to be agglomerated are prepared from the following raw materials in percentage by weight:

0.5-2% of polymer agglomerant emulsion dry basis

The latex to be agglomerated is 100% dry.

6. The use of a polymeric agglomerant emulsion according to claim 5, comprising the steps of:

(1) synthetic polymer agglomerant

Adding a mixed monomer of deionized water, an emulsifier, ethyl acrylate and methyl methacrylate into a reaction kettle according to a certain proportion, fully stirring and emulsifying, heating to 70 ℃, after the temperature is stable, continuously adding an aqueous solution prepared from the mixed monomer of ethyl acrylate and methyl methacrylate, the emulsifier and an initiator into the reaction kettle at a constant speed within 2 hours, and after the addition is finished, continuously stirring at the temperature for 2 hours to finish the reaction, thus obtaining a milky emulsion, namely the high-molecular agglomerant;

(2) saponification of polymer agglomerant

Adding 1 part of emulsifier into 100 parts of deionized water, fully dissolving, adding 5-20 parts of polymer agglomerating agent, uniformly stirring to obtain polymer agglomerating agent emulsion, and calculating the dry basis weight of the polymer agglomerating agent in the polymer agglomerating agent emulsion;

(3) weighing the polymer agglomerant emulsion, adding the polymer agglomerant emulsion into the latex to be agglomerated according to the dry part ratio of 0.5-2:100, quickly and uniformly stirring, slowly stirring for 30 minutes and discharging.

7. The use of the polymeric agglomerating agent emulsion according to claim 6, wherein the agglomerated latex is stirred at room temperature for half an hour, and the effective particle size of the latex to be attached is increased from 80-110nm to 280-330 nm.

Technical Field

The invention relates to a preparation method of polymer agglomerated latex and an application technology thereof, in particular to a method for preparing small-particle rubber latex into large-particle rubber latex by using a polymer agglomeration method.

Background

The polybutadiene latex needs at least 40h to enlarge the particle size in the general polymerization process. In order to shorten the latex reaction time and increase the particle size, the process of agglomeration amplification is currently used industrially, i.e., a small particle size latex is synthesized and then enlarged by various agglomeration methods. There are various agglomeration methods such as a freeze agglomeration method, a pressure agglomeration method, a mechanical agitation agglomeration method, a chemical agglomeration method, a polymer latex agglomeration method, and the like. Compared with other agglomeration methods, the polymer agglomeration method has higher requirements on agglomeration equipment, harsh agglomeration conditions and difficult control of particle size, and the polymer agglomeration method is a suitable polymer agglomerating agent synthesized and can realize particle size increase by uniformly stirring the polymer agglomerating agent and latex to be agglomerated at normal temperature. The agglomeration method is simple, the particle size is easy to increase and control, and the agglomerated latex has good stability and can be applied to an industrial device.

CN 103044580A discloses a method for synthesizing polymer agglomerant, which comprises the steps of taking butyl acrylate, methacrylic acid and styrene as raw materials, adding auxiliary agents such as sodium bicarbonate, sodium dodecyl sulfate, potassium persulfate and dodecyl mercaptan, polymerizing for 1-4 hours at 50-70 ℃, raising the temperature to 70-85 ℃, and stirring for 0.5-2 hours to finish the reaction.

CN 102321211A discloses an acrylic ester agglomerating agent, the effective components of the agglomerating agent are acrylic ester and unsaturated acid, the acrylic ester is butyl acrylate, ethyl acrylate or the mixed monomer thereof, and the unsaturated acid is acrylic acid or methacrylic acid. Compounding emulsifier and deionized water, adding initiator at 60-85 deg.c, maintaining the temperature for 6-8 hr and finishing the reaction.

CN 102115506A discloses a polymer agglomerant which is a copolymer of alkyl acrylate and carboxyl monomer, and is initiated by a first-stage water-soluble initiator and a second-stage oil-soluble initiator in the preparation process, and the average particle size of the agglomerant is adjusted by a cross-linking agent to prepare a large-particle-size latex.

The article of the Yankeenming of Qingdao science and technology university adopts EA and itaconic acid as raw materials, an emulsifier, an initiator and other auxiliary agents are added, and the temperature is raised to 75 ℃ under the protection of nitrogen to start the reaction. And cooling and discharging after the conversion rate meets the requirement to obtain the agglomerating agent latex.

According to the technology, during agglomeration, some polymer agglomerants are directly dripped into the latex to be agglomerated, some latex to be agglomerated is firstly prepared and then the polymer agglomerants are dripped for agglomeration, the invention adopts the technology that the polymer agglomerants are firstly prepared and then the agglomerated latex is prepared, the agglomerated latex prepared by the technology has good stability, and the particle size and the like can reach a stable state after agglomeration for half an hour.

Disclosure of Invention

The invention aims to provide a preparation method of polymer agglomeration latex and an application technology thereof, and particularly relates to a method for preparing small-particle rubber latex into large-particle rubber latex by using a polymer agglomeration method. In order to achieve the above object of the present invention, the following technical solutions are adopted.

A high-molecular agglomerant emulsion comprises the following raw materials in percentage by weight:

100 percent of deionized water

0.5 to 2 percent of emulsifier

1-20% of polymer agglomerant.

The polymer agglomerant comprises the following raw materials in percentage by weight:

the emulsifier is sodium dodecyl benzene sulfonate or potassium oleate or potassium disproportionate abietate.

The initiator is potassium persulfate or sodium persulfate.

The application of the polymer agglomerant emulsion comprises the following raw materials in percentage by weight:

0.5-2% of polymer agglomerant emulsion dry basis

The latex to be agglomerated is 100% dry.

The method specifically comprises the following steps:

(1) synthetic polymer agglomerant

Adding a mixed monomer of deionized water, an emulsifier, ethyl acrylate and methyl methacrylate into a reaction kettle according to a certain proportion, fully stirring and emulsifying, heating to 70 ℃, after the temperature is stable, continuously adding an aqueous solution prepared from the mixed monomer of ethyl acrylate and methyl methacrylate, the emulsifier and an initiator into the reaction kettle at a constant speed within 2 hours, and after the addition is finished, continuously stirring at the temperature for 2 hours to finish the reaction, thus obtaining a milky emulsion, namely the high-molecular agglomerant;

(2) saponification of polymer agglomerant

Adding 1 part of emulsifier into 100 parts of deionized water, fully dissolving, adding 5-20 parts of polymer agglomerating agent, uniformly stirring to obtain polymer agglomerating agent emulsion, and calculating the dry basis weight of the polymer agglomerating agent in the polymer agglomerating agent emulsion;

(3) weighing the polymer agglomerant emulsion, adding the polymer agglomerant emulsion into the latex to be agglomerated according to the dry part ratio of 0.5-2:100, quickly and uniformly stirring, slowly stirring for 30 minutes and discharging.

The agglomerated latex is stirred for half an hour at normal temperature, and the effective particle size of the latex to be attached is increased from 80-110nm to 280-330 nm.

The invention has the advantages of

The invention has simple process, can be realized at normal temperature by common stirring, the agglomerated latex has very good stability, the particle size, surface tension, mechanical stability and the like of the latex are not greatly changed within half an hour to one month, the agglomerated latex with small particle size of 80-110nm accounts for 10-50 percent, the agglomerated latex with large particle size of 40-600nm accounts for 50-90 percent, the glossiness and impact strength of the product can be effectively adjusted by adjusting the adding amount of the polymer agglomerated latex, and the ABS resin with excellent physical properties is prepared.

Detailed Description

The present invention will be described in detail with reference to the following examples, but the present invention is not limited to the following examples and should not be construed as being limited thereto.

Example 1:

(1) synthetic polymer agglomerant

Adding a mixed monomer of deionized water, sodium dodecyl benzene sulfonate, ethyl acrylate and methyl methacrylate into a reaction kettle according to a certain proportion, fully stirring and emulsifying, heating to 70 ℃, after the temperature is stable, continuously adding the mixed monomer prepared according to a certain proportion of ethyl acrylate and methyl methacrylate, an aqueous solution prepared from sodium dodecyl benzene sulfonate and sodium persulfate into the reaction kettle at a constant speed within 2 hours, and after the addition is finished, continuously stirring at the temperature for 2 hours to finish the reaction, thus obtaining a milky white emulsion, namely the high polymer agglomerant.

(2) Saponification of polymer agglomerant

Adding 1 part of sodium dodecyl benzene sulfonate into 100 parts of deionized water, fully dissolving, adding 5-20 parts of polymer agglomerating agent, and uniformly stirring. Calculating the dry basis weight of the polymer agglomerant in the polymer agglomerant emulsion.

(3) Weighing the polymer agglomerant emulsion, adding the polymer agglomerant emulsion into the to-be-agglomerated latex with the particle size of 102.5nm according to the dry part ratio of 0.8:100, quickly and uniformly stirring, slowly stirring for 30 minutes and discharging. The effective particle size is 280nm when the particle size is tested.

Example 2:

(1) synthetic polymer agglomerant

Adding deionized water, potassium oleate, mixed monomers of ethyl acrylate and methyl methacrylate into a reaction kettle according to a certain proportion, fully stirring and emulsifying, heating to 70 ℃, after the temperature is stable, continuously adding the mixed monomers of ethyl acrylate and methyl methacrylate, potassium oleate and sodium persulfate into the reaction kettle at a constant speed within 2 hours, and after the addition is finished, continuously stirring at the temperature for 2 hours to finish the reaction, thus obtaining milky emulsion, namely the polymer agglomerant.

(2) Saponification of polymer agglomerant

Adding 1 part of potassium oleate into 100 parts of deionized water, fully dissolving, adding 5-20 parts of polymer agglomerant, and uniformly stirring. Calculating the dry basis weight of polymer agglomeration in the polymer agglomerant emulsion.

(3) Weighing the polymer agglomerant emulsion, adding the polymer agglomerant emulsion into the to-be-agglomerated latex with the particle size of 102.5nm according to the dry part ratio of 1:100, quickly and uniformly stirring, slowly stirring for 30 minutes and discharging. The effective particle size is 295nm when the particle size is tested.

Example 3:

(1) synthetic polymer agglomerant

Adding deionized water, disproportionated rosin potassium, ethyl acrylate, methyl methacrylate and the like into a reaction kettle according to a certain proportion, fully stirring and emulsifying, heating to 70 ℃, after the temperature is stable, continuously adding a mixed monomer prepared from the ethyl acrylate and the methyl methacrylate, a water solution prepared from the disproportionated rosin potassium and sodium persulfate into the reaction kettle at a constant speed within 2 hours, and after the addition is finished, continuously stirring at the temperature for 2 hours to finish the reaction, thus obtaining a milky emulsion, namely the high-molecular agglomerant.

(2) Saponification of polymer agglomerant

Adding 1 part of disproportionated potassium rosinate into 100 parts of deionized water, fully dissolving, adding 5-20 parts of polymer agglomerating agent, and uniformly stirring. Calculating the dry basis weight of polymer agglomeration in the polymer agglomerant emulsion.

(3) Weighing the polymer agglomerant emulsion, adding the polymer agglomerant emulsion into the to-be-agglomerated latex with the particle size of 102.5nm according to the dry part ratio of 1:100, quickly and uniformly stirring, slowly stirring for 30 minutes and discharging. The particle size was measured and the effective particle size was 305 nm.

Example 4:

(1) synthetic polymer agglomerant

Adding deionized water, sodium dodecyl benzene sulfonate, a mixed monomer of ethyl acrylate and methyl methacrylate into a reaction kettle according to a certain proportion, fully stirring and emulsifying, heating to 65 ℃, after the temperature is stable, continuously adding the mixed monomer of ethyl acrylate and methyl methacrylate, an aqueous solution prepared from sodium dodecyl benzene sulfonate and sodium persulfate into the reaction kettle at a constant speed within 2.5 hours, and after the addition is finished, continuously stirring at the temperature for 2 hours to finish the reaction, thus obtaining milky white emulsion which is the polymer agglomerant.

(2) Saponification of polymer agglomerant

Adding 1 part of sodium dodecyl benzene sulfonate into 100 parts of deionized water, fully dissolving, adding 5-20 parts of polymer agglomerating agent, and uniformly stirring. Calculating the dry basis weight of the polymer agglomerant in the polymer agglomerant emulsion.

(3) Weighing the polymer agglomerant emulsion, adding the polymer agglomerant emulsion into the to-be-agglomerated latex with the particle size of 102.5nm according to the dry part ratio of 1.2:100, quickly and uniformly stirring, slowly stirring for 30 minutes and discharging. The effective particle size is 320nm when the particle size is tested.

Example 5:

(1) synthetic polymer agglomerant

Adding deionized water, sodium dodecyl benzene sulfonate, a mixed monomer of ethyl acrylate and methyl methacrylate into a reaction kettle according to a certain proportion, fully stirring and emulsifying, heating to 63 ℃, after the temperature is stable, continuously adding the mixed monomer of ethyl acrylate and methyl methacrylate, an aqueous solution prepared from sodium dodecyl benzene sulfonate and sodium persulfate into the reaction kettle at a constant speed within 2 hours, and after the addition is finished, continuously stirring at the temperature for 3 hours, and finishing the reaction to obtain a milky emulsion, namely the polymer agglomerant.

(2) Saponification of polymer agglomerant

Adding 1 part of sodium dodecyl benzene sulfonate into 100 parts of deionized water, fully dissolving, adding 5-20 parts of polymer agglomerating agent, and uniformly stirring. Calculating the dry basis weight of polymer agglomeration in the polymer agglomerant emulsion.

(3) Weighing the polymer agglomerant emulsion, adding the polymer agglomerant emulsion into the to-be-agglomerated latex with the particle size of 102.5nm according to the dry part ratio of 1.5:100, quickly and uniformly stirring, slowly stirring for 30 minutes and discharging. The effective particle size is 325nm when the particle size is tested.

Example 6:

(1) synthetic polymer agglomerant

Adding deionized water, sodium dodecyl benzene sulfonate, a mixed monomer of ethyl acrylate and methyl methacrylate into a reaction kettle according to a certain proportion, fully stirring and emulsifying, heating to 70 ℃, after the temperature is stable, continuously adding the mixed monomer of ethyl acrylate and methyl methacrylate, an aqueous solution prepared from sodium dodecyl benzene sulfonate and sodium persulfate into the reaction kettle at a constant speed within 2 hours, and after the addition is finished, continuously stirring at the temperature for 2 hours to finish the reaction, thus obtaining a milky emulsion, namely the polymer agglomerant.

(2) Saponification of polymer agglomerant

Adding 1 part of sodium dodecyl benzene sulfonate into 100 parts of deionized water, fully dissolving, adding 5-20 parts of polymer agglomerating agent, and uniformly stirring. Calculating the dry basis weight of polymer agglomeration in the polymer agglomerant emulsion.

(3) Weighing the polymer agglomerant emulsion, adding the polymer agglomerant emulsion into the to-be-agglomerated latex with the particle size of 102.5nm according to the dry part ratio of 1.8:100, quickly and uniformly stirring, slowly stirring for 30 minutes and discharging. The particle size was measured and the effective particle size was 330 nm.