CN115417945A - Method for preparing polyacrylic acid/attapulgite composite thickener with assistance of ultrasound - Google Patents
Method for preparing polyacrylic acid/attapulgite composite thickener with assistance of ultrasound Download PDFInfo
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Abstract
The invention belongs to the field of new materials, and particularly discloses a method for preparing a polyacrylic acid/attapulgite composite thickening agent by ultrasonic assistance, which comprises the steps of firstly dissociating attapulgite rod crystals by utilizing the activation and dispersion effects of ultrasonic, and then initiating polymerization under ultrasonic irradiation to realize polymer coating of the dissociated attapulgite and improve the compatibility of the dissociated attapulgite rod crystals and a polymer matrix; in the inverse emulsion polymerization process, ultrasonic irradiation is adopted to replace the traditional stirring, and 2-acrylamide-2-methyl-propanesulfonic acid and acrylic monomers are selected for copolymerization, so that the obtained composite thickener has excellent thickening performance and good electrolyte resistance.
Description
Technical Field
The invention belongs to the field of new materials, and particularly relates to a method for preparing a polyacrylic acid/attapulgite composite thickener with the assistance of ultrasound.
Background
The polyacrylic acid thickener is an important variety of printing thickeners, has the advantages of small addition amount, good rheological property, good printing effect and the like, but a polyacrylic acid macromolecular chain contains a large amount of anions, so that the polyacrylic acid macromolecular chain is sensitive to electrolyte, the viscosity is greatly reduced after the polyacrylic acid macromolecular chain meets salt electrolyte, and the printing process requirement can be met only by increasing the using amount; this not only increases the cost of use, but also increases the number of washes of the printed fabric.
Attapulgite clay (attapulgite for short) is a porous chain-layered water-containing Mg-Al-rich silicate clay mineral with attapulgite as main ingredient. Most of the natural attapulgite rod crystals are gathered in a shape of hacks, the gathered attapulgite rod crystals are difficult to disperse well in water, and a stable colloid network structure cannot be formed among the rod crystals. The maximum viscosity of the completely dissociated attapulgite suspension can reach 2800 mPas, but dissociated attapulgite rod crystals are easy to aggregate secondarily. The attapulgite and the polyacrylic acid are compounded to obtain the polyacrylic acid/attapulgite composite thickener with excellent performance, but the good compatibility of the attapulgite and a polymer matrix is the key of success.
Disclosure of Invention
The purpose of the invention is: the method comprises the steps of firstly utilizing multiple functions of ultrasonic activation, dispersion, initiated polymerization and the like to realize the dissociation of attapulgite and the coating modification of monomers on the surface of dissociated attapulgite rod crystals; then in the presence of modified attapulgite, adopting inverse emulsion polymerization to prepare the polyacrylic acid/attapulgite composite thickener.
The invention provides a method for preparing a polyacrylic acid/attapulgite composite thickener with the assistance of ultrasound, which comprises the following steps:
(1) Adding attapulgite clay and deionized water into an ultrasonic reactor, installing an ultrasonic amplitude transformer, inserting the bottom of the amplitude transformer into the solution for 1-2cm, carrying out ultrasonic treatment for 30-60min under the power of 900-1200W, introducing circulating constant-temperature water into an interlayer of the reactor to maintain the temperature of the system at 15-45 ℃ in the treatment process, then adding a mixed solution of an initiator, a nonionic monomer and a silane coupling agent, adjusting the output power of ultrasonic waves to 450-600W, and carrying out ultrasonic irradiation for 30-60min to prepare a modified attapulgite suspension;
wherein the mass volume ratio of the attapulgite clay to the deionized water is 1;
the nonionic monomer is one of hydroxyethyl acrylate, hydroxyethyl methacrylate and acrylamide, and accounts for 0.5-1.0% of the attapulgite clay by mass;
the silane coupling agent is one of vinyl triethoxysilane, vinyl trimethoxysilane and vinyl tri (beta-methoxyethoxy) silane, and the mass of the silane coupling agent accounts for 1.0-2.0% of the mass of the attapulgite clay;
the initiator is one of terpene alkyl hydrogen peroxide, cumene hydrogen peroxide and tert-amyl hydrogen peroxide, and the mass of the initiator accounts for 0.5 to 1.0 percent of the total mass of the nonionic monomer and the silane coupling agent.
(2) Dissolving acrylic monomers and water-soluble monomers in deionized water, adjusting the pH value to 6-7 by using ammonia water, uniformly stirring, and preparing into an aqueous phase solution for later use;
wherein, the acrylic monomer is one of acrylic acid, methacrylic acid, maleic acid and maleic anhydride; the water-soluble monomer is 2-acrylamide-2-methyl-propanesulfonic acid, and the mass of the water-soluble monomer accounts for 5-10% of that of the acrylic monomer; the mass of the deionized water accounts for 15-30% of the total weight of the raw materials in the step (2) and the step (3).
(3) And (3) under the stirring condition, uniformly mixing solvent oil, a water-in-oil emulsifier, a cross-linking agent, a modified attapulgite suspension and the aqueous phase solution obtained in the step (2), homogenizing for 2-5min by using a homogenizer, transferring the homogenized emulsion into an ultrasonic reactor, installing an ultrasonic amplitude transformer, inserting the bottom of the amplitude transformer into the solution for 1-2cm, carrying out ultrasonic reaction for 30-60min under the ultrasonic power of 450-600W, introducing circulating constant-temperature water into an interlayer of the reactor in the reaction process to maintain the system temperature at 15-45 ℃, after the reaction is finished, carrying out reduced pressure distillation and concentration on the polymer emulsion until the solid content is 40-50%, cooling to the room temperature, adding an oil-in-water emulsifier, and uniformly stirring.
Wherein the crosslinking agent is one of 1, 6-hexanediol diacrylate and 1, 4-butanediol diacrylate, and the mass of the crosslinking agent accounts for 0.5-1.0% of that of the acrylic monomer.
The solvent oil is one of exxonmobil isoparaffin Isopar C/E/G/H/L/M, and the mass ratio of the solvent oil to the acrylic monomer is 1;
the water-in-oil emulsifier is span80 or span60, and the mass of the water-in-oil emulsifier accounts for 3-5% of that of the solvent oil;
the mass of the modified attapulgite suspension accounts for 20-40% of that of the acrylic monomer.
The oil-in-water type emulsifier is one of Tween60, tween80 and AEO-9, and the amount of the emulsifier is 3-5% of the mass of the acrylic monomer.
The invention firstly utilizes the activation and dispersion effects of ultrasound to dissociate attapulgite rod crystals, and then initiates polymerization under the irradiation of the ultrasound to realize the polymer coating of the dissociated attapulgite; the hydroperoxide has amphipathy, the terminal hydroxyl is adsorbed on the surface of the attapulgite and is condensed with the hydroxyl on the surface of the attapulgite to a certain degree, under the action of ultrasound, a peroxide bond is broken, an active center is generated on the surface of the attapulgite, and the nonionic monomer is initiated to polymerize on the surface of the attapulgite; silanol formed by hydrolysis of the silane coupling agent is easy to condense with hydroxyl on the surface of attapulgite to form a strong chemical bond effect, and double bonds are introduced to participate in polymerization reaction.
The beneficial effects of the invention are:
(1) The polymer is coated on the surface of the attapulgite by adopting ultrasonic irradiation polymerization, so that the compatibility of the polymer and polyacrylic acid is improved.
(2) 2-acrylamide-2-methyl-propanesulfonic acid is selected to be copolymerized with acrylic monomers, so that the thickening performance and the electrolyte resistance of the polyacrylic thickener are improved.
Description of the drawings:
FIG. 1 the infrared spectrum of the thickener obtained in example 1.
Detailed Description
The present invention will be described in further detail with reference to specific examples. It will be understood that these examples are intended to illustrate the invention and are not intended to limit the scope of the invention in any way.
Example 1
(1) Adding 5g of attapulgite clay and 100mL of deionized water into an ultrasonic reactor, installing an ultrasonic amplitude transformer, inserting the bottom of the amplitude transformer into a solution for 1cm, carrying out ultrasonic treatment for 60min under 900W, introducing circulating constant-temperature water into an interlayer of the reactor in the treatment process to maintain the temperature of the system at 15 ℃, then adding hydroxyethyl acrylate accounting for 0.5 percent of the mass of the attapulgite clay, vinyl triethoxysilane accounting for 1.0 percent of the mass of the attapulgite clay and p-menthane hydrogen peroxide accounting for 0.5 percent of the total mass of the hydroxyethyl acrylate and the vinyl triethoxysilane, adjusting the output power of ultrasonic waves to 450W, and carrying out ultrasonic irradiation for 60min to prepare a modified attapulgite suspension;
(2) Dissolving acrylic acid and 2-acrylamide-2-methyl-propanesulfonic acid accounting for 5% of the mass of the acrylic acid in deionized water, adjusting the pH value to 6 by using ammonia water, uniformly stirring, and preparing into an aqueous phase solution for later use, wherein the mass of the deionized water accounts for 15% of the total weight of the raw materials in the step (2) and the step (3);
(3) Under the stirring condition, the mass ratio of the cross-linking agent 1, 6-hexanediol diacrylate and the Exxon Mobil isoalkane Isopar C accounting for 0.5 percent of the mass of the acrylic acid to the mass of the acrylic acid is 1.25; mixing evenly span80 accounting for 3% of Isopar C and modified attapulgite suspension accounting for 20% of acrylic acid, homogenizing for 2min by a homogenizer, transferring the homogenized emulsion into an ultrasonic reactor, installing an ultrasonic amplitude transformer, inserting the bottom of the amplitude transformer into the solution for 1cm, carrying out ultrasonic reaction for 60min under the ultrasonic power of 450W, introducing circulating constant-temperature water into an interlayer of the reactor in the reaction process to maintain the temperature of the system at 15 ℃, after the reaction is finished, carrying out reduced pressure distillation and concentration on the polymer emulsion until the solid content is 40%, cooling to room temperature, adding Tween60 accounting for 3% of acrylic acid, and stirring evenly.
Comparative example 1
(1) Dissolving acrylic acid and 2-acrylamide-2-methyl-propanesulfonic acid accounting for 5% of the mass of the acrylic acid in deionized water, adjusting the pH value to 6 by using ammonia water, uniformly stirring, and preparing into an aqueous phase solution for later use, wherein the mass of the deionized water accounts for 15% of the total weight of the raw materials in the step (1) and the step (2);
(2) Under the stirring condition, the cross-linking agent 1, 6-hexanediol diacrylate accounting for 0.5 percent of the mass of the acrylic acid and the Exxon Mobil isoparaffin Isopar C are mixed, and the mass ratio of the cross-linking agent to the mass of the acrylic acid is 1.25; mixing span80 accounting for 3% of Isopar C and attapulgite accounting for 1.0% of acrylic acid, homogenizing for 2min by a homogenizer, transferring the homogenized emulsion into an ultrasonic reactor, installing an ultrasonic amplitude transformer, inserting the bottom of the amplitude transformer into the solution for 1cm, carrying out ultrasonic reaction for 60min under the ultrasonic power of 450W, introducing circulating constant-temperature water into an interlayer of the reactor in the reaction process to maintain the temperature of the system at 15 ℃, after the reaction is finished, carrying out reduced pressure distillation and concentration on the polymer emulsion until the solid content is 40%, cooling to room temperature, adding Tween60 accounting for 3% of acrylic acid, and stirring uniformly.
Comparative example 2
(1) Adding 5g of attapulgite clay and 100mL of deionized water into a four-neck flask, stirring at a high speed of 2000 rpm for 60min, then adding hydroxyethyl acrylate accounting for 0.5% of the mass of the attapulgite clay, vinyl triethoxysilane accounting for 1.0% of the mass of the attapulgite clay and p-menthane hydrogen peroxide accounting for 0.5% of the total mass of the hydroxyethyl acrylate and the vinyl triethoxysilane, heating in a water bath to 78 ℃ to initiate polymerization, and reacting for 60min to prepare a modified attapulgite suspension;
(2) Dissolving acrylic acid and 2-acrylamide-2-methyl-propanesulfonic acid accounting for 5% of the mass of the acrylic acid in deionized water, adjusting the pH value to 6 by using ammonia water, uniformly stirring, and preparing into an aqueous phase solution for later use, wherein the mass of the deionized water accounts for 15% of the total weight of the raw materials in the step (2) and the step (3);
(3) Under the stirring condition, the cross-linking agent 1, 6-hexanediol diacrylate accounting for 0.5 percent of the mass of the acrylic acid and the Exxon Mobil isoparaffin Isopar C are mixed, and the mass ratio of the cross-linking agent to the mass of the acrylic acid is 1.25; mixing span80 accounting for 3% of Isopar C and modified attapulgite suspension accounting for 20% of acrylic acid, homogenizing for 2min by a homogenizer, transferring the homogenized emulsion into a four-neck flask, heating to 60 ℃ under the stirring condition of 300 revolutions per minute, preserving heat for 60min, after the reaction is finished, carrying out reduced pressure distillation and concentration on the polymer emulsion until the solid content is 40%, cooling to room temperature, adding Tween60 accounting for 3% of acrylic acid, and stirring uniformly.
Comparative example 3
(1) Adding 5g of attapulgite clay and 100mL of deionized water into an ultrasonic reactor, installing an ultrasonic amplitude transformer, inserting the bottom of the amplitude transformer into a solution for 1cm, carrying out ultrasonic treatment for 60min at 900W, introducing circulating constant-temperature water into an interlayer of the reactor in the treatment process to maintain the temperature of the system at 15 ℃, then adding hydroxyethyl acrylate accounting for 0.5 percent of the mass of the attapulgite clay, vinyl triethoxysilane accounting for 1.0 percent of the mass of the attapulgite clay and terpene alkyl hydrogen peroxide accounting for 0.5 percent of the total mass of the hydroxyethyl acrylate and the vinyl triethoxysilane, adjusting the output power of ultrasonic waves to 450W, and carrying out ultrasonic irradiation for 60min to prepare a modified attapulgite suspension;
(2) Dissolving acrylic acid in deionized water, adjusting the pH value to 6 by using ammonia water, uniformly stirring, and preparing into an aqueous phase solution for later use, wherein the mass of the deionized water accounts for 15% of the total weight of the raw materials in the step (2) and the step (3);
(3) Under the stirring condition, the cross-linking agent 1, 6-hexanediol diacrylate accounting for 0.5 percent of the mass of the acrylic acid and the Exxon Mobil isoparaffin Isopar C are mixed, and the mass ratio of the cross-linking agent to the mass of the acrylic acid is 1.25; mixing evenly span80 accounting for 3% of Isopar C mass and modified attapulgite suspension accounting for 20% of acrylic acid mass, homogenizing for 2min by a homogenizer, transferring the homogenized emulsion into an ultrasonic reactor, installing an ultrasonic amplitude transformer, inserting the bottom of the amplitude transformer into the solution for 1cm, carrying out ultrasonic reaction for 60min under the ultrasonic power of 450W, introducing circulating constant-temperature water into an interlayer of the reactor in the reaction process to maintain the temperature of the system at 15 ℃, after the reaction is finished, carrying out reduced pressure distillation and concentration on the polymer emulsion until the solid content is 40%, cooling to room temperature, adding Tween60 accounting for 3% of acrylic acid mass, and stirring evenly.
Example 2
(1) Adding 5g of attapulgite clay and 150mL of deionized water into an ultrasonic reactor, installing an ultrasonic amplitude transformer, inserting the bottom of the amplitude transformer into the solution for 2cm, carrying out ultrasonic treatment for 30min under 1200W of power, introducing circulating constant-temperature water into an interlayer of the reactor in the treatment process to maintain the temperature of the system at 45 ℃, then adding hydroxyethyl methacrylate accounting for 1.0 percent of the mass of the attapulgite clay, vinyltrimethoxysilane accounting for 2.0 percent of the mass of the attapulgite clay and cumene hydroperoxide accounting for 1.0 percent of the total mass of the hydroxyethyl methacrylate and the vinyltrimethoxysilane, adjusting the output power of ultrasonic waves to 600W, and carrying out ultrasonic irradiation for 30min to prepare a modified attapulgite suspension;
(2) Dissolving methacrylic acid and 2-acrylamide-2-methyl-propanesulfonic acid accounting for 10% of the mass of the methacrylic acid in deionized water, adjusting the pH value to 7 by using ammonia water, uniformly stirring to prepare an aqueous phase solution for later use, wherein the mass of the deionized water accounts for 30% of the total weight of the raw materials in the step (2) and the step (3);
(3) Under the stirring condition, 1, 4-butanediol diacrylate as a cross-linking agent accounting for 1.0 percent of the mass of the methacrylic acid and Isopar E as an Exxon Mobil isoparaffin are mixed, wherein the mass ratio of the 1, 4-butanediol diacrylate to the methacrylic acid monomer is 1; mixing evenly a span60 accounting for 5% of Isopar E mass and a modified attapulgite suspension accounting for 40% of methacrylic acid mass, homogenizing for 5min by a homogenizer, transferring the homogenized emulsion into an ultrasonic reactor, installing an ultrasonic amplitude transformer, inserting the bottom of the amplitude transformer into the solution for 2cm, carrying out ultrasonic reaction for 30min under 600W ultrasonic power, introducing circulating constant-temperature water into an interlayer of the reactor in the reaction process to maintain the system temperature at 45 ℃, after the reaction is finished, carrying out reduced pressure distillation and concentration on the polymer emulsion until the solid content is 50%, cooling to room temperature, adding Tween80 accounting for 5% of methacrylic acid mass, and stirring evenly.
Example 3
(1) Adding 5g of attapulgite clay and 120mL of deionized water into an ultrasonic reactor, installing an ultrasonic amplitude transformer, inserting the bottom of the amplitude transformer into the solution for 1.5cm, carrying out ultrasonic treatment for 45min under the power of 1000W, introducing circulating constant-temperature water into an interlayer of the reactor in the treatment process to maintain the temperature of the system at 30 ℃, then adding acrylamide accounting for 0.75 percent of the mass of the attapulgite clay, vinyl tri (beta-methoxyethoxy) silane accounting for 1.5 percent of the mass of the attapulgite clay and tert-amyl hydrogen peroxide accounting for 0.75 percent of the total mass of the acrylamide and the vinyl tri (beta-methoxyethoxy) silane, adjusting the output power of ultrasonic waves to 500W, and carrying out ultrasonic irradiation for 45min to prepare a modified attapulgite suspension;
(2) Dissolving maleic acid, namely 2-acrylamide-2-methyl-propanesulfonic acid accounting for 7.5 percent of the mass of the maleic acid in deionized water, adjusting the pH value to 6.5 by using ammonia water, uniformly stirring, and preparing into an aqueous phase solution for later use, wherein the mass of the deionized water accounts for 25 percent of the total weight of the raw materials in the step (2) and the step (3);
(3) Under the stirring condition, the mass ratio of the cross-linking agent 1, 6-hexanediol diacrylate accounting for 0.75 percent of the mass of the maleic acid and the Isopar G of the Exxon Mobil isoalkane is 1; the preparation method comprises the following steps of uniformly mixing span80 accounting for 4% of Isopar G by mass and modified attapulgite suspension accounting for 30% of maleic acid by mass, homogenizing for 3min by using a homogenizer, transferring the homogenized emulsion into an ultrasonic reactor, installing an ultrasonic amplitude transformer, inserting the bottom of the amplitude transformer into the solution for 1.5cm, carrying out ultrasonic reaction for 45min under 500W of ultrasonic power, introducing circulating constant-temperature water into an interlayer of the reactor in the reaction process to maintain the temperature of the system at 30 ℃, after the reaction is finished, carrying out reduced pressure distillation and concentration on the polymer emulsion until the solid content is 45%, cooling to room temperature, adding AEO-9 accounting for 4% of maleic acid by mass, and uniformly stirring.
Example 4
(1) Adding 5g of attapulgite clay and 115mL of deionized water into an ultrasonic reactor, installing an ultrasonic amplitude transformer, inserting the bottom of the amplitude transformer into the solution for 1.2cm, carrying out ultrasonic treatment for 40min under 1100W power, introducing circulating constant-temperature water into an interlayer of the reactor in the treatment process to maintain the temperature of the system at 35 ℃, then adding hydroxyethyl acrylate accounting for 0.6 percent of the mass of the attapulgite clay, vinyl trimethoxy silane accounting for 1.2 percent of the mass of the attapulgite clay and cumene hydroperoxide accounting for 0.6 percent of the total mass of the hydroxyethyl acrylate and the vinyl trimethoxy silane, adjusting the output power of ultrasonic waves to 550W, and carrying out ultrasonic irradiation for 40min to prepare a modified attapulgite suspension;
(2) Dissolving maleic anhydride and 2-acrylamide-2-methyl-propanesulfonic acid accounting for 6% of the mass of the maleic anhydride in deionized water, adjusting the pH value to 6 by using ammonia water, uniformly stirring, and preparing into an aqueous phase solution for later use, wherein the mass of the deionized water accounts for 20% of the total weight of the raw materials in the step (2) and the step (3);
(3) Under the stirring condition, a cross-linking agent 1, 4-butanediol diacrylate accounting for 0.6 percent of the mass of the maleic anhydride and an exxonmobil isoalkane Isopar H are mixed, wherein the mass ratio of the cross-linking agent to the mass of the maleic anhydride is 1; the preparation method comprises the following steps of uniformly mixing span60 accounting for 3.5% of Isopar H mass and modified attapulgite suspension accounting for 35% of maleic anhydride mass, homogenizing for 4min by using a homogenizer, transferring the homogenized emulsion into an ultrasonic reactor, installing an ultrasonic amplitude transformer, inserting the bottom of the amplitude transformer into the solution for 1.2cm, carrying out ultrasonic reaction for 40min under 550W ultrasonic power, introducing circulating constant-temperature water into an interlayer of the reactor in the reaction process to maintain the temperature of the system at 35 ℃, after the reaction is finished, carrying out reduced pressure distillation and concentration on the polymer emulsion until the solid content is 42%, cooling to room temperature, adding Tween80 accounting for 3.5% of maleic anhydride mass, and uniformly stirring.
Example 5
Accurately weighing 2g of thickening agent, adding 98g of distilled water, stirring, dropwise adding 0.2mL of ammonia water, and fully stirring to prepare white slurry with the mass fraction of 2%. The viscosity of the white slurry was measured at room temperature using a Brookfield DV-II + Pro viscometer at 10 rpm (spindle 6) at a constant speed.
Electrolyte resistance expressed in terms of viscosity retentionThe viscosity of the thickener white slurry was measured at 0.05% NaCl (solids) added, and the viscosity retention = η After adding NaCl /η Before adding NaCl The higher the viscosity retention, the better the electrolyte resistance.
The printing paste comprises the following components:
the method comprises the following steps of mixing the reactive dye into a slurry state by using deionized water, dissolving urea and anti-dyeing salt S into a small amount of hot water, uniformly mixing the reactive dye color paste with a mixed solution of the urea and the anti-dyeing salt, fully stirring to completely dissolve the dye, adding the thickener raw paste, uniformly stirring, and adding sodium carbonate before use. Reactive dye printing was performed according to the following process, and the results of comparison of K/S value, permeability, color unevenness, paste removal rate, and dry and wet crockfastness of the printed fabrics are shown in Table 2.
Color paste preparation → printing → drying (60 ℃) → steaming (102-103 ℃,10 min) → washing with water (cold water first and hot water later) → soap boiling (soap chips 2g/L, boiling for 10 min) → washing with water (hot water first and cold water later) → drying (60 ℃)
TABLE 1 thickening Properties of the samples
| Viscosity of white paste (mPa. S) | Viscosity Retention (%) | |
| Example 1 | 16690 | 92.6 |
| Comparative example1 | 8280 | 45.7 |
| Comparative example 2 | 9830 | 50.4 |
| Comparative example 3 | 13570 | 72.5 |
| Example 2 | 18550 | 95.1 |
| Example 3 | 17890 | 93.6 |
| Example 4 | 17360 | 94.3 |
As can be seen from the above table, the thickeners obtained in examples 1 to 4 have strong thickening ability and excellent electrolyte resistance. In comparative example 1, the attapulgite is not modified, the compatibility with polyacrylic acid is poor, and the thickening ability and electrolyte resistance of the obtained thickening agent are inferior to those of example 1. In comparative example 2, the traditional stirring process is adopted, the attapulgite clay cannot be effectively dissociated and cannot be effectively compounded with polyacrylic acid macromolecules in the stirring process, and the thickening capacity and the electrolyte resistance of the obtained thickener are not as good as those of example 1. In comparative example 3, the water-soluble monomer 2-acrylamide-2-methyl-propanesulfonic acid was not added, and the electrolyte resistance of the obtained thickener was significantly inferior to that of example 1, and the thickening ability was slightly inferior to that of example 1.
TABLE 2K/S value, permeability, depasting Rate of reactive dye printed Fabric
The larger the K/S value of the front surface of the printed fabric is, the better the coloring effect is; the higher the permeability, the better the printing transparency of the color paste. The thickener mainly plays a role in transferring dye in the printing process, and after printing is finished, the thickener needs to be washed off from the fabric, otherwise, the hand feeling of the printed fabric is influenced, and the higher the paste removal rate is, the softer the hand feeling of the printed fabric is. As can be seen from the table above, the thickener printed fabric obtained in example 1 has a high K/S value on the front surface, and the obtained fabric has high color quantity, good permeability, high paste removal rate and good washing effect. Because the thickening ability and electrolyte resistance of the thickening agent obtained in comparative examples 1,2 and 3 are poor, the concentration of the raw paste of the thickening agent in the printing process is higher than that in example 1 (the concentration of the raw paste in comparative examples 1 and 2 is 3.5%, the concentration of the raw paste in comparative examples 1 and 2 is 3.0%, and the concentration of the raw paste in the examples is 2%), the thickening agent remained on the fabric after printing is high, and the paste removal rate is low.
Claims (9)
1. The method for preparing the polyacrylic acid/attapulgite composite thickener by ultrasonic assistance is characterized by comprising the following steps:
(1) Adding attapulgite clay and deionized water into an ultrasonic reactor, installing an ultrasonic amplitude transformer, inserting the bottom of the amplitude transformer into the solution for 1-2cm, carrying out ultrasonic treatment for 30-60min at the power of 900-1200W, introducing circulating constant-temperature water into an interlayer of the reactor in the treatment process to maintain the system temperature at 15-45 ℃, then adding a mixed solution of an initiator, a nonionic monomer and a silane coupling agent, adjusting the output power of ultrasonic waves to 450-600W, and carrying out ultrasonic irradiation for 30-60min to prepare a modified attapulgite suspension;
(2) Dissolving acrylic monomers and water-soluble monomers in deionized water, adjusting the pH value to 6-7 by using ammonia water, uniformly stirring, and preparing into an aqueous phase solution for later use;
(3) And (3) under the stirring condition, uniformly mixing solvent oil, a water-in-oil emulsifier, a cross-linking agent, a modified attapulgite suspension and the aqueous solution obtained in the step (2), homogenizing for 2-5min by using a homogenizer, transferring the homogenized emulsion into an ultrasonic reactor, installing an ultrasonic amplitude transformer, inserting the bottom of the amplitude transformer into the solution for 1-2cm, carrying out ultrasonic reaction for 30-60min under the ultrasonic power of 450-600W, introducing circulating constant-temperature water into an interlayer of the reactor in the reaction process to maintain the system temperature at 15-45 ℃, after the reaction is finished, carrying out reduced pressure distillation and concentration on the polymer emulsion until the solid content is 40-50%, cooling to room temperature, adding an oil-in-water emulsifier, and uniformly stirring to obtain the polyacrylic acid/attapulgite composite thickener.
2. The method for preparing polyacrylic acid/attapulgite composite thickener by ultrasonic assistance according to claim 1, wherein the nonionic monomer in step (1) is one of hydroxyethyl acrylate, hydroxyethyl methacrylate and acrylamide, the silane coupling agent is one of vinyltriethoxysilane, vinyltrimethoxysilane and vinyltris (beta-methoxyethoxy) silane, and the initiator is one of p-menthane hydroperoxide, cumene hydroperoxide and tert-amyl hydroperoxide.
3. The method for preparing the polyacrylic acid/attapulgite composite thickener with the assistance of the ultrasound according to the claim 1, wherein the mass-to-volume ratio of the attapulgite clay to the deionized water in the step (1) is 1; the mass of the nonionic monomer accounts for 0.5-1.0% of the mass of the attapulgite clay; the mass of the silane coupling agent accounts for 1.0-2.0% of the mass of the attapulgite clay; the mass of the initiator accounts for 0.5 to 1.0 percent of the total mass of the nonionic monomer and the silane coupling agent.
4. The method for preparing the polyacrylic acid/attapulgite composite thickener by the assistance of the ultrasound according to the claim 1, wherein the acrylic monomer in the step (2) is one of acrylic acid, methacrylic acid, maleic acid and maleic anhydride; the water-soluble monomer is 2-acrylamide-2-methyl-propanesulfonic acid.
5. The method for preparing the polyacrylic acid/attapulgite composite thickener by the assistance of the ultrasound as claimed in claim 1, wherein the water-soluble monomer accounts for 5 to 10 percent of the mass of the acrylic monomer in the step (2); the mass of the deionized water accounts for 15-30% of the total weight of the raw materials in the step (2) and the step (3).
6. The method for preparing the polyacrylic acid/attapulgite composite thickener by the ultrasonic assistance as claimed in claim 1, wherein the solvent oil in the step (3) is one of exxonmobil isoparaffin Isopar C/E/G/H/L/M, and the mass ratio of the solvent oil to the acrylic monomer is 1.
7. The method for preparing the polyacrylic acid/attapulgite composite thickener by the assistance of the ultrasound as claimed in claim 1, wherein the water-in-oil emulsifier in the step (3) is span80 or span60, and the mass of the water-in-oil emulsifier accounts for 3-5% of the mass of the solvent oil.
8. The method for preparing the polyacrylic acid/attapulgite composite thickener by the assistance of the ultrasonic waves as claimed in claim 1, wherein the cross-linking agent in the step (3) is one of 1, 6-hexanediol diacrylate and 1, 4-butanediol diacrylate, and the mass of the cross-linking agent is 0.5-1.0% of that of the acrylic monomer.
9. The method for preparing the polyacrylic acid/attapulgite composite thickener by the assistance of the ultrasonic wave as claimed in claim 1, wherein the modified attapulgite suspension in the step (3) accounts for 20-40% of the acrylic monomer by mass; the oil-in-water type emulsifier is one of Tween60, tween80 and AEO-9, and the dosage of the emulsifier accounts for 3-5% of the mass of the acrylic monomer.
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| PCT/CN2023/107813 WO2023241730A1 (en) | 2022-09-16 | 2023-07-18 | Ultrasonic-assisted method for preparing polyacrylic acid/attapulgite composite thickening agent |
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|---|---|---|---|---|
| US3211708A (en) * | 1960-09-14 | 1965-10-12 | Hoechst Ag | Oil-in-water bead polymerization of water-soluble monomers |
| CN108641048A (en) * | 2018-05-11 | 2018-10-12 | 常州大学 | A kind of preparation method of the recessed native complex thickener of salt tolerant |
| CN110885396A (en) * | 2019-12-03 | 2020-03-17 | 江苏麦阁吸附剂有限公司 | Salt-tolerant attapulgite/polyacrylic acid composite thickening agent and preparation method thereof |
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| JP5393581B2 (en) * | 2010-04-22 | 2014-01-22 | 一般財団法人川村理化学研究所 | Method for producing organic-inorganic composite dispersion |
| CN110951015B (en) * | 2019-12-03 | 2020-08-04 | 江苏麦阁吸附剂有限公司 | Polyacrylic acid thickener taking modified attapulgite as cross-linking agent and preparation method thereof |
| CN113930984A (en) * | 2021-11-19 | 2022-01-14 | 江苏麦阁吸附剂有限公司 | Preparation method of modified attapulgite-polyacrylic acid salt-resistant thickening agent |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US3211708A (en) * | 1960-09-14 | 1965-10-12 | Hoechst Ag | Oil-in-water bead polymerization of water-soluble monomers |
| CN108641048A (en) * | 2018-05-11 | 2018-10-12 | 常州大学 | A kind of preparation method of the recessed native complex thickener of salt tolerant |
| CN110885396A (en) * | 2019-12-03 | 2020-03-17 | 江苏麦阁吸附剂有限公司 | Salt-tolerant attapulgite/polyacrylic acid composite thickening agent and preparation method thereof |
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