Production method of macroporous acrylic high-molecular polymer

Abstract

The invention belongs to the technical field of resin production, and particularly relates to a production method of a macroporous acrylic high-molecular polymer. The preparation method comprises the following steps: adding gelatin, Tween 20 and hydroxyethyl cellulose into softened water to prepare a water phase; mixing methyl acrylate, acrylonitrile, trimethylolpropane trimethacrylate, benzoyl peroxide, ethylene glycol dimethacrylate and methylbenzene to prepare an organic phase, adding the organic phase into the water phase, shearing and emulsifying to obtain emulsion, and performing polymerization reaction to obtain polymerized spheres; and finally, adding a cross-linking agent into a mixed solution of benzoyl peroxide and propylene carbonate, and carrying out cross-linking reaction again to obtain the high-molecular polymer. The specific reagent is combined with secondary crosslinking, so that not only can the preparation of the macroporous high-molecular polymer be realized, but also the pore channel structure can be accurately controlled, and the product performance is ensured. The prepared high-molecular polymer is high in porosity, large in aperture and excellent in effect; and the method is easy to operate, easy to realize industrial production and wide in application prospect.

Description

Technical Field

[0001] The present invention belongs to the technical field of resin production, and particularly relates to a production method of a macroporous acrylic polymer. Background Art

[0002] Ion exchange resins are a class of polymer functional materials with a three-dimensional cross-linked network structure, in which active functional groups with ion exchange ability are fixedly distributed in the molecular chain; such substances achieve reversible ion exchange reactions through the functional groups in the backbone. This material system includes three core components: (1) Rigid matrix network: an insoluble spatial framework composed of cross-linked polymers, providing mechanical stability; (2) Functional coordination unit: specific reactive groups covalently bonded to the backbone, determining the resin properties; (3) Dynamic exchange ions: counterions that balance the charge of the functional groups, realizing the material exchange function. Moreover, there are many types of ion exchange resin products; classified according to the characteristics of active groups, they can be divided into cationic, anionic, and special functional types. Among them, cationic types include strong acid type (sulfonic group) and weak acid type (carboxylic group); anionic types include strong base type (quaternary ammonium group) and weak base type (primary amine group); special functional types include chelating type, zwitterionic type, and redox type. The applications of ion exchange resins mainly include three aspects: water treatment resins, adsorption and separation resins, and catalytic reaction resins.

[0003] At present, in the field of polymer synthesis technology, there is a diversified development trend, and the main research includes the following core methods: (1) Suspension polymerization, achieving polymerization through the stable dispersion of monomer droplets in the continuous phase; (2) Dispersion polymerization, forming a homogeneous reaction system at the colloidal scale; (3) Emulsion polymerization, constructing a microreaction environment using surfactants; (4) Seed swelling polymerization, regulating the particle size gradient based on the prepolymer. For example, some literature uses the emulsification method to prepare macroporous polymers. The scheme is to first prepare a water-in-oil-in-water double emulsion as a template for supermacroporous polymers, then use the solvent removal method to solidify the oil phase, and finally crosslink the microsphere skeleton molecules; although it can obtain macroporous polymers, its method is relatively complex and not conducive to actual production applications. Summary of the Invention

[0004] In view of the deficiencies of the prior art, the present invention provides a production method of a macroporous acrylic polymer. The prepared polymer not only has a simple and easy-to-operate method, but also has super-large pores and good performance.

[0005] To achieve the above objectives, the present invention adopts the following technical solutions;

[0006] A production method of a macroporous acrylic polymer, the specific steps are as follows:

[0007] (1) Prepare the aqueous phase: Add gelatin to softened water, heat to dissolve, then add Tween 20 and hydroxyethyl cellulose, and heat and stir evenly to obtain the aqueous phase for standby; the dosage relationship of the softened water, gelatin, Tween 20 and hydroxyethyl cellulose is 1000 - 1200 ml: 5 - 10 g: 2 - 4 g: 3 - 5 g;

[0008] (2) Prepare the organic phase: Mix methyl acrylate, acrylonitrile and trimethylolpropane trimethacrylate in proportion and add them to the batching kettle; then add benzoyl peroxide to ethylene glycol dimethacrylate, stir evenly, and then add it to the batching kettle. Finally, add toluene and stir evenly to obtain the organic phase for standby; among them, the mass ratio of methyl acrylate, acrylonitrile, trimethylolpropane trimethacrylate, benzoyl peroxide, ethylene glycol dimethacrylate and toluene is 25 - 40: 120 - 150: 10 - 15: 1 - 3: 1 - 3: 60 - 70;

[0009] (3) Add the organic phase prepared in step (2) to the aqueous phase prepared in step (1), perform shear emulsification, and form an O / W type emulsion after emulsification; then transfer the O / W type emulsion to the reaction kettle, heat up to 50 - 55 °C, maintain the reaction for 1 - 2 h, then heat up to 82 - 86 °C and maintain the reaction for 2 - 3 h. After the reaction is completed, transfer it to the oil blowing kettle, filter out the reaction liquid, and obtain polymer spheres;

[0010] (4) Add the crosslinking agent and benzoyl peroxide to propylene carbonate, then transfer it to the reaction kettle, and add the polymer spheres obtained in step (3) to the reaction kettle. Heat up to 80 - 82 °C and maintain the reaction for 2 - 4 h to achieve the re-crosslinking reaction of polymer molecules. The crosslinking agent consists of ethylene glycol dimethacrylate and divinylbenzene; after the reaction, wash to obtain the high molecular polymer.

[0011] Preferably, the temperature for heating and dissolving in step (1) is 60 - 70 °C.

[0012] Preferably, the temperature for heating and stirring in step (1) is 50 - 55 °C; the stirring time is 20 - 30 min.

[0013] Preferably, the mass ratio of the organic phase to the aqueous phase in step (3) is 1: 6 - 10.

[0014] Preferably, the shear emulsification conditions in step (3) are: 10000 - 20000 rpm, time 2 - 4 min.

[0015] Preferably, the mass ratio of the polymer spheres to propylene carbonate in step (4) is 1: 5 - 10.

[0016] Preferably, in step (4), the mass ratio of the crosslinking agent, benzoyl peroxide and propylene carbonate is 0.01 - 0.05:0.01 - 0.05:1.

[0017] Preferably, in step (4), the mass ratio of ethylene glycol dimethacrylate and divinylbenzene is 2:0.5 - 1.

[0018] The beneficial effects of the present invention are as follows:

[0019] (1) In the preparation process of the aqueous phase of the present invention, gelatin is added. Gelatin is a natural amphiphilic macromolecule with excellent surface activity. Using it as an emulsifier can improve the stability of the final emulsion. At the same time, cellulose is used as a dispersant in the aqueous phase and Tween 20 is used as an active agent, which can make the emulsion more stable, so that the sphericity of the prepared polymer can be more rounded. In addition, the use of trimethylolpropane trimethacrylate in the present invention can effectively improve the anti-pollution, high strength, large pore size, heat resistance, corrosion resistance, antioxidant and other properties of the product. At the same time, by combining ethylene glycol dimethacrylate to participate in the copolymerization polymer, the hardness of the product can be increased, and the heat resistance, weather resistance and solvent resistance can be improved, which is beneficial to subsequent processing and application.

[0020] (2) Traditional methods often require a relatively high aqueous phase, reaching dozens or even hundreds of times, when preparing emulsions. However, the present invention does not require the addition of a high proportion of aqueous phase. By combining process control and controlling the conditions of shear emulsification, an emulsion structure with high internal phase characteristics can be prepared. Finally, the present invention crosslinks the polymer spheres, effectively realizing the preparation of a macroporous polymer, and ensuring that the polymer has good properties.

[0021] (3) The polymer prepared by the present invention has a high porosity, large pore size and excellent comprehensive performance. Moreover, the operation is simple, and it is easy to realize the industrial production of the polymer, with broad application prospects. Detailed Embodiments

[0022] It should be understood that the terms described in the present invention are only for describing specific embodiments and are not used to limit the present invention. In addition, for the numerical ranges in the present invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Each intermediate value within any stated value or stated range, as well as each smaller range between any other stated value or intermediate value within the stated range, is also included in the present invention. The upper and lower limits of these smaller ranges may be independently included or excluded within the range.

[0023] Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. Although this invention has been described only with reference to preferred methods and materials, any methods and materials similar or equivalent to those described herein may also be used in the practice or testing of this invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and / or materials related to the documents. In case of conflict with any incorporated document, the content of this specification shall prevail.

[0024] Various modifications and variations of the specific embodiments of the description of this invention will be apparent to those skilled in the art without departing from the scope or spirit of this invention. Other embodiments derived from the description of this invention will be apparent to those skilled in the art. The description and examples of this invention are merely exemplary.

[0025] Example 1:

[0026] A porous acrylic polymer is prepared as follows:

[0027] (1) Prepare the aqueous phase: Add 500 g of gelatin to 100 L of softened water and heat to 65 °C for dissolution; then add 400 g of Tween 20 and 300 g of hydroxyethyl cellulose, and stir for 30 min at a heating temperature of 50 °C to obtain a uniformly stirred aqueous phase.

[0028] (2) Prepare the organic phase: Mix 4 Kg of methyl acrylate, 12 Kg of acrylonitrile, and 1.5 Kg of trimethylolpropane trimethacrylate; then add 300 g of benzoyl peroxide to 300 g of ethylene glycol dimethacrylate, stir evenly, and add it to the batching kettle together with the mixture of methyl acrylate and trimethylolpropane trimethacrylate. Finally, add 6.5 Kg of toluene and stir evenly to obtain the organic phase for standby;

[0029] (3) Add the organic phase prepared in step (2) to the aqueous phase prepared in step (1) at a ratio of 1:8 for shear emulsification under the conditions of 20000 rpm for 2 min; after emulsification, form an O / W emulsion, then transfer the O / W emulsion to a reaction kettle, heat up to 55 °C, maintain the reaction for 2 h, then heat up to 82 °C and maintain the reaction for 2 h. After the reaction is completed, filter off the reaction liquid to obtain polymer spheres;

[0030] (4) Add 400 g of ethylene glycol dimethacrylate, 200 g of divinylbenzene, and 300 g of benzoyl peroxide to 10 kg of propylene carbonate, then transfer it to a reaction kettle, and add 1.5 kg of the polymer spheres obtained in step (3) to the reaction kettle. Heat up to 80 °C and maintain the reaction for 4 h to achieve the re-crosslinking reaction of polymer molecules. After the reaction, wash it to obtain a high molecular polymer. The index test results are shown in Table 1.

[0031] Example 2:

[0032] The preparation steps of the porous acrylic-based high molecular polymer are as follows:

[0033] (1) Prepare the aqueous phase: Add 500 g of gelatin to 100 L of softened water and heat it to 65 °C for dissolution; then add 200 g of Tween 20 and 300 g of hydroxyethyl cellulose, and stir for 30 min at a heating temperature of 50 °C to make it evenly mixed to obtain the aqueous phase.

[0034] (2) Prepare the organic phase: Mix 3 kg of methyl acrylate, 14 kg of acrylonitrile, and 1.0 kg of trimethylolpropane trimethacrylate; then add 300 g of benzoyl peroxide to 200 g of ethylene glycol dimethacrylate, stir evenly, and add it to the mixing kettle together with the mixture of methyl acrylate and trimethylolpropane trimethacrylate. Finally, add 6.5 kg of toluene and stir evenly to obtain the organic phase for standby;

[0035] (3) Add the organic phase prepared in step (2) to the aqueous phase prepared in step (1) at a ratio of 1:10, and perform shear emulsification under the conditions of: 20000 rpm and a time of 2 min; after emulsification, an O / W type emulsion is formed, and then transfer the O / W type emulsion to a reaction kettle, heat up to 55 °C, maintain the reaction for 2 h, then heat up to 82 °C and maintain the reaction for 2 h. After the reaction is completed, filter off the reaction liquid to obtain polymer spheres;

[0036] (4) Add 400 g of ethylene glycol dimethacrylate, 100 g of divinylbenzene, and 400 g of benzoyl peroxide to 10 kg of propylene carbonate, then transfer it to a reaction kettle, and add 1.5 kg of the polymer spheres obtained in step (3) to the reaction kettle. Heat up to 82 °C and maintain the reaction for 4 h to achieve the re-crosslinking reaction of polymer molecules. After the reaction, wash it to obtain a high molecular polymer. The index test results are shown in Table 1.

[0037] Example 3:

[0038] The preparation steps of the porous acrylic-based high molecular polymer are as follows:

[0039] (1) Preparation of aqueous phase: Add 600 g of gelatin to 100 L of softened water and heat to 65 °C for dissolution; then add 300 g of Tween 20 and 400 g of hydroxyethyl cellulose, and stir for 30 min at a heating temperature of 50 °C. Stir evenly to obtain the aqueous phase.

[0040] (2) Preparation of organic phase: Mix 2.5 Kg of methyl acrylate, 15 Kg of acrylonitrile and 1.5 Kg of trimethylolpropane trimethacrylate; then add 100 g of benzoyl peroxide to 300 g of ethylene glycol dimethacrylate, stir evenly, and add it to the mixing kettle together with the mixture of methyl acrylate and trimethylolpropane trimethacrylate. Finally, add 6.5 Kg of toluene and stir evenly to prepare the organic phase for standby;

[0041] (3) Add the organic phase prepared in step (2) to the aqueous phase prepared in step (1) at a ratio of 1:6, and perform shear emulsification under the conditions of 20000 rpm and a time of 2 min; after emulsification, form an O / W type emulsion, then transfer the O / W type emulsion to the reaction kettle, heat up to 55 °C, maintain the reaction for 2 h, then heat up to 82 °C and maintain the reaction for 2 h. After the reaction is completed, filter off the reaction liquid to obtain polymer spheres;

[0042] (4) Add 400 g of ethylene glycol dimethacrylate, 200 g of divinylbenzene and 300 g of benzoyl peroxide to 10 Kg of propylene carbonate, then transfer it to the reaction kettle, and add 1.5 Kg of the polymer spheres obtained in step (3) to the reaction kettle. Heat up to 80 °C and maintain the reaction for 4 h to achieve the re-crosslinking reaction of polymer molecules. After the reaction, wash to obtain the high molecular polymer. The test results of the indicators are shown in Table 1.

[0043] Comparative Example 1:

[0044] (1) Preparation of aqueous phase: Add 500 g of gelatin to 100 L of softened water and heat to 65 °C for dissolution; then add 400 g of Tween 20 and 300 g of hydroxyethyl cellulose, and stir for 30 min at a heating temperature of 50 °C. Stir evenly to obtain the aqueous phase.

[0045] (2) Preparation of organic phase: Mix 4 Kg of methyl acrylate, 12 Kg of acrylonitrile and 1.5 Kg of trimethylolpropane trimethacrylate; then add 300 g of benzoyl peroxide to 300 g of ethylene glycol dimethacrylate, stir evenly, and add it to the mixing kettle together with the mixture of methyl acrylate and trimethylolpropane trimethacrylate. Finally, add 6.5 Kg of toluene and stir evenly to prepare the organic phase for standby;

[0046] (3) Add the organic phase prepared in step (2) to the aqueous phase prepared in step (1) at a ratio of 1:8, and perform shear emulsification under the conditions of 20000 rpm for 2 min; after emulsification, an O / W emulsion is formed, and then the O / W emulsion is transferred to a reaction kettle, heated to 55 °C, and the reaction is maintained for 2 h, then heated to 82 °C and maintained for 2 h. After the reaction is completed, filter off the reaction liquid to obtain polymer spheres. The test results of the indicators are shown in Table 1.

[0047] Comparative Example 2:

[0048] (1) Prepare the aqueous phase: Add 500 g of hydroxyethyl cellulose to 100 L of softened water, and stir at a heating temperature of 50 °C for 30 min, and stir evenly to obtain the aqueous phase.

[0049] (2) Prepare the organic phase: Mix 4 Kg of methyl acrylate, 12 Kg of acrylonitrile and 1.5 Kg of trimethylolpropane trimethacrylate; then add 300 g of benzoyl peroxide to 300 g of ethylene glycol dimethacrylate, stir evenly, and then add it to the mixing kettle together with the mixture of methyl acrylate and trimethylolpropane trimethacrylate, and finally add 6.5 Kg of toluene, stir evenly, and prepare the organic phase for standby;

[0050] (3) Add the organic phase prepared in step (2) to the aqueous phase prepared in step (1) at a ratio of 1:8, and perform shear emulsification under the conditions of 20000 rpm for 2 min; after emulsification, an O / W emulsion is formed, and then the O / W emulsion is transferred to a reaction kettle, heated to 55 °C, and the reaction is maintained for 2 h, then heated to 82 °C and maintained for 2 h. After the reaction is completed, filter off the reaction liquid to obtain polymer spheres. The test results of the indicators are shown in Table 1.

[0051] Table 1: Index detection of polymer:

[0052]

[0053] Reference: According to GB / T 6003.1-2012 "Technical Requirements and Inspection of Test Sieves - Part 1: Test Sieves of Metal Wire Mesh", the particle size distribution is determined by standard sieve analysis; according to GB / T 21650.2-2008 "Determination of Pore Size Distribution and Porosity of Solid Materials by Mercury Intrusion and Gas Adsorption - Part 2: Gas Adsorption Method for Analysis of Mesopores and Macropores", the pore size distribution is determined by gas adsorption or mercury porosimeter. Combining with GB / T 19587-2017 "Determination of Specific Surface Area of Solid Substances by Gas Adsorption BET Method", the pore size and specific surface area can be analyzed synchronously; the pores are filled with a replacement liquid (such as water or ethanol), and the porosity is calculated based on the volume change; based on GB / T19077-2016, D 10 and D60 Value, calculate the coefficient of uniformity.

[0054] As can be seen from Table 1, the macroporous acrylic polymer prepared by the present invention has a high porosity, large pore size, and excellent comprehensive performance, realizing the production of macroporous acrylic polymers; moreover, the process provided by the present invention is simple to operate and easy to realize the industrial production of polymers, with broad application prospects.

[0055] Note: The above embodiments are only used to illustrate the present invention and do not limit the technical solutions described in the present invention; therefore, although the present specification has described the present invention in detail with reference to the above embodiments, those of ordinary skill in the art should understand that the present invention can still be modified or equivalently replaced; and all technical solutions and their improvements that do not depart from the spirit and scope of the present invention should be covered within the scope of the claims of the present invention.

Claims

1. A production method of a macroporous acrylic polymer, characterized in that, The steps are as follows: (1) Prepare the aqueous phase: Add gelatin to softened water, heat to dissolve, then add Tween 20 and hydroxyethyl cellulose, and heat and stir evenly to obtain the aqueous phase for standby; the dosage relationship of the softened water, gelatin, Tween 20 and hydroxyethyl cellulose is 1000-1200 ml: 5-10 g: 2-4 g: 3-5 g; (2) Prepare the organic phase: Mix methyl acrylate, acrylonitrile and trimethylolpropane trimethacrylate in proportion and add them to the batching kettle; then add benzoyl peroxide to ethylene glycol dimethacrylate, stir evenly, and then add it to the batching kettle. Finally, add toluene and stir evenly to obtain the organic phase for standby; among them, the mass ratio of methyl acrylate, acrylonitrile, trimethylolpropane trimethacrylate, benzoyl peroxide, ethylene glycol dimethacrylate and toluene is 25-40: 120-150: 10-15: 1-3: 1-3: 60-70; (3) Add the organic phase prepared in step (2) to the aqueous phase prepared in step (1), perform shear emulsification to form an O / W type emulsion after emulsification; then transfer the O / W type emulsion to the reaction kettle, heat up to 50-55 °C, maintain the reaction for 1-2 h, and then heat up to 82-86 °C and maintain the reaction for 2-3 h. After the reaction is completed, transfer it to the oil blowing kettle, filter off the reaction liquid to obtain polymer spheres; (4) Add the crosslinking agent and benzoyl peroxide to propylene carbonate, then transfer it to the reaction kettle, and add the polymer spheres obtained in step (3) to the reaction kettle. Heat up to 80-82 °C and maintain the reaction for 2-4 h to achieve the re-crosslinking reaction of polymer molecules. The crosslinking agent is composed of ethylene glycol dimethacrylate and divinylbenzene; after the reaction, wash to obtain a high molecular polymer.

2. The production method of a macroporous acrylic polymer according to claim 1, characterized in that, The temperature for heating and dissolving in step (1) is 60-70 °C.

3. The production method of a macroporous acrylic polymer according to claim 1, characterized in that, The temperature for heating and stirring in step (1) is 50-55 °C; the stirring time is 20-30 min.

4. The production method of a macroporous acrylic polymer according to claim 1, characterized in that, In step (3), the mass ratio of the organic phase to the aqueous phase is 1:6-10.

5. The production method of a macroporous acrylic polymer according to claim 1, characterized in that, The shear emulsification conditions in step (3) are: 10000-20000 rpm, time 2-4 min.

6. The production method of a macroporous acrylic polymer according to claim 1, characterized in that In step (4), the mass ratio of the polymer spheres to propylene carbonate is 1:5-10.

7. A production method of a macroporous acrylic polymer according to claim 1, characterized in that, In step (4), the mass ratio of the crosslinking agent, benzoyl peroxide and propylene carbonate is 0.01-0.05: 0.01-0.05:

1.

8. The production method of a macroporous acrylic polymer according to claim 1, characterized in that, In step (4), the mass ratio of ethylene glycol dimethacrylate and divinylbenzene is 2: 0.5-1.

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