CN115417945B - Method for preparing polyacrylic acid/attapulgite clay composite thickener with assistance of ultrasound - Google Patents
Method for preparing polyacrylic acid/attapulgite clay 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 thickener by ultrasonic assistance, which comprises the steps of firstly dissociating attapulgite rod crystals by utilizing the activation and dispersion effects of ultrasonic waves, and then initiating polymerization under ultrasonic irradiation to realize polymer coating of dissociated attapulgite, so as to improve the compatibility of the dissociated attapulgite rod crystals with a polymer matrix; in the inverse emulsion polymerization process, ultrasonic irradiation is adopted to replace the traditional stirring, and meanwhile, 2-acrylamide-2-methyl-propane sulfonic acid and acrylic acid 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 clay composite thickener by ultrasonic assistance.
Background
The polyacrylic acid thickener is an important variety of printing thickener, has the advantages of small addition amount, good rheological property, good printing effect and the like, but the polyacrylic acid macromolecular chain contains a large amount of anions, so that the polyacrylic acid thickener is sensitive to electrolyte, and after salt electrolyte is encountered, the viscosity is greatly reduced, and the printing process requirement can be met by increasing the use amount; this not only increases the cost of use, but also increases the number of washings of the printed fabric.
Attapulgite clay (attapulgite for short) is a porous chain layered water-containing magnesium-rich aluminosilicate clay mineral with attapulgite as main component. The natural attapulgite rod crystals are mostly gathered in a diesel stack shape, the gathered attapulgite rod crystals are difficult to be well dispersed in water, and stable colloid network structures cannot be formed among the rod crystals. The maximum viscosity of the completely dissociated attapulgite suspension can reach 2800 mPa.s, but the dissociated attapulgite crystals are easy to be secondarily aggregated. The attapulgite and polyacrylic acid are compounded to obtain the polyacrylic acid/attapulgite composite thickener with excellent performance, but the good compatibility of the attapulgite and the polymer matrix is the key of success.
Disclosure of Invention
The purpose of the invention is that: the method firstly utilizes multiple functions of ultrasonic activation, dispersion, polymerization initiation and the like to realize the dissociation of the attapulgite and the coating modification of a monomer on the surface of the dissociated attapulgite crystal; then adopting inverse emulsion polymerization to prepare the polyacrylic acid/attapulgite composite thickener in the presence of modified attapulgite.
The invention provides a method for preparing a polyacrylic acid/attapulgite composite thickener by ultrasonic assistance, 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, performing ultrasonic treatment for 30-60min under 900-1200W power, introducing circulating constant temperature water into an interlayer of the reactor in the treatment process to maintain the temperature of the system 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 performing 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 1:20-1:30g/mL;
the nonionic monomer is one of hydroxyethyl acrylate, hydroxyethyl methacrylate and acrylamide, and the mass of the nonionic monomer accounts for 0.5-1.0% of the mass of the attapulgite clay;
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 hydrogen peroxide, cumene hydroperoxide and tert-amyl hydroperoxide, and the mass of the initiator accounts for 0.5-1.0% of the total mass of the nonionic monomer and the silane coupling agent.
(2) Dissolving acrylic acid monomer and water-soluble monomer in deionized water, regulating pH value to 6-7 with ammonia water, stirring uniformly, and preparing into aqueous solution for 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-propane sulfonic acid, and the mass of the water-soluble monomer accounts for 5-10% of that of the acrylic monomer; the mass of deionized water accounts for 15-30% of the total weight of the raw materials in the step (2) and the step (3).
(3) Under the stirring condition, uniformly mixing solvent oil, a water-in-oil type 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, mounting an ultrasonic amplitude transformer, inserting the bottom of the amplitude transformer into the solution for 1-2cm, performing 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, concentrating the polymer emulsion by reduced pressure distillation to the solid content of 40-50%, cooling to the room temperature, adding the oil-in-water type emulsifier, and uniformly stirring.
Wherein the cross-linking agent is one of 1, 6-hexanediol diacrylate and 1, 4-butanediol diacrylate, and the mass of the cross-linking agent accounts for 0.5-1.0% of the mass of the acrylic monomer.
The solvent oil is one of Isopar C/E/G/H/L/M, and the mass ratio of the solvent oil to the acrylic monomer is 1:0.25-1:0.6;
the water-in-oil emulsifier is span80 or span60, and the mass of the water-in-oil emulsifier accounts for 3% -5% of the mass of the solvent oil;
the mass of the modified attapulgite suspension accounts for 20-40% of the mass of the acrylic monomer.
The oil-in-water type emulsifier is one of Tween60, tween80 and AEO-9, and the dosage of the oil-in-water type emulsifier accounts for 3-5% of the mass of the acrylic monomer.
The invention firstly utilizes the activation and dispersion effects of ultrasound to dissociate the attapulgite rod crystal, and then initiates polymerization under the irradiation of ultrasound to realize the polymer coating of dissociated attapulgite; the hydroperoxide has amphipathy, the hydroxyl end is adsorbed on the surface of the attapulgite and condensed with the hydroxyl on the surface to a certain extent, and under the action of ultrasound, the peroxide bond is broken to generate an active center on the surface of the attapulgite, so that the nonionic monomer is initiated to polymerize on the surface of the attapulgite; silanol formed by hydrolysis of the silane coupling agent is extremely 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 as follows:
(1) And the polymer is coated on the surface of the attapulgite by adopting ultrasonic irradiation polymerization, so that the compatibility of the attapulgite with polyacrylic acid is improved.
(2) 2-acrylamide-2-methyl-propane sulfonic acid is selected to be copolymerized with acrylic monomers, so that the thickening performance and electrolyte resistance of the polyacrylic thickener are improved.
Description of the drawings:
FIG. 1 is an 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 should 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 the solution for 1cm, performing ultrasonic treatment for 60min under 900W power, 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% of the mass of the attapulgite clay, vinyl triethoxysilane accounting for 1.0% of the mass of the attapulgite clay, and terpene hydrogen peroxide accounting for 0.5% of the total mass of the hydroxyethyl acrylate and the vinyl triethoxysilane, adjusting the output power of ultrasonic waves to 450W, and performing ultrasonic irradiation for 60min to prepare a modified attapulgite suspension;
(2) Dissolving acrylic acid and 2-acrylamide-2-methyl-propane sulfonic acid accounting for 5% of the mass of the acrylic acid in deionized water, regulating the pH value to 6 by ammonia water, uniformly stirring to prepare aqueous phase solution for standby, 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, a cross-linking agent 1, 6-hexanediol diacrylate accounting for 0.5 percent of the mass of acrylic acid and an Ekksen mobil isoparaar C are mixed, wherein the mass ratio of the cross-linking agent 1, 6-hexanediol diacrylate to the mass of acrylic acid is 1:0.25; span80 accounting for 3% of Isopar C mass, modified attapulgite suspension accounting for 20% of acrylic acid mass, uniformly mixing, homogenizing for 2min 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 1cm, ultrasonically reacting for 60min under 450W ultrasonic power, introducing circulating constant-temperature water into a reactor interlayer in the reaction process to maintain the system temperature at 15 ℃, after the reaction is finished, decompressing, distilling and concentrating the polymer emulsion to have the solid content of 40%, cooling to room temperature, adding Tween60 accounting for 3% of acrylic acid mass, and uniformly stirring.
Comparative example 1
(1) Dissolving acrylic acid and 2-acrylamide-2-methyl-propane sulfonic acid accounting for 5% of the mass of the acrylic acid in deionized water, regulating the pH value to 6 by ammonia water, uniformly stirring to prepare aqueous phase solution for standby, 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, a cross-linking agent 1, 6-hexanediol diacrylate accounting for 0.5 percent of the mass of acrylic acid and an Ekksen mobil isoparaar C are mixed, wherein the mass ratio of the cross-linking agent 1, 6-hexanediol diacrylate to the mass of acrylic acid is 1:0.25; span80 accounting for 3% of Isopar C mass and attapulgite accounting for 1.0% of acrylic acid mass are uniformly mixed, a homogenizer is used for homogenizing for 2min, the homogenized emulsion is transferred into an ultrasonic reactor, an ultrasonic amplitude transformer is arranged, the bottom of the amplitude transformer is inserted into the solution for 1cm, ultrasonic reaction is carried out for 60min under the ultrasonic power of 450W, circulating constant-temperature water is introduced into an interlayer of the reactor in the reaction process to maintain the system temperature at 15 ℃, after the reaction is finished, the polymer emulsion is distilled and concentrated to have the solid content of 40% under reduced pressure, cooled to the room temperature, tween60 accounting for 3% of the acrylic acid mass is added, and stirring is uniform.
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 weight of the attapulgite clay, vinyltriethoxysilane accounting for 1.0% of the weight of the attapulgite clay, and terpene hydroperoxide accounting for 0.5% of the total weight of the hydroxyethyl acrylate and vinyltriethoxysilane, heating in a water bath to 78 ℃ to initiate polymerization, and reacting for 60min to prepare a modified attapulgite clay suspension;
(2) Dissolving acrylic acid and 2-acrylamide-2-methyl-propane sulfonic acid accounting for 5% of the mass of the acrylic acid in deionized water, regulating the pH value to 6 by ammonia water, uniformly stirring to prepare aqueous phase solution for standby, 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, a cross-linking agent 1, 6-hexanediol diacrylate accounting for 0.5 percent of the mass of acrylic acid and an Ekksen mobil isoparaar C are mixed, wherein the mass ratio of the cross-linking agent 1, 6-hexanediol diacrylate to the mass of acrylic acid is 1:0.25; span80 accounting for 3% of Isopar C mass, modified attapulgite suspension accounting for 20% of acrylic acid mass, uniformly mixing, homogenizing for 2min by a homogenizer, transferring the homogenized emulsion into a four-neck flask, heating to 60 ℃ under the condition of 300 r/min stirring, preserving heat for 60min, concentrating the polymer emulsion by reduced pressure distillation to the solid content of 40% after the reaction is finished, cooling to room temperature, adding Tween60 accounting for 3% of acrylic acid mass, and uniformly stirring.
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 the solution for 1cm, performing ultrasonic treatment for 60min under 900W power, 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% of the mass of the attapulgite clay, vinyl triethoxysilane accounting for 1.0% of the mass of the attapulgite clay, and terpene hydrogen peroxide accounting for 0.5% of the total mass of the hydroxyethyl acrylate and the vinyl triethoxysilane, adjusting the output power of ultrasonic waves to 450W, and performing ultrasonic irradiation for 60min to prepare a modified attapulgite suspension;
(2) Dissolving acrylic acid in deionized water, regulating the pH value to 6 by ammonia water, and uniformly stirring to prepare aqueous solution for standby, 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, a cross-linking agent 1, 6-hexanediol diacrylate accounting for 0.5 percent of the mass of acrylic acid and an Ekksen mobil isoparaar C are mixed, wherein the mass ratio of the cross-linking agent 1, 6-hexanediol diacrylate to the mass of acrylic acid is 1:0.25; span80 accounting for 3% of Isopar C mass, modified attapulgite suspension accounting for 20% of acrylic acid mass, uniformly mixing, homogenizing for 2min 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 1cm, ultrasonically reacting for 60min under 450W ultrasonic power, introducing circulating constant-temperature water into a reactor interlayer in the reaction process to maintain the system temperature at 15 ℃, after the reaction is finished, decompressing, distilling and concentrating the polymer emulsion to have the solid content of 40%, cooling to room temperature, adding Tween60 accounting for 3% of acrylic acid mass, and uniformly stirring.
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, performing ultrasonic treatment for 30min under the power of 1200W, 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 vinyltrimethoxysilane, adjusting the output power of ultrasonic waves to 600W, and performing ultrasonic irradiation for 30min to prepare a modified attapulgite suspension;
(2) Dissolving methacrylic acid, namely 2-acrylamide-2-methyl-propane sulfonic acid accounting for 10 percent of the mass of the methacrylic acid, in deionized water, regulating the pH value to 7 by ammonia water, uniformly stirring to prepare aqueous phase solution for standby, wherein the mass of the deionized water accounts for 30 percent of the total weight of the raw materials in the step (2) and the step (3);
(3) Under the stirring condition, 1.0 percent of cross-linking agent 1, 4-butanediol diacrylate accounting for the mass of methacrylic acid and the Ekksen mobil isoparaar E are mixed, wherein the mass ratio of the cross-linking agent 1, 4-butanediol diacrylate to the mass of methacrylic acid monomer is 1:0.6; and (3) uniformly mixing a span60 accounting for 5% of Isopar E by mass and a modified attapulgite suspension accounting for 40% of methacrylic acid by mass, homogenizing for 5min by using a homogenizer, transferring the homogenized emulsion into an ultrasonic reactor, mounting an ultrasonic amplitude transformer, inserting the bottom of the amplitude transformer into the solution for 2cm, ultrasonically reacting for 30min under 600W ultrasonic power, introducing circulating constant-temperature water into a reactor interlayer in the reaction process to maintain the system temperature at 45 ℃, and after the reaction is finished, carrying out reduced pressure distillation and concentration on the polymer emulsion to reach a solid content of 50%, cooling to room temperature, adding Tween80 accounting for 5% of methacrylic acid by mass, and uniformly stirring.
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, performing 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% of the mass of the attapulgite clay, vinyl tri (beta-methoxyethoxy) silane accounting for 1.5% of the mass of the attapulgite clay, tertiaryamyl hydrogen peroxide accounting for 0.75% of the total mass of the acrylamide and the vinyl tri (beta-methoxyethoxy) silane, adjusting the output power of ultrasonic waves to 500W, and performing ultrasonic irradiation for 45min to prepare a modified attapulgite suspension;
(2) Dissolving maleic acid, wherein the mass of the maleic acid is 7.5 percent of that of 2-acrylamide-2-methyl-propane sulfonic acid in deionized water, regulating the pH value to 6.5 by ammonia water, uniformly stirring to prepare aqueous phase solution for standby, and the mass of the deionized water is 25 percent 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 0.75 percent of the mass of the maleic acid and the isoparaar G of the Ekksen mobil isoparaffin are mixed, wherein the mass ratio of the cross-linking agent to the maleic acid is 1:0.5; the method comprises the steps of (1) uniformly mixing span80 accounting for 4% of Isopar G and modified attapulgite suspension accounting for 30% of maleic acid, 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, ultrasonically reacting for 45min under 500W ultrasonic power, introducing circulating constant-temperature water into a reactor interlayer in the reaction process to maintain the system temperature 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, 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, performing ultrasonic treatment for 40min under the power of 1100W, 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, vinyltrimethoxysilane 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 vinyltrimethoxysilane, adjusting the output power of ultrasonic waves to 550W, and performing ultrasonic irradiation for 40min to prepare a modified attapulgite suspension;
(2) Dissolving maleic anhydride and 2-acrylamide-2-methyl-propane sulfonic acid accounting for 6% of the mass of the maleic anhydride in deionized water, regulating the pH value to 6 by ammonia water, and uniformly stirring to prepare an aqueous solution for standby, 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 is adopted, and the mass ratio of the cross-linking agent 1, 4-butanediol diacrylate to the mass of the maleic anhydride is 1:0.4; span60 accounting for 3.5 percent of Isopar H mass, modified attapulgite suspension accounting for 35 percent of maleic anhydride mass, uniformly mixing, homogenizing for 4 minutes 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, ultrasonically reacting for 40 minutes under 550W ultrasonic power, introducing circulating constant temperature water into an interlayer of the reactor in the reaction process to maintain the system temperature at 35 ℃, after the reaction is finished, decompressing, distilling and concentrating the polymer emulsion to solid content of 42 percent, cooling to room temperature, adding Tween80 accounting for 3.5 percent of maleic anhydride mass, and uniformly stirring.
Example 5
Accurately weighing 2g of thickener, adding 98g of distilled water, stirring, dripping 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 a constant speed of 10 revolutions per minute (rotor No. 6).
Electrolyte resistance is expressed as viscosity retention, and the viscosity of the thickener white slurry added with 0.05% NaCl (solid) white slurry is measured, and 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 reactive dye is prepared into slurry by deionized water, urea and anti-dyeing salt S are dissolved into a small amount of hot water, then the reactive dye color paste is uniformly mixed with the mixed solution of the urea and the anti-dyeing salt, after the dye is fully dissolved by full stirring, the thickener raw paste is added, the mixture is uniformly stirred, and sodium carbonate is added before use. Reactive dye printing was performed according to the following process, and the K/S value, permeability, color unevenness, de-pasting rate, and dry and wet rubbing fastness of the printed fabric were compared, and the results are shown in table 2.
Preparing color paste, printing, drying (60 ℃), steaming (102-103 ℃ for 10 min), washing (cold water before hot water), soap boiling (soap flake 2g/L, boiling for 10 min), washing (hot water before cold water), drying (60 ℃)
Table 1 sample thickening properties
| White paste viscosity (mPa. S) | Viscosity retention (%) | |
| Example 1 | 16690 | 92.6 |
| Comparative example 1 | 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 a strong thickening ability and are excellent in electrolyte resistance. The attapulgite clay of comparative example 1 was not modified, and its compatibility with polyacrylic acid was poor, and the thickening ability and electrolyte resistance of the resulting thickener were inferior to those of example 1. In comparative example 2, the conventional stirring process was adopted, the attapulgite clay could not be effectively dissociated during stirring, and could not be effectively compounded with the polyacrylic acid macromolecules, and the thickening ability and electrolyte resistance of the obtained thickener were also inferior to those of example 1. In comparative example 3, the electrolyte resistance of the resulting thickener was significantly inferior to that of example 1, and the thickening ability was slightly inferior to that of example 1, without adding the water-soluble monomer 2-acrylamide-2-methyl-propane sulfonic acid.
TABLE 2K/S value, permeability, de-pasting Rate of reactive dye printed fabrics
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 is, the better the printing penetration performance of the color paste is. The thickener mainly plays a role in transferring dye in the printing process, and after printing is finished, the thickener must be washed out of the fabric, otherwise, the hand feeling of the printed fabric is affected, and the higher the paste removal rate is, the softer the hand feeling of the printed fabric is. As can be seen from the above table, the thickener obtained in example 1 has a high K/S value on the front side, i.e. a high color yield, good permeability, high de-pasting rate and good washing effect. Because the thickeners obtained in comparative examples 1,2 and 3 have poor thickening ability and electrolyte resistance, the raw thickener paste concentration in the printing process is higher than that in example 1 (the raw paste concentration in comparative examples 1 and 2 is 3.5%, the raw paste concentration in comparative examples 1 and 2 is 3.0%, and the raw paste concentration in examples is 2%), and after printing is completed, the residual thickener on the fabric is high and the paste removal rate is low.
Claims (8)
1. The ultrasonic-assisted method for preparing the polyacrylic acid/attapulgite composite thickener is characterized by comprising the following steps of:
(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, performing ultrasonic treatment for 30-60min under 900-1200W power, introducing circulating constant temperature water into an interlayer of the reactor in the treatment process to maintain the temperature of the system 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 performing ultrasonic irradiation for 30-60min to prepare a modified attapulgite suspension;
(2) Dissolving the monomer 1 and the monomer 2 in deionized water, regulating the pH value to 6-7 by ammonia water, and uniformly stirring to prepare an aqueous solution for later use;
the monomer 1 is one of acrylic acid, methacrylic acid, maleic acid and maleic anhydride; monomer 2 is 2-acrylamide-2-methyl-propane sulfonic acid;
(3) Under the stirring condition, uniformly mixing solvent oil, a water-in-oil type 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, mounting an ultrasonic amplitude transformer, inserting the bottom of the amplitude transformer into the solution for 1-2cm, performing 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, concentrating the polymer emulsion by reduced pressure distillation to the solid content of 40-50%, cooling to the room temperature, adding the oil-in-water type emulsifier, and uniformly stirring to obtain the polyacrylic acid/attapulgite composite thickener.
2. The method for preparing the polyacrylic acid/attapulgite clay composite thickener with the assistance of ultrasound according to claim 1, wherein the nonionic monomer in the 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 terpene hydroperoxide, cumene hydroperoxide and tert-amyl hydroperoxide.
3. The method for preparing the polyacrylic acid/attapulgite composite thickener with the assistance of ultrasound according to claim 1, wherein the mass-volume ratio of the attapulgite clay to the deionized water in the step (1) is 1:20-1:30g/mL; the mass of the nonionic monomer accounts for 0.5 to 1.0 percent 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 clay composite thickener with the assistance of ultrasound according to claim 1, wherein the mass of the water-soluble monomer in the step (2) accounts for 5-10% of the mass of the acrylic monomer; the mass of deionized water accounts for 15-30% of the total weight of the raw materials in the step (2) and the step (3).
5. The method for preparing the polyacrylic acid/attapulgite clay composite thickener according to claim 1, wherein the solvent oil in the step (3) is one of Isopar C/E/G/H/L/M, and the mass ratio of the solvent oil to acrylic monomers is 1:0.25-1:0.6.
6. The method for preparing the polyacrylic acid/attapulgite clay composite thickener with the assistance of ultrasound according to claim 1, wherein the water-in-oil type emulsifier in the step (3) is span80 or span60, and the mass of the water-in-oil type emulsifier accounts for 3% -5% of the mass of the solvent oil.
7. The method for preparing the polyacrylic acid/attapulgite clay composite thickener with the assistance of ultrasound according to 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 accounts for 0.5% -1.0% of the mass of the acrylic monomer.
8. The method for preparing the polyacrylic acid/attapulgite composite thickener with the assistance of ultrasound according to claim 1, wherein the mass of the modified attapulgite suspension in the step (3) accounts for 20-40% of the mass of the acrylic monomer; the oil-in-water type emulsifier is one of Tween60, tween80 and AEO-9, and the dosage of the oil-in-water type 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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| 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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