CN112724461A - High-humidity-heat-resistant stable aqueous anti-yellowing agent for high-water-absorptivity resin - Google Patents
High-humidity-heat-resistant stable aqueous anti-yellowing agent for high-water-absorptivity resin Download PDFInfo
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Abstract
The main component of the aqueous anti-yellowing agent is sulfinate, the sulfinate with a chelating structure can be directly used as the aqueous anti-yellowing agent, and the sulfinate has a very stable structure, can resist high temperature, high humidity and acid and alkali, has a good anti-yellowing effect, can not deteriorate after being placed for a long time under the conditions of high temperature and high humidity, has excellent anti-yellowing performance under the conditions of high humidity and heat, and effectively overcomes the defect that the aqueous anti-yellowing agent is easy to deteriorate; in addition, the use method is simple, and the addition of the high water absorption resin in any step of the preparation of the high water absorption resin has good anti-yellowing effect.
Description
Technical Field
The invention belongs to the technical field of anti-yellowing agents, and particularly relates to a high-humidity-heat-resistant stable aqueous anti-yellowing agent for high-water-absorptivity resin.
Background
Super Absorbent Resin (SAR) is also known as Super Absorbent Polymer (SAP), water Absorbent Polymer material, Super Absorbent water Absorbent agent and the like, has a slightly crosslinked three-dimensional network structure, can absorb and maintain water which is hundreds to thousands of times of the weight of the Super Absorbent Polymer, and is widely applied to the fields of baby diapers, women sanitary products, adult incontinence pads, agriculture and forestry water retention, desert control and the like.
Yellowing is a common problem in high molecular materials, and according to the characteristics and reasons of yellowing, the yellowing mechanism can be roughly divided into three types:
the first method comprises the following steps: the polymer chain is broken to change a conjugated system, so that chromophore is generated to cause yellowing, and the main inducement is light and heat;
and the second method comprises the following steps: oxidative yellowing, wherein residual reducing impurities and metal catalysts in a system can induce yellowing under the action of an oxidant, for example, phenolic substances are oxidized into quinone luminescent groups;
and the third is that: the substance containing the nitrogen group is easy to generate azo group chromophore under the influence of light, moist heat and ultraviolet rays under the action of active hydrogen.
To inhibit yellowing of SAP products, anti-yellowing agents are often added. The common water-based anti-yellowing agent on the market is mainly a water-soluble reducing agent. Common water-soluble reducing agents are sodium sulfite, sodium bisulfite, sodium thiosulfate, sodium metabisulfite, and the like.
Chinese patent CN102936348A discloses 'an acrylic acid water-absorbing resin with excellent water retention and yellowing resistance and a preparation method thereof', which adds 10-1000ppm of yellowing resistance polymerization inhibitor in acrylic acid and adopts sulfite as a reducing agent. The water-absorbent resin product prepared by the method has the advantages of excellent water-retaining property and yellowing resistance.
Chinese patent CN107915852A discloses a method for preparing a clean and yellowing-resistant water-absorbent resin, which is characterized in that in the pre-neutralization method and the post-neutralization method, a chelating agent and a water-soluble reducing agent are added into the water-absorbent resin to improve the whiteness of the water-absorbent resin and enhance the yellowing resistance of the product. The water-soluble reducing agent in the patent is mainly sodium thiosulfate, sodium sulfite, sodium metabisulfite and sodium hydrosulfite. The water-soluble reducing agents have stronger reducibility, are easy to be weathered into sodium sulfate when being exposed in the air, and influence the anti-yellowing effect.
At present, the common aqueous anti-yellowing agents are selected sulfites which are easy to deteriorate and have odor, so that the usage of the sulfites in SAP is influenced.
Disclosure of Invention
The invention aims to provide a high-humidity and high-heat-stability aqueous anti-yellowing agent for a high-water-absorptivity resin, which has excellent anti-yellowing performance under high-humidity and high-heat conditions, effectively overcomes the defect that the aqueous anti-yellowing agent is easy to deteriorate, is simple in use method, and has good anti-yellowing effect when added in any step of the high-water-absorptivity resin production.
In order to achieve the purpose, the invention provides the following technical scheme:
the high-humidity-heat-stability-resistant water-based anti-yellowing agent for the high-water-absorptivity resin mainly comprises sulfinate, and is characterized in that the sulfinate has the following structural formula:
wherein M is1、M2Is a metal element.
Further, said M1Is a group IIA metal element in the periodic table, preferably magnesium, calcium or zinc.
Further, said M2Is a metal element of IA group in the periodic table, preferably sodium or potassium.
The high-humidity-heat-stability-resistant aqueous anti-yellowing agent for the super absorbent resin is characterized in that the sulfinate is prepared by the following steps:
1) glyoxylic acid and M1Reacting the oxide or the hydroxide in an aqueous solution at the temperature of 0-5 ℃ for 30-60 min to obtain a solution a;
2) adding M into the solution a obtained in the step 1)2The temperature of the bisulfite is controlled to be 0-5 ℃, the reaction is carried out for 2-3 h, then the temperature is increased to 80-90 ℃, the stirring reaction is carried out for 2-3 h, and then the temperature is reducedCooling to room temperature;
3) and after the reaction is finished, precipitating, filtering and drying to obtain a product sulfinate, wherein the product sulfinate in the filtrate is obtained by a method of spray drying or solvent evaporation.
Preferably, the glyoxylic acid and M in the step 1) are1After the reaction of the oxide or hydroxide, the pH of the aqueous solution is 5.0 to 6.0.
Preferably, the glyoxylic acid and M are1Oxide or hydroxide of, M2The amount ratio of the bisulfite to the water is 2:1:2 to 2.1.
Preferably, the spray drying conditions are: the temperature is 110-130 ℃, the frequency of a fan is 55-60 HZ, the rotating speed of a peristaltic pump is 8-10R/min, and the needle passing interval time is 2-3 s.
The main component of the high-humidity-heat-resistant stable aqueous anti-yellowing agent prepared by the invention is sulfinate. The sulfinate prepared by the method has strong reducibility, can be combined with oxygen to react, and can be decomposed into non-toxic byproducts, namely hydrosulfate, formate and carbon dioxide, so that the oxygen content in an SAP system is reduced, and the anti-yellowing effect is achieved.
The sulfinates of the invention are in the form of chelates, M1Selecting group IIA metal elements with strong affinity to O, preferably Mg2+、Ca2+And Zn2+The chelate formed when acting as a central ion is more stable. One central ion in the chelate is provided with two chelate ligands of sulfinate, so that the anti-yellowing capability is stronger compared with common sulfinate. In addition, the invention introduces M in the preparation of sulfinate2The group IA element, preferably sodium, potassium, and the like, provides the sulfinate with excellent anti-yellowing properties and excellent water solubility. The anti-yellowing agent prepared by using the sulfinate has good water solubility.
In the process for preparing sulfinates, the metal M is introduced in neutralized form with glyoxylic acid1Not only has the function of adjusting pH, but also has the function of introducing central ions. By adding M2The bisulfite of (a) can undergo nucleophilic addition to the aldehyde group of glyoxylic acidTo obtain the sulfinate. And (3) the sulfinate does not have a chelating structure, so that the temperature is increased to 80-90 ℃ for reaction for 2-3 h, and the sulfinate is chelated to obtain the final sulfinate with the chelating structure.
Compared with the prior art, the invention has the following beneficial effects:
1. the sulfinate with a chelating structure can be directly used as a water-based anti-yellowing agent, and the sulfinate has a very stable structure, can resist high temperature, high humidity and acid and alkali, has a good anti-yellowing effect, and cannot deteriorate after being placed for a long time under the conditions of high temperature and high humidity.
2. The aqueous anti-yellowing agent prepared by the invention has good water solubility and simple use method, can be added in any step of the preparation of the high water-absorbent resin and has good anti-yellowing effect, and the sulfite anti-yellowing agent has good anti-yellowing effect only when added in an acid environment.
Drawings
FIG. 1 is a schematic diagram of wet heat oxidation resistance of SAP dry powder in an embodiment of the invention.
FIG. 2 is an infrared schematic of the sulfinate salt just prepared in example 4 of the present invention.
FIG. 3 is a schematic infrared image of a sulfinate prepared in example 4 of the present invention after conventional storage for one year.
Detailed Description
The present invention is further illustrated by the following specific examples.
Example 1
Weighing 29.6g of glyoxylic acid, placing the glyoxylic acid in a 250mL beaker, adding 100g of deionized water, placing the beaker in an ice-water bath, starting stirring, adding 7.4g of calcium hydroxide into the solution in the stirring process, stirring for reacting for 30min, adding 20.8g of sodium bisulfite into the solution after 30min, continuing stirring for reacting for 2h, then heating to 80 ℃, keeping the temperature for 2h, cooling to room temperature, filtering and drying to obtain a product sulfinate (disodium calcium acetate sulfinyl hydroxy acid), and obtaining the product sulfinate (disodium calcium acetate sulfinyl hydroxy acid) in the filtrate by spray drying.
Example 2
Weighing 29.6g of glyoxylic acid, placing the glyoxylic acid in a 250mL beaker, adding 100g of deionized water, placing the beaker in an ice-water bath, starting stirring, adding 9.39g of zinc hydroxide into the solution in the stirring process, stirring for reacting for 1h, then adding 24.0g of potassium bisulfite into the solution, continuing stirring for reacting for 2h, then heating to 80 ℃, and preserving heat for 2 h. And cooling to room temperature, filtering and drying to obtain a product sulfinate (hydroxyl sulfinic acid zinc dipotassium acetate), spray-drying the product sulfinate in the filtrate, and directly using the obtained product sulfinate (hydroxyl sulfinic acid zinc dipotassium acetate) as an anti-yellowing agent.
Example 3
Weighing 29.6g of glyoxylic acid in a 250mL beaker, adding 100g of deionized water, placing the beaker in an ice-water bath, starting stirring, adding 4.0g of magnesium oxide into the solution in the stirring process, stirring for reacting for 30min, then adding 25.2g of potassium bisulfite into the solution, and continuing stirring for reacting for 3 h. And then heating to 80 ℃, keeping the temperature for 2h, cooling to room temperature, filtering and drying to obtain a product sulfinate (hydroxyl sulfinic acid magnesium acetate dipotassium), wherein the product sulfinate in the filtrate is obtained by spray drying, and the obtained product sulfinate (hydroxyl sulfinic acid magnesium acetate dipotassium) can be directly used as an anti-yellowing agent.
Example 4
Weighing 29.6g of glyoxylic acid in a 250mL beaker, adding 100g of deionized water, placing the beaker in an ice-water bath, starting stirring, adding 5.8g of magnesium hydroxide into the solution in the stirring process, stirring for reaction for 1h, then adding 21.84g of sodium bisulfite into the solution, continuing stirring for reaction for 3h, then heating to 90 ℃, keeping the temperature for 2h, cooling to room temperature, filtering and drying to obtain a product sulfinate (disodium magnesium acetate sulfinyl hydroxy sulfinate), and obtaining the product sulfinate (disodium magnesium acetate sulfinyl hydroxy sulfinate) by spray drying, wherein the obtained product sulfinate can be directly used as an anti-yellowing agent.
Example 5
Adding acrylic acid into distilled water to prepare an acrylic acid solution, adding the disodium calcium acetate hydroxysulfinate prepared in the embodiment 1 into the acrylic acid aqueous solution, wherein the adding amount of the disodium calcium acetate hydroxysulfinate is 0.1 percent of the mass of the acrylic acid, then summarizing the mixed solution, slowly adding a NaOH solution, and continuously stirring.
Adding ammonium persulfate, acrylamide and N, N-methylene-bisacrylamide into the neutralized acrylic acid solution, and stirring until the ammonium persulfate, the acrylamide and the N, N-methylene-bisacrylamide are completely dissolved. Introducing nitrogen for 30 minutes, discharging oxygen, and heating to 80 ℃ for reaction for 6 hours. Obtaining colorless transparent gel after the reaction is finished, drying the gel, and crushing the gel by using a universal crusher to obtain the super absorbent resin.
Example 6
Adding acrylic acid into distilled water to prepare an acrylic acid solution, and slowly adding the mixture of the zinc dipotassium hydroxysulfinate acetate prepared in the example 2 and the NaOH solution into the acrylic acid solution under the condition of stirring, wherein the using amount of the zinc dipotassium hydroxysulfinate acetate is 0.1 percent of the mass of the acrylic acid.
Adding ammonium persulfate, acrylamide and N, N-methylene-bisacrylamide into the neutralized acrylic acid solution, and stirring until the ammonium persulfate, the acrylamide and the N, N-methylene-bisacrylamide are completely dissolved. Introducing nitrogen for 30 minutes, discharging oxygen, and heating to 80 ℃ for reaction for 6 hours. Obtaining colorless transparent gel after the reaction is finished, drying the gel, and crushing the gel by using a universal crusher to obtain the super absorbent resin.
Example 7
The water-soluble anti-yellowing agent of example 4 was stored for 1 year to prepare a 0.1% aqueous solution, and a predetermined amount of the surface-crosslinked super absorbent resin (CR 720, satellite petrochemical company, ltd.) was uniformly sprayed on the surface of the resin particles.
Example 8
Adding acrylic acid into distilled water to prepare an acrylic acid solution, and slowly adding a NaOH solution into the acrylic acid solution under the stirring condition. Ammonium persulfate, acrylamide and N, N-methylenebisacrylamide were then added to the neutralized acrylic acid solution, stirred to complete dissolution, and the disodium calcium hydroxysulfinate acetate prepared in example 4, which was conventionally stored for one year, was then added to the solution in an amount of 0.1% of the amount of acrylic acid. Introducing nitrogen for 30 minutes, discharging oxygen, and heating to 80 ℃ for reaction for 6 hours. Obtaining colorless transparent gel after the reaction is finished, drying the gel, and crushing the gel by using a universal crusher to obtain the super absorbent resin.
Comparative examples
Adding acrylic acid into distilled water to prepare an acrylic acid solution, adding a comparison sample S1000 into the acrylic acid aqueous solution, wherein the dosage of the comparison sample S1000 is 0.1 percent of that of the acrylic acid, and then slowly adding a NaOH solution into the solution under the condition of stirring. Then ammonium persulfate, acrylamide and N, N-methylene-bisacrylamide are added into the neutralized acrylic acid solution, and the mixture is stirred until the mixture is completely dissolved. Introducing nitrogen for 30 minutes, discharging oxygen, and heating to 80 ℃ for reaction for 6 hours. Obtaining colorless transparent gel after the reaction is finished, drying the gel, and crushing the gel by using a universal crusher to obtain the super absorbent resin.
The water-soluble anti-yellowing agents in the above examples 1 to 4 and the comparative sample S1000 were respectively prepared into 0.1% aqueous solutions, a certain amount of surface-crosslinked super absorbent resin (CR 720, manufactured by satellite petrochemical corporation, zhejiang) was uniformly sprayed on the surfaces of the resin particles, and the resin particles, the examples 5 to 8, the comparative example, and the blank were placed in a constant temperature and humidity chamber, and the whiteness value of the super absorbent resin was measured at 70 ℃ and 90% relative humidity, and the measurement results are shown in table 1.
As can be seen from Table 1, when the water-soluble anti-yellowing agent of the present invention is added to an acidic solution or an alkaline solution during the preparation process, or sprayed on the surface of the final product, the free expansion rate, the centrifugal retention capacity, the 0.3psi absorption capacity under pressure, the absorption rate, and other properties of the SAP do not change significantly. Whereas the comparative sample S1000 was added, the performance of the prepared SAP was reduced.
FIG. 1 is a schematic diagram showing the wet-heat oxidation resistance of the SAP dry powder in the embodiment of the present invention, and the result obtained from the diagram is that the blank sample without adding the anti-yellowing agent has a more obvious yellowing effect, and the blank sample after adding the anti-yellowing agent has a yellowing retarding effect, and the anti-yellowing effect of the water-soluble anti-yellowing agent of the present invention is better than that of the comparative sample S1000, corresponding to the results in Table 1.
FIG. 2 is a schematic infrared diagram of the sulfinate prepared just after the sulfinate of the embodiment 4 of the present invention is prepared, FIG. 3 is a schematic infrared diagram of the sulfinate prepared in the embodiment 4 of the present invention after being conventionally stored for one year, comparing the spectrum findings of FIG. 2 and FIG. 3 and the two spectra are consistent, and combining the results of Table 1 and the embodiment 7 and the embodiment 8 in FIG. 1, it can be seen that the anti-yellowing effect is not reduced even if the sulfinate is stored for one year, which indicates that the sulfinate is very stable. In addition, in the preparation process of the sulfinate, when the product in the filtrate is separated by spray drying, the temperature is controlled to be 110-130 ℃, and the high temperature resistance of the prepared sulfinate can also be proved to be good.
Claims (7)
1. The high-humidity-heat-stability-resistant water-based anti-yellowing agent for the high-water-absorptivity resin mainly comprises sulfinate, and is characterized in that the sulfinate has the following structural formula:
wherein M is1、M2Is a metal element.
2. The high humid heat stability resistant aqueous anti-yellowing agent for super absorbent resin according to claim 1, wherein M is1Is a group IIA metal element in the periodic table, preferably magnesium, calcium or zinc.
3. The high humidity heat resistant stable water for super absorbent resin according to claim 1An anti-yellowing agent, wherein M is2Is a metal element of IA group in the periodic table, preferably sodium or potassium.
4. The high-humidity-heat-stability-resistant aqueous anti-yellowing agent for the high-water-absorption resin as claimed in claims 1 to 3, wherein the sulfinate is prepared by the following steps:
1) glyoxylic acid and M1Reacting the oxide or the hydroxide in an aqueous solution at the temperature of 0-5 ℃ for 30-60 min to obtain a solution a;
2) adding M into the solution a obtained in the step 1)2Controlling the temperature of the bisulfite to be 0-5 ℃, reacting for 2-3 h, then heating to 80-90 ℃, reacting for 2-3 h, and then cooling to room temperature;
3) and after the reaction is finished, precipitating, filtering and drying to obtain a product sulfinate, wherein the product sulfinate in the filtrate is obtained by a method of spray drying or solvent evaporation.
5. The high humid heat stability resistant aqueous anti-yellowing agent for high water absorption resin as claimed in claim 4, wherein the glyoxylic acid and M in step 1) are1After the reaction of the oxide or hydroxide, the pH of the aqueous solution is 5.0 to 6.0.
6. The high humid heat stability resistant aqueous anti-yellowing agent for super absorbent resin according to claim 4, wherein the glyoxylic acid, M is1Oxide or hydroxide of, M2The amount ratio of the bisulfite to the water is 2:1:2 to 2.1.
7. The high humid heat stability resistant aqueous anti-yellowing agent for super absorbent resin according to claim 4, wherein the spray drying conditions are: the temperature is 110-130 ℃, the frequency of a fan is 55-60 HZ, the rotating speed of a peristaltic pump is 8-10R/min, and the needle passing interval time is 2-3 s.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114891174A (en) * | 2022-06-29 | 2022-08-12 | 万华化学集团股份有限公司 | Waterborne polyurethane resin and preparation method thereof |
| CN116143672A (en) * | 2023-02-28 | 2023-05-23 | 卫星化学股份有限公司 | Water-soluble antioxidant and preparation method and application thereof |
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| CN109251361A (en) * | 2018-09-13 | 2019-01-22 | 浙江卫星石化股份有限公司 | A kind of anti-yellowing dose of water solubility for super absorbent resin |
| CN110088083A (en) * | 2016-12-13 | 2019-08-02 | L.布鲁格曼有限及两合公司 | Sulfonate composition and its purposes for colour stable |
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| US20130256593A1 (en) * | 2012-03-30 | 2013-10-03 | Basf Se | Color-Stable Superabsorbent |
| CN110088083A (en) * | 2016-12-13 | 2019-08-02 | L.布鲁格曼有限及两合公司 | Sulfonate composition and its purposes for colour stable |
| CN109251361A (en) * | 2018-09-13 | 2019-01-22 | 浙江卫星石化股份有限公司 | A kind of anti-yellowing dose of water solubility for super absorbent resin |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114891174A (en) * | 2022-06-29 | 2022-08-12 | 万华化学集团股份有限公司 | Waterborne polyurethane resin and preparation method thereof |
| CN116143672A (en) * | 2023-02-28 | 2023-05-23 | 卫星化学股份有限公司 | Water-soluble antioxidant and preparation method and application thereof |
| CN116143672B (en) * | 2023-02-28 | 2024-03-29 | 卫星化学股份有限公司 | Water-soluble antioxidant and preparation method and application thereof |
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