CN115677924A - Low-molecular-weight polyacrylamide colloidal particle and preparation method thereof - Google Patents
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Abstract
The invention discloses a low molecular weight polyacrylamide colloidal particle and a preparation method thereof, belonging to the technical field of water-soluble polyacrylamide. The polyacrylamide colloid with the molecular weight less than 100w is prepared by redox reaction, and in order to prevent the low molecular weight polyacrylamide colloid from being soft and high in viscosity after the concentration exceeds 50%, a colloid reinforcing agent consisting of a reactive cross-linking agent, a non-reactive micromolecule and a non-reactive polar oligomer is added into a polymerization system. The low molecular weight polyacrylamide colloidal particles avoid the generation of insoluble substances caused by overhigh temperature in the fluidized bed drying process, greatly reduce the energy loss in the drying process, can be applied to the modification of paper fibers, and have simple, continuous, high-efficiency and high-yield preparation method.
Description
Technical Field
The invention relates to the technical field of water-soluble polyacrylamide correlation, in particular to low-molecular-weight polyacrylamide colloidal particles and a preparation method thereof.
Background
Polyacrylamide is a generic name for acrylamide homopolymers or polymers obtained by copolymerizing acrylamide with other monomers, and is one of the most widely used species of water-soluble polymers. Because the polyacrylamide structural unit contains amide groups and is easy to form hydrogen bonds, the polyacrylamide structural unit has good water solubility and high chemical activity, and various modifiers with branched chains or net structures can be easily obtained through grafting or crosslinking, so that the polyacrylamide structural unit can be widely applied to industries such as oil exploitation, water treatment, spinning, papermaking, mineral separation, medicines, agriculture and the like.
The polyacrylamide products are various in types, mainly comprise three types of solid, liquid and emulsion, and can achieve the effect of modifying paper fibers by improving the distribution, the binding capacity and the retention of paper pulp fibers in the paper making industry. However, the existing polyacrylamide products for improving the paper strength mainly take aqueous solution type products as main materials, the content is low, the transportation cost is high, the production period is long, continuous production is difficult to realize, the quality guarantee period of the products is short, and the product quality is easily influenced by environmental factors to cause the deterioration or index fluctuation of the products. The low molecular weight solid polyacrylamide colloid has high softness and viscosity, and is easy to cause excessive physical extrusion during processing and granulation, thereby causing the adverse effects of increasing insoluble substances and the like; when fluidized bed drying is carried out at a drying temperature of 85 ℃ or higher, crosslinking is likely to occur, resulting in an increase in insoluble substances.
Therefore, a low molecular weight polyacrylamide colloidal particle which has simple preparation process, high yield, economic production cost and difficult bonding is needed.
Disclosure of Invention
In order to solve the prior technical problem, 1. A preparation method of low molecular weight polyacrylamide colloidal particles is characterized by comprising the following steps:
preparing a monomer aqueous solution: uniformly mixing deionized water, an ionic monomer, solid acrylamide, a chain transfer agent, a chelating agent, a colloid reinforcing agent and an acid-base buffer to form a polymerization solution; the polymerization liquid comprises the following components in percentage by mass: 56 to 59 percent of acrylamide, 10 to 20 percent of ionic monomer, 0.005 to 0.02 percent of chain transfer agent, 0.008 to 0.04 percent of chelating agent, 0.8 to 0.9 percent of colloid reinforcing agent and the balance of deionized water;
preparing colloidal particles through polymerization: controlling the height of a polymerization solution, adjusting the pH, adding an oxidant, a reducing agent and an azo initiator into the polymerization solution, heating to 55-65 ℃, reacting for 5-10min, then increasing the reaction temperature to 120-140 ℃, naturally cooling for 10-20min, performing primary granulation before hardening a colloid to obtain a polymer colloid with the particle size of 3-5mm, and obtaining the polymer colloid after the reaction is finished;
cooling and granulating: and crushing the cooled colloid, drying, cooling, grinding and screening to obtain the paper fiber modifier colloidal particles.
Preferably or optionally, the height of the polymer liquid is controlled to be 3 to 4cm, and the pH value of the polymer liquid is adjusted to be 2.5 to 4.5.
Preferably or alternatively, the colloidal strengthening agent includes a reactive cross-linking agent, a non-reactive small molecule compound, and a non-reactive polar oligomer.
Preferably or alternatively, the reactive crosslinker comprises N, N-methylenebisacrylamide, N-methylolacrylamide, polyallylamine; the non-reactive small molecule compound comprises urea, sodium chloride, ammonium sulfate, acetamide, ammonium adipate and ammonium chloride; the non-reactive polar oligomer comprises polyethylene oxide with the molecular weight less than 10000, polyvinyl alcohol and polyamine.
Preferably or optionally, the dosage of the azo initiator is 0.03 to 0.05 percent of the mass of acrylamide and the ionic monomer, the dosage of the oxidant is 0.5 to 0.8 percent of the mass of acrylamide and the ionic monomer, and the dosage of the reducing agent is 80 to 120 percent of the oxidant.
Preferably or alternatively, the chelating agent comprises EDTA-2Na, DTPA-5Na; the buffer comprises hydrochloric acid, sulfuric acid, acetic acid, phosphoric acid, nitric acid, citric acid, formic acid, acetic acid, propionic acid, adipic acid, benzoic acid, sodium hydroxide, potassium hydroxide and sodium carbonate; the chain transfer agent includes a lower aliphatic alcohol, polyethylene glycol, benzyl alcohol, hypophosphite, formate, alkylsulfonate, (meth) allylsulfonate, mercaptoethanol, or alkylthiol.
Preferably or optionally, the oxidant solution comprises 5 mass percent of ammonium persulfate, sodium persulfate, potassium persulfate, hydrogen peroxide, tert-butyl hydroperoxide, benzoyl peroxide, sodium bromate and potassium bromate; the reducing agent solution comprises 5 mass percent of sodium bisulfite, sodium sulfite, sodium metabisulfite, sodium hydrosulfite, ferrous sulfate, ammonium ferrous sulfate, triethylamine, triethanolamine and tetramethylethylenediamine.
The low molecular weight polyacrylamide gel particles prepared by the preparation method of the low molecular weight polyacrylamide gel particles are characterized in that the solid content of the low molecular weight polyacrylamide gel particles is not less than 80%.
Has the advantages that: the invention has proposed a low molecular weight polyacrylamide colloidal particle and its preparation method, the polyacrylamide colloid that the molecular weight prepared through redox reaction is smaller than 100w, in order to prevent the low molecular weight polyacrylamide colloidal concentration from presenting the characteristic that the texture is soft, viscidity is big after exceeding 50%, the invention participates in the polymerization reaction with the solid acrylamide directly, the polymerization system has added reactive cross-linking agent, non-reactive micromolecule and colloid reinforcing agent that non-reactive polar oligomer makes up, reactive cross-linking agent can form the network, branched structure, improve the density of physical entanglement point among the molecular chains, can improve the integral intensity of the polyacrylamide colloid; the non-reactive small molecular compound can improve the solid content of the product, improve the hardness of polyacrylamide colloid and improve the solubility of the product; the non-reactive polar oligomer can improve the number of hydrogen bonds of the whole polyacrylamide colloid, the number of hydrogen bond binding points is increased, the internal stress of the colloid is greater than the adhesive force between the colloid and equipment, and the colloid is convenient to separate from the equipment, so that the strength of the colloid is improved, and the viscosity is reduced. Compared with the existing method for preparing the high-concentration polyacrylamide colloid, the method adopts single-stage polymerization instead of a mode of combining redox initiation and ultraviolet initiation, so that the prepared polymerization product is the polyacrylamide colloid with extremely high solid content instead of the polyacrylamide colloid solution with the mass concentration of less than 60 percent, the polymerization temperature of the method is as high as 130 ℃, and the polymerization heat does not need to be removed in the reaction process. The prepared high-solid-content colloidal particles avoid the generation of insoluble substances caused by overhigh temperature in the fluidized bed drying process, and meanwhile, the energy loss is greatly reduced in the drying process.
Detailed Description
In the following description, numerous specific details are set forth in order to provide a more thorough understanding of the present invention. It will be apparent, however, to one skilled in the art, that the present invention may be practiced without one or more of these specific details. In other instances, well-known features have not been described in order to avoid obscuring the invention.
The invention will now be further described with reference to the following examples, which are intended to be illustrative of the invention and are not to be construed as limiting the invention. The examples, where specific techniques and reaction conditions are not indicated, can be carried out according to the techniques or conditions or product specifications described in the literature in the field. Reagents, instruments or equipment of any manufacturer not indicated are commercially available.
A preparation method of low molecular weight polyacrylamide colloidal particles comprises the following steps:
preparing solid acrylamide and a comonomer into an aqueous solution; solid acrylamide and copolymerization are prepared into an aqueous solution with the monomer concentration of 70-75 wt%, wherein the monomer concentration is formed by combining monomers with different activities, and the content of the acrylamide in the total monomers accounts for 66-71wt%;
step two, adding a chain transfer agent, a chelating agent, a colloid reinforcing agent and an acid-base buffering agent into the aqueous solution prepared in the step one, and uniformly mixing to form a polymerization solution;
step three, controlling the height of the polymerization liquid to enable the height range of the polymerization liquid to be 3-4cm; the pH value is adjusted to 2.5-4.5 by sulfuric acid or sodium hydroxide; heating the polymerization solution to 55-65 ℃, and adding an oxidant solution with the mass concentration of 5-10wt% and a reducing agent solution with the mass concentration of 5-10wt% to perform polymerization reaction; in the present embodiment, when the polymerization solution is subjected to polymerization reaction, the mass concentrations of the components are as follows: 46-49wt% of acrylamide, 10-20wt% of comonomer, 0.005-0.02wt% of chain transfer agent, 0.008-0.04wt% of chelating agent, 0.8-0.9wt% of colloid reinforcing agent, 0.03-0.05wt% of azo initiator, 0.5-0.8wt% of oxidant solution and 0.5-0.8wt% of reducing agent solution. In the tests, to better promote the polymerization and the cooling of the colloid: the excessive thinness of the colloid can cause heat dissipation of polymerization reaction and influence polymerization; the excessive thickness of the colloid can cause large heat release of polymerization, prolong the cooling time of the colloid and is not beneficial to cutting and granulating; experiments prove that the thickness of the rubber block of 3 to 4cm has the best effect on polymerization reaction, cooling of the rubber body, cutting of the rubber body and granulation.
Step four, after the polymerization reaction in step three is carried out for 5-10min, polyacrylamide colloid with the molecular weight below 60w is obtained; in the embodiment, the polymerization reaction process is carried out in an open place with heat exchange outside, the highest temperature is 120-140 ℃, the temperature is naturally reduced for 10-20min after the highest temperature is reached, primary granulation is carried out before the colloid becomes hard, and the particle size is 3-5mm;
step five, placing the colloidal particles obtained in the step four in a dry environment for natural cooling, cooling to room temperature, wherein the water content of the colloidal particles is 10-15%, and the colloidal particles can be directly ground and sieved to obtain products with three particle size specifications: is more than 20 meshes, 20-60 meshes and less than 60 meshes.
The colloid reinforcing agent has a wide selection range, and can be prepared by one or more of a reactive cross-linking agent, a non-reactive small molecular compound for increasing the solid content and a non-reactive polar oligomer for increasing the hydrogen bond; the reactive crosslinking agent comprises one or more of N, N-methylene bisacrylamide, N-hydroxymethyl acrylamide and polyallylamine; the small molecule compound comprises one or more of urea, sodium chloride, ammonium sulfate, acetamide, ammonium adipate and ammonium chloride; the polar oligomer comprises one or more of polyethylene oxide with molecular weight less than 10000, polyvinyl alcohol and polyamine. In the preparation method of the embodiment, the polyacrylamide colloid with the molecular weight of less than 100w is still soft and has large viscosity even if the concentration exceeds 50%, and the defects can be well compensated by adopting the colloid reinforcing agent; the reactive cross-linking agent is added to form a net-shaped structure, a branched structure and the like, physical entanglement points are increased, and the overall strength of the polyacrylamide colloid is improved; after the micromolecular compound is added, on one hand, the solid content of the product can be improved, the colloid hardness is improved, the continuous production is convenient, and on the other hand, the micromolecular compound can promote the dissolution of the product; the polar oligomer is added, so that the number of hydrogen bonds of the whole polyacrylamide colloid can be increased, the number of hydrogen bond binding points is increased, the internal stress of the colloid is greater than the adhesive force between the colloid and equipment, the colloid is convenient to separate from the equipment, and the strength and the viscosity of the colloid are improved. The appropriate medicament can be selected according to the situation, and the selection of the colloid strengthening agent is added or deleted according to the product.
Example 1
In this embodiment, according to the preparation method of the low molecular weight polyacrylamide micelle, experimental data of specific numerical values are used to verify that the preparation method comprises the following steps:
firstly, preparing a polymerization solution according to the contents in the first step to the third step, adding 5g of glacial acetic acid, 5g of anhydrous citric acid, 110g of solid acrylamide, 5.625g of methacryloyloxyethyl trimethyl ammonium chloride with the mass fraction of 80%, 23.55g of methacryloyloxyethyl dimethyl benzyl ammonium chloride with the mass fraction of 60%, 5g of functional monomer dimethylaminoethyl methacrylate, 0.1g of chelating agent ethylenediamine tetraacetic acid pentasodium, 2.56gN, N-dimethylacrylamide, 0.3g of cross-linking agent diallyl amine, 2g of polar oligomer PEG-8000, 0.5g of chain transfer agent sodium hypophosphite with the mass fraction of 10%, 2g of anhydrous ethanol, 5g of anionic monomer itaconic acid, 7.5g of industrial salt for improving the colloidal strength, 7.5g of cosolvent urea and 55g of deionized water into a reaction vessel, and refining and uniformly stirring and dissolving;
then, after detecting that the pH value of the polymerization solution is 4.0, raising the temperature of the polymerization solution to 60 ℃ through a hot water bath, adding an oxidant solution while stirring, and adding a reducing agent solution at an interval of about 30s, wherein in this embodiment, the oxidant solution is preferably 0.8g of a 5% tert-butyl hydroperoxide solution, and the reducing agent solution is preferably 0.8g of a 5% sodium metabisulfite solution; with the addition of the initiator, the viscosity and the temperature of the polymerization liquid rise, a large amount of water vapor is released, after the reaction reaches the maximum temperature of 132.5 ℃, the polymerization liquid is gelatinized, and then the temperature is naturally reduced;
and (3) after the polymerization reaction is finished, removing water vapor, cooling the colloid to about 80 ℃, taking out the colloid, granulating in a dry environment, blowing dry and cooling the colloid particles by using dry and cold gas, wherein the moisture of the obtained colloid particles is 12.18 percent, directly grinding the colloid particles, then screening the colloid particles by using a screen mesh to obtain three kinds of colloid particles with different particle size specifications, wherein the molecular weight of the obtained colloid particles is 55.8 ten thousand, and the content of insoluble substances is less than 0.05ml/L.
Example 2
The preparation method and the verification method of the low molecular weight polyacrylamide micelle of the embodiment are the same as those of the embodiment 1.
Preparing a polymerization solution according to the contents of the first step to the third step, adding 5g of glacial acetic acid, 5g of anhydrous citric acid, 110g of solid acrylamide, 5.625g of 80 mass percent of methacryloyloxyethyl trimethyl ammonium chloride, 23.55g of 60 mass percent of methacryloyloxyethyl dimethyl benzyl ammonium chloride, 5g of functional monomer dimethylaminoethyl methacrylate, 0.1g of chelating agent pentasodium ethylene diamine tetraacetate, 2.56gN, N-dimethylacrylamide, 0.3g of crosslinking agent diallyl amine, 2g of polar oligomer PEG-8000, 0.5g of chain transfer agent 10 mass percent sodium hypophosphite, 2g of anhydrous ethanol, 5g of anionic monomer itaconic acid, 7.5g of industrial refined salt for improving the colloid strength, 7.5g of cosolvent urea and 55g of deionized water into a reaction vessel, and stirring to dissolve uniformly;
then, adjusting the pH of the polymerization solution to 3.0 by using sulfuric acid, heating the polymerization solution after the pH adjustment to 60 +/-1 ℃ through a hot water bath, adding an oxidant solution while stirring, and adding a reducing agent solution at intervals of about 30s, wherein the oxidant solution is preferably 0.8g of tert-butyl hydroperoxide solution with the concentration of 5%, and the reducing agent solution is preferably 0.8g of sodium metabisulfite solution with the concentration of 5%; with the addition of the initiator, the viscosity and the temperature of the polymerization liquid rise, a large amount of water vapor is released, after the reaction reaches the maximum temperature of 132.5 ℃, the polymerization liquid is gelatinized, and then the temperature is naturally reduced;
and (3) after the polymerization reaction is finished, removing water vapor, cooling the colloid to about 100 ℃, taking out the colloid, granulating in a dry environment, blowing dry and cooling the colloid particles by using dry and cold gas, wherein the moisture of the obtained colloid particles is 9.88%, the colloid particles can be directly ground, then screening by using a screen mesh, and screening into three kinds of colloid particles with different particle size specifications, wherein the molecular weight of the obtained colloid particles is 52.8 ten thousand, and the content of insoluble substances is less than 0.05ml/L.
Example 3
The preparation method and the verification method of the low molecular weight polyacrylamide micelle of the embodiment are the same as those of the embodiment 1.
Preparing a polymerization solution according to the contents of the first step to the third step, adding 5g of glacial acetic acid, 5g of anhydrous citric acid, 110g of solid acrylamide, 5.625g of 80 mass percent of methacryloyloxyethyl trimethyl ammonium chloride, 23.55g of 60 mass percent of methacryloyloxyethyl dimethyl benzyl ammonium chloride, 5g of functional monomer dimethylaminoethyl methacrylate, 0.1g of chelating agent pentasodium ethylene diamine tetraacetate, 2.56gN, N-dimethylacrylamide, 0.3g of crosslinking agent diallyl amine, 2g of polar oligomer PEG-8000, 0.5g of chain transfer agent 10 mass percent sodium hypophosphite, 2g of anhydrous ethanol, 5g of anionic monomer itaconic acid, 7.5g of industrial refined salt for improving the colloid strength, 7.5g of cosolvent urea and 40g of deionized water into a reaction vessel, and stirring and dissolving uniformly;
then, the pH of the polymerization solution was measured to be 4.0, the temperature of the polymerization solution was raised to 60 ℃ by passing through a hot water bath, and an oxidizing agent solution, preferably 0.8g of a 5% strength t-butyl hydroperoxide solution in this example, and a reducing agent solution, preferably 0.8g of a 5% strength sodium metabisulfite solution, were added with stirring at intervals of about 30 seconds; with the addition of the initiator, the viscosity and the temperature of the polymerization solution rise, a large amount of water vapor is released, after the reaction is carried out to the maximum temperature of 136.5 ℃, the polymerization solution is gelled, and then the temperature is naturally reduced;
and (3) after the polymerization reaction is finished, removing water vapor, cooling the colloid to about 80 ℃, taking out the colloid, granulating in a dry environment, blowing dry and cooling the colloid particles by using dry and cold gas, wherein the moisture of the obtained colloid particles is 11.78%, the colloid particles can be directly ground, then screening by using a screen mesh, and screening into three kinds of colloid particles with different particle size specifications, wherein the molecular weight of the obtained colloid particles is 54.3 ten thousand, and the content of insoluble substances is less than 0.05ml/L.
Example 4
The preparation method and the verification method of the low molecular weight polyacrylamide micelle of the embodiment are the same as those of the embodiment 1.
Preparing a polymerization solution according to the contents in the first step to the third step, adding 5g of glacial acetic acid, 5g of anhydrous citric acid, 110g of solid acrylamide, 5.625g of methacryloyloxyethyl trimethyl ammonium chloride with the mass fraction of 80%, 23.55g of methacryloyloxyethyl dimethyl benzyl ammonium chloride with the mass fraction of 60%, 5g of dimethylaminoethyl methacrylate as a functional monomer, 0.1g of pentasodium ethylenediamine tetraacetate as a chelating agent, 2.56g of N, N-dimethylacrylamide, 0.3g of diallyl amine as a crosslinking agent, 2g of a polar oligomer PEG-8000, 0.5g of 10% sodium hypophosphite with the mass fraction as a chain transfer agent, 2g of anhydrous ethanol, 5g of an anionic monomer itaconic acid, 7.5g of an industrial refined salt for improving the colloidal strength, 7.5g of a cosolvent urea and 40g of deionized water into a reaction vessel, and stirring and uniformly dissolving;
then, adjusting the pH of the polymerization solution to 3.0 by using sulfuric acid, heating the polymerization solution after the pH adjustment to 60 +/-1 ℃ through a hot water bath, adding an oxidant solution while stirring, and adding a reducing agent solution at intervals of about 30s, wherein the oxidant solution is preferably 0.8g of tert-butyl hydroperoxide solution with the concentration of 5%, and the reducing agent solution is preferably 0.8g of sodium metabisulfite solution with the concentration of 5%; with the addition of the initiator, the viscosity and the temperature of the polymerization liquid rise along with the addition of the initiator, a large amount of water vapor is released, after the reaction reaches the maximum temperature of 136.2 ℃, the polymerization liquid is gelatinized, and then the polymerization liquid is naturally cooled;
and (3) after the polymerization reaction is finished, removing water vapor, cooling the colloid to about 100 ℃, taking out the colloid, granulating in a dry environment, blowing dry and cooling the colloid particles by using dry and cold gas, wherein the moisture of the obtained colloid particles is 9.58 percent, directly grinding the colloid particles, then screening the colloid particles by using a screen mesh to obtain three kinds of colloid particles with different particle size specifications, wherein the molecular weight of the obtained colloid particles is 48.88 ten thousand, and the content of insoluble substances is less than 0.05ml/L.
Comparative example 1
The preparation method and the verification method of the low molecular weight polyacrylamide gel particles of the comparative example are the same as those of example 1. The polymerization product is dried and cooled in a fluidized bed manner.
Comparative example 2
The preparation method and the verification method of the low molecular weight polyacrylamide gel particles of the comparative example are the same as those of example 2. The polymerization product is dried and cooled in a fluidized bed manner.
Comparative example 3
The preparation method and the verification method of the low molecular weight polyacrylamide gel particles of the comparative example are the same as those of example 3. The polymerization product is dried and cooled in a fluidized bed.
Comparative example 4
The preparation method and the verification method of the low molecular weight polyacrylamide micelle of the comparative example are the same as those of example 4. The polymerization product is dried and cooled in a fluidized bed manner.
Comparative example 5
Adding 238.3g of acrylamide solution with the mass fraction of 50%, 30.8g of acryloyloxyethyl trimethyl ammonium chloride with the mass fraction of 80%, 12.6g of dimethylaminopropyl methacrylamide, 0.2g of sodium formate as a chain transfer agent, 3g of PEG-800 as a polar oligomer, 0.1g of pentasodium ethylene diamine tetraacetate as a chelating agent and 5g of deionized water into a reaction kettle, and stirring and dissolving uniformly; adding a photoinitiator and an azo initiator into the reaction kettle, wherein the photoinitiator is preferably 0.15g of Darocur1173 solution with the concentration of 1wt%, namely 2-hydroxy-2-methyl-1-phenyl-1-acetone, the azo initiator is preferably 0.2g of VA-044 solution with the concentration of 1wt%, namely azobisisobutylimidazoline hydrochloride, and 0.1g of V-50 solution with the concentration of 1wt%, namely azobisisobutylamidine dihydrochloride, stirring and mixing uniformly, and then adjusting the pH value of the polymerization solution to 4.5 by using sulfuric acid; then, controlling the solution temperature of the polymerization solution after the pH value adjustment by water bath at 10 ℃, starting to introduce nitrogen to remove oxygen, introducing nitrogen for 20min, then adding an oxidant solution, continuing to introduce nitrogen for 2min, and then adding a reducing agent solution, wherein in the embodiment, the oxidant solution is preferably a tert-butyl hydroperoxide solution with the concentration of 6g and the concentration of 10wt%, and the reducing agent solution is preferably a sodium bisulfite solution with the concentration of 6g and the concentration of 10 wt%; and stopping introducing nitrogen after the polymerization liquid is sticky, standing for 1h for prepolymerization reaction, wherein the highest temperature in the prepolymerization reaction process is 84.3 ℃, naturally cooling after the highest temperature is reached to 84.3 ℃, and then placing the reaction kettle under ultraviolet lamp light for 1h. Finally, the polymerization product is dried and cooled in a fluidized bed manner.
And (3) performance comparison:
the molecular weights and insoluble contents of the polyacrylamide gel particles obtained in examples 1 to 4 and comparative examples 1 to 4 are shown in the following tables.
Watch (CN)
According to the table, the molecular weights of the polyacrylamide colloidal particles prepared in the embodiments 1 to 4 are all lower than 60w, wherein the insoluble content in each liter of colloidal particles after grinding and sieving is lower than 0.05mL. The molecular weights of the polyacrylamide colloidal particles prepared in comparative examples 1 to 4 are extremely dispersed, the products prepared in comparative examples 1 and 2 are almost insoluble, the insoluble contents of the products prepared in comparative examples 3 and 4 are far greater than those of the examples, and comparative example 5 prepares polyacrylamide colloid with the polymer concentration of 50wt% by a segmented initiation polymerization mode combining redox initiation and ultraviolet initiation, but the polymerization temperature of the method is lower, a large amount of reaction heat needs to be removed to prevent the product from being too soft, so the molecular weight of the product is lower, meanwhile, the solid content of the product is only 50%, the polymerization product still needs to be dried in a fluidized bed mode, and the generated insoluble content is about 6mL/L.
As noted above, while the present invention has been shown and described with reference to certain preferred embodiments, it is not to be construed as limited to the invention itself. Various changes in form and detail may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. The individual features described in the above embodiments may be combined in any suitable manner without contradiction. The invention is not described in detail in order to avoid unnecessary repetition.
Claims (8)
1. The preparation method of the low molecular weight polyacrylamide colloidal particles is characterized by comprising the following steps:
preparing a monomer aqueous solution: uniformly mixing deionized water, an ionic monomer, solid acrylamide, a chain transfer agent, a chelating agent, a colloid reinforcing agent and an acid-base buffer agent to form a polymerization solution; the polymerization liquid comprises the following components in percentage by mass: 56-59% of acrylamide, 10-20% of ionic monomer, 0.005-0.02% of chain transfer agent, 0.008-0.04% of chelating agent, 0.8-0.9% of colloid reinforcing agent and the balance of deionized water;
preparing colloidal particles through polymerization: controlling the height of the polymerization solution, adjusting the pH, adding an oxidant, a reducing agent and an azo initiator into the polymerization solution, heating to 55-65 ℃, reacting for 5-10min, raising the reaction temperature to 120-140 ℃, naturally cooling for 10-20min, performing primary granulation before the colloid is hardened to obtain a polymer colloid with the particle size of 3-5mm, and obtaining the polymer colloid after the reaction is finished;
cooling and granulating: and crushing the cooled colloid, drying, cooling, grinding and screening to obtain the paper fiber modifier colloidal particles.
2. The method for preparing low molecular weight polyacrylamide gel particles according to claim 1, wherein the height of the polymerization solution is controlled to be 3 to 4cm, and the pH is adjusted to 2.5 to 4.5.
3. The method for preparing low molecular weight polyacrylamide micelle according to claim 1, wherein the colloidal reinforcing agent comprises a reactive cross-linking agent, a non-reactive small molecule compound and a non-reactive polar oligomer.
4. The method for preparing a low molecular weight polyacrylamide micelle according to claim 3, wherein said reactive cross-linking agent comprises N, N-methylenebisacrylamide, N-methylolacrylamide, polyallylamine; the non-reactive small molecule compound comprises urea, sodium chloride, ammonium sulfate, acetamide, ammonium adipate and ammonium chloride; the non-reactive polar oligomer comprises polyethylene oxide with the molecular weight less than 10000, polyvinyl alcohol and polyamine.
5. The preparation method of the low molecular weight polyacrylamide micelle according to claim 1, wherein the amount of the azo initiator is 0.03 to 0.05% of the total mass of the solid acrylamide and the ionic monomer, the amount of the oxidant is 0.5 to 0.8% of the total mass of the solid acrylamide and the ionic monomer, and the amount of the reducing agent is 80 to 120% of the oxidant.
6. The method for preparing low molecular weight polyacrylamide gel particles according to claim 1, wherein the chelating agent comprises EDTA-2Na, DTPA-5Na; the buffer comprises hydrochloric acid, sulfuric acid, acetic acid, phosphoric acid, nitric acid, citric acid, formic acid, acetic acid, propionic acid, adipic acid, benzoic acid, sodium hydroxide, potassium hydroxide and sodium carbonate; the chain transfer agent includes a lower aliphatic alcohol, polyethylene glycol, benzyl alcohol, hypophosphite, formate, alkylsulfonate, (meth) allylsulfonate, mercaptoethanol, or alkylthiol.
7. The method for preparing low molecular weight polyacrylamide gel particles according to claim 1, wherein the oxidant solution comprises 5 mass% of ammonium persulfate, sodium persulfate, potassium persulfate, hydrogen peroxide, tert-butyl hydroperoxide, benzoyl peroxide, sodium bromate, potassium bromate; the reducing agent solution comprises 5 mass percent of sodium bisulfite, sodium sulfite, sodium metabisulfite, sodium hydrosulfite, ferrous sulfate, ferrous ammonium sulfate, triethylamine, triethanolamine and tetramethylethylenediamine.
8. A low molecular weight polyacrylamide micelle obtained based on the method for preparing a low molecular weight polyacrylamide micelle of any one of claims 1 to 7, wherein the solid content of the low molecular weight polyacrylamide micelle is not less than 80%.
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| CN101921365A (en) * | 2010-09-09 | 2010-12-22 | 广东省工程技术研究所 | Preparation method for instant cationic polyacrylamide |
| CN109232812A (en) * | 2018-06-28 | 2019-01-18 | 江苏富淼科技股份有限公司 | A kind of cross-linking modified type water-soluble solid polyacrylamide and application thereof |
| CN112592429A (en) * | 2020-12-14 | 2021-04-02 | 江苏富淼科技股份有限公司 | Preparation method of high-concentration polyacrylamide colloid |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101921365A (en) * | 2010-09-09 | 2010-12-22 | 广东省工程技术研究所 | Preparation method for instant cationic polyacrylamide |
| CN109232812A (en) * | 2018-06-28 | 2019-01-18 | 江苏富淼科技股份有限公司 | A kind of cross-linking modified type water-soluble solid polyacrylamide and application thereof |
| CN112592429A (en) * | 2020-12-14 | 2021-04-02 | 江苏富淼科技股份有限公司 | Preparation method of high-concentration polyacrylamide colloid |
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