Super absorbent resin material with in-situ deodorization function as well as preparation method and application of super absorbent resin material

Abstract

The invention provides a super absorbent resin material with an in-situ deodorization function as well as a preparation method and application thereof, and belongs to the technical field of super absorbent resin. Adding acrylic acid and water into a neutralization kettle, uniformly stirring, dropwise adding a sodium hydroxide aqueous solution, stirring for reaction after dropwise adding, and naturally cooling after reaction to obtain a neutralization solution; adding the obtained neutralization solution into a polymerization reaction kettle, adding zinc diricinoleate while stirring, uniformly stirring, dropwise adding an aqueous solution of an initiator, and carrying out polymerization reaction while stirring to obtain polymer soft colloid; and drying the obtained soft colloid, and crushing to obtain a granular material. Zinc diricinoleate is used as a deodorant and a cross-linking agent of polymerization reaction, and is chemically combined into a polymerization network of super absorbent resin, so that the super absorbent resin can be used for deodorizing liquid with peculiar smell and can also be used as an air purifying agent.

Description

Technical Field

[0001] The present invention belongs to the technical field of superabsorbent resins, and particularly relates to a superabsorbent resin material with an in-situ deodorization function, a preparation method thereof, and an application thereof. Background Art

[0002] At present, more than 80% of the superabsorbent resins in the world are used in the field of disposable sanitary products. The superabsorbent resins applied in this aspect will directly contact the human body. Excreta contains odor sources such as ammonia and sulfides. Disposable sanitary products will generate odors during use, irritating the olfactory senses of the human body and causing potential harm to people's physiology and psychology. Especially for superabsorbent resins used in adult diapers, etc., in addition to the above absorption characteristics, it is more desirable to have additional functions of deodorization and odor removal. Therefore, developing a superabsorbent resin with a long-lasting deodorization function for application in the field of disposable sanitary products is of great significance to human health.

[0003] Zinc ricinoleate has been proven to be an efficient new deodorant, and it has also been used as a deodorant in many patents. For example, Chinese Patent CN119615627A uses it in polyester filaments with deodorization function; Chinese Patent CN119506021A uses it in handmade soaps with deodorization function; Chinese Patent CN118767191A applies it to pet odor removal; while Chinese Patent CN118681399A applies it to air purification. Especially Chinese Patent CN114854161A uses it in combination with other deodorants for deodorization and odor removal of superabsorbent resins. However, in these patents, the use of zinc ricinoleate is to physically mix it with the matrix resin or small molecules, and it is difficult to overcome the problem of its dissolution and failure, so the deodorization function cannot be maintained for a long time. Chinese Patent CN102585415A discloses a composition with a long-lasting deodorization effect, which has a three-layer core-shell structure. After the outer layer contacts and dissolves with water, etc., the inner layer fragrance substance will slowly release through the middle layer, achieving a long-lasting deodorization effect. However, obviously this deodorizing superabsorbent resin can only be used after absorbing water, that is, it can only be used for deodorization of liquid samples and cannot be used for removing odors in a simple space environment. Summary of the Invention

[0004] In view of the above problems, the present invention uses zinc ricinoleate as a cross-linking agent in the preparation of superabsorbent resins, which can be stably chemically bonded to the structure of superabsorbent resins and is suitable for deodorization of gases in liquid and space environments.

[0005] One object of the present invention is to provide a superabsorbent resin material.

[0006] Another object of the present invention is to provide a preparation method of the superabsorbent resin material.

[0007] A third object of the present invention is to provide an application of the superabsorbent resin material in gas deodorization in liquid and space environments.

[0008] To achieve the above objects of the present invention, the following technical solutions are specifically adopted:

[0009] In a first aspect, the present invention provides a superabsorbent resin material with an in-situ deodorization function, and the polyester resin is prepared by polymerization from raw materials including the following parts by mass:

[0010] 300 - 400 parts of acrylic acid;

[0011] 70 - 100 parts of water;

[0012] 10 - 15 parts of zinc ricinoleate;

[0013] An aqueous sodium hydroxide solution, including: 180 - 250 parts of sodium hydroxide and 600 - 800 parts of water;

[0014] An aqueous solution of an initiator, including: 4 - 6 parts of an oxidant, 2 - 3 parts of a reductant, and 20 - 30 parts of water.

[0015] The neutralization degree of the acrylic acid is 75% - 90%;

[0016] The zinc ricinoleate is used both as a deodorant and as a cross-linking agent for the synthesis of the superabsorbent resin, and its chemical structural formula is as follows:

[0017]

[0018] The oxidant is one of ammonium persulfate, potassium persulfate, hydrogen peroxide, and tert-butyl hydroperoxide.

[0019] The reductant is one of sodium bisulfite, sodium sulfite, and ascorbic acid.

[0020] The water is deionized water.

[0021] Typical but non-limiting parts by mass of acrylic acid are, for example, 300, 310, 320, 330, 340, 350, 360, 370, 380, 390, 400 parts; typical but non-limiting parts by mass of zinc ricinoleate are, for example, 10, 11, 12, 13, 14, 15 parts; typical but non-limiting parts by mass of the aqueous sodium hydroxide solution are, for example, 200, 210, 220, 225, 230, 240, 250 parts; typical but non-limiting parts by mass of the oxidant are, for example, 4, 5, 6 parts; typical but non-limiting parts by mass of the reductant are, for example, 2, 2.5, 3 parts; typical but non-limiting parts by mass of water are, for example, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200 parts.

[0022] In a second aspect, the present invention provides a method for preparing the above-mentioned superabsorbent resin material with in-situ deodorizing function, comprising the following steps:

[0023] 1) Neutralization reaction of acrylic acid: Add acrylic acid and water into a neutralization kettle, stir evenly, dropwise add an aqueous sodium hydroxide solution, and stir for reaction after dropping is completed, and then naturally cool after the reaction to obtain a neutralized solution;

[0024] 2) Polymerization reaction: Add the obtained neutralized solution into a polymerization reaction kettle, add zinc ricinoleate under stirring, stir evenly, then dropwise add an aqueous solution of an initiator, and carry out a polymerization reaction under stirring to obtain a polymer soft colloid;

[0025] 3) Drying and pulverizing: Dry the obtained soft colloid and pulverize it into granular materials.

[0026] In some embodiments, in step 1), the reaction temperature is lower than 50 °C and the reaction time is 20 - 30 minutes;

[0027] In some embodiments, in step 2), the polymerization reaction temperature is 20 °C - 40 °C and the polymerization reaction time is 10 - 20 minutes;

[0028] In some embodiments, in step 3), the drying temperature is 100 °C - 180 °C and the drying time is 50 - 120 minutes.

[0029] In a specific embodiment, the method for preparing the superabsorbent resin material with in-situ deodorizing function comprises the following steps:

[0030] 1) Neutralization reaction of acrylic acid: Add acrylic acid and water into a neutralization kettle, stir evenly, dropwise add an aqueous sodium hydroxide solution, control the reaction temperature to be lower than 50 °C, stir for reaction for 20 - 30 minutes after dropping is completed, and then naturally cool to obtain a neutralized solution;

[0031] 2) Polymerization reaction: Add the obtained neutralized solution into a polymerization reaction kettle, add zinc ricinoleate under stirring, stir evenly, then dropwise add an aqueous solution of an initiator, and carry out a polymerization reaction under stirring at 20 °C - 40 °C for 10 - 20 minutes to obtain a polymer soft colloid;

[0032] 3) Drying and pulverizing: Dry the obtained soft colloid at 100 °C - 180 °C for 50 - 120 minutes and pulverize it into granular materials.

[0033] In a third aspect, the present invention provides an application of the above-mentioned superabsorbent resin material with in-situ deodorizing function in gas deodorization in liquid and space environments.

[0034] The application methods include but are not limited to:

[0035] 1) Similar to ordinary superabsorbent resins, it can be used as a hygiene product for deodorization purposes, such as diapers and sanitary napkins, or it can be put into a suitable breathable bag for air purification;

[0036] 2) It can be used in any proportion by mixing with ordinary superabsorbent resins and / or highly blood-absorbent resins;

[0037] 3) After mixing with ordinary superabsorbent resins and / or highly blood-absorbent resins in any proportion, 1%-5% by weight of zinc ricinoleate is further mixed in.

[0038] Beneficial effects:

[0039] Using zinc ricinoleate as a deodorant and a cross-linking agent for polymerization reactions, zinc ricinoleate is chemically bonded to the polymerization network of the superabsorbent resin, avoiding the loss of deodorizing effect due to its dissolution as a small molecule. It can be used alone with water absorption and deodorization functions, or it can be used in combination with ordinary superabsorbent resins, and can also be further mixed with zinc ricinoleate. It can be used for deodorizing odorous liquids and can also be used as an air purifier.

[0040] The present invention has been described in detail above, but the above embodiments are essentially illustrative only and are not intended to limit the present invention. In addition, the present invention is not restricted by any theory described in the foregoing prior art or the invention content or the following examples. Specific embodiments

[0041] The following further illustrates the present invention with reference to embodiments. It should be noted that the following embodiments are provided for illustrative purposes only and do not constitute a limitation on the scope of protection required by the present invention.

[0042] Unless otherwise specified, the raw materials, reagents, methods, etc. used in the embodiments are all conventional raw materials, reagents, and methods in the art.

[0043] Example 1

[0044] Weigh 180 kg of sodium hydroxide and prepare a 30% aqueous solution, then let it cool; add 350 kg of acrylic acid and 100 kg of deionized water to a neutralization kettle, stir and dissolve evenly, then dropwise add the prepared sodium hydroxide aqueous solution, control the temperature of the neutralization kettle below 50°C. After the dropping is completed, stir and react for 20 - 30 minutes, and then add 12 kg of zinc ricinoleate and stir evenly.

[0045] Weigh 4.5 kg of ammonium persulfate and 2.2 kg of sodium sulfite, dissolve them in 23 kg of deionized water, add them to a polymerization kettle, and then add the solution obtained above. Polymerize at 20 - 40°C for 15 minutes to obtain a soft colloid of the deodorizing superabsorbent resin.

[0046] The obtained soft colloid is dried at 100°C - 180°C for 50 - 120 minutes and then crushed into granular materials.

[0047] Example 2

[0048] Weigh 200 kg of sodium hydroxide, prepare it into a 30% aqueous solution, and let it cool; add 375 kg of acrylic acid and 80 kg of deionized water to the neutralization kettle, stir and dissolve them evenly, then dropwise add the above-prepared sodium hydroxide aqueous solution, control the temperature of the neutralization kettle below 50°C. After the dropping is completed, stir and react for 20 - 30 minutes, and then add 16 kg of zinc ricinoleate and stir evenly.

[0049] Weigh 4.5 kg of ammonium persulfate and 2.4 kg of sodium sulfite, dissolve them in 30 kg of deionized water, add them to the polymerization kettle, and add the neutralized solution of the above-obtained mixed monomers. Polymerize at 20 - 40°C for 15 minutes to obtain a soft colloid of deodorant superabsorbent resin.

[0050] The obtained soft colloid is dried at 100°C - 180°C for 50 - 120 minutes and then crushed into granular materials.

[0051] Example 3

[0052] Weigh 180 kg of sodium hydroxide, prepare it into a 30% aqueous solution, and let it cool; add 350 kg of acrylic acid and 100 kg of deionized water to the neutralization kettle, stir and dissolve them evenly, then dropwise add the above-prepared sodium hydroxide aqueous solution, control the temperature of the neutralization kettle below 50°C. After the dropping is completed, stir and react for 20 - 30 minutes, and then add 15 kg of zinc ricinoleate and stir and mix evenly.

[0053] Weigh 4.4 kg of ammonium persulfate and 2.3 kg of sodium sulfite, dissolve them in 24 kg of deionized water, add them to the polymerization kettle, and add the neutralized solution of the above-obtained mixed monomers. Polymerize at 20 - 40°C for 18 minutes to obtain a soft colloid of deodorant superabsorbent resin.

[0054] The obtained soft colloid is dried at 100°C - 180°C for 50 - 120 minutes and then crushed into granular materials.

[0055] Example 4

[0056] Weigh 205 kg of sodium hydroxide, prepare it into a 30% aqueous solution, and let it cool; add 375 kg of acrylic acid and 75 kg of deionized water to the neutralization kettle, stir and dissolve them evenly, then dropwise add the above-prepared sodium hydroxide aqueous solution, control the temperature of the neutralization kettle below 50°C. After the dropping is completed, stir and react for 20 - 30 minutes, and then add 14 kg of zinc ricinoleate and stir and mix evenly.

[0057] Weigh 4.9 kg of potassium persulfate and 2.2 kg of sodium bisulfite, dissolve them in 28 kg of deionized water, add the solution to the polymerization kettle, and then add the neutralized solution of the mixed monomers obtained above. Carry out a polymerization reaction at 20 - 40 °C for 20 minutes to obtain a soft colloid of the deodorant superabsorbent resin.

[0058] Dry the obtained soft colloid at 100 °C - 180 °C for 50 - 120 minutes, and crush it into granular materials.

[0059] Example 5

[0060] Weigh 194 kg of sodium hydroxide, prepare it into a 30% aqueous solution, and let it cool. Add 370 kg of acrylic acid and 85 kg of deionized water to the neutralization kettle. After stirring and dissolving evenly, dropwise add the prepared sodium hydroxide aqueous solution, control the temperature of the neutralization kettle below 50 °C. After the dropping is completed, stir and react for 20 - 30 minutes, and then add 14 kg of zinc ricinoleate and stir to mix evenly.

[0061] Weigh 4.8 kg of ammonium persulfate and 2.4 kg of ascorbic acid, dissolve them in 29 kg of deionized water, add the solution to the polymerization kettle, and then add the neutralized solution of acrylic acid and its functional monomers obtained above. Carry out a polymerization reaction at 20 - 40 °C for 15 minutes to obtain a soft colloid of the deodorant superabsorbent resin.

[0062] Dry the obtained soft colloid at 100 °C - 180 °C for 50 - 120 minutes, and crush it into granular materials.

[0063] Comparative Example

[0064] Weigh 180 kg of sodium hydroxide, prepare it into a 30% aqueous solution, and let it cool. Add 350 kg of acrylic acid and 100 kg of deionized water to the neutralization kettle. After stirring and dissolving evenly, dropwise add the prepared sodium hydroxide aqueous solution, control the temperature of the neutralization kettle below 50 °C. After the dropping is completed, stir and react for 20 - 30 minutes.

[0065] Weigh 4.5 kg of ammonium persulfate, 2.2 kg of sodium sulfite and 10 kg of diacetone acrylamide crosslinking agent, dissolve them in 23 kg of deionized water, add the solution to the polymerization kettle, and then add the solution obtained above. Carry out a polymerization reaction at 20 - 40 °C for 15 minutes to obtain a soft colloid of the superabsorbent resin.

[0066] Dry the obtained soft colloid at 100 °C - 180 °C for 50 - 120 minutes, and crush it into granular materials (superabsorbent resin particles).

[0067] Mix 350 kg of the obtained superabsorbent resin particles with 12 kg of zinc ricinoleate, and stir evenly.

[0068] Test Example

[0069] An evaluation experiment on the deodorization and odor removal of the prepared deodorant resin material was carried out, including two indicators: removal rate and sustainable time. Since the traditional deodorization detection method is to evaluate through the olfactory senses of people, and the individual differences are relatively large, we quantitatively determined by the removal rates of two main source substances of odors, namely ammonia and hydrogen sulfide gas. The deodorant material obtained in the examples was used for the deodorization experiment of 5% concentration ammonia water and 2 g / L hydrogen sulfide aqueous solution. 1 g of the deodorant material obtained in the examples was added to 100 ml of the corresponding solution, and after shaking for 10 minutes, the concentrations of residual ammonia and hydrogen sulfide were measured, and then the removal rates of the two were calculated; for the determination of the deodorization duration, after deodorizing once a day, the ammonia water and hydrogen sulfide solution were filtered off, new ammonia water and hydrogen sulfide solution were supplemented, and then the deodorization rate was measured. The number of times when the final deodorization rate decreased to half of the original value was the number of uses. The experimental results are listed in Table 1. From the data in the table, it can be seen that compared with the deodorant resin obtained by physical mixing, the deodorant resin obtained by chemical polymerization has a comparable primary removal rate for ammonia and hydrogen sulfide. However, its number of uses far exceeds the deodorization effect of the resin obtained by physical mixing.

[0070] Table 1 Deodorization effect of deodorant resin material

[0071]

[0072]

[0073] The above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit them. Although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that: within the scope of the spirit and essence defined by the claims of the present invention, the technical solutions recorded in the foregoing embodiments can be modified, or some or all of the technical features can be equivalently replaced; and these modifications or replacements are still within the scope defined by the claims of the present invention.

Claims

1. A superabsorbent resin material with in-situ deodorizing function, characterized in that, The superabsorbent resin material with in-situ deodorization function is prepared by polymerization from raw materials including the following parts by mass: 300 - 400 parts of acrylic acid; 70 - 100 parts of water; 10 - 15 parts of zinc ricinoleate; Sodium hydroxide aqueous solution, including: 180 - 250 parts of sodium hydroxide and 600 - 800 parts of water; Aqueous solution of initiator, including: 4 - 6 parts of oxidant, 2 - 3 parts of reductant, and 20 - 30 parts of water.

2. The superabsorbent resin material with in-situ deodorizing function according to claim 1, characterized in that, The neutralization degree of the acrylic acid is 75% - 90%.

3. The superabsorbent resin material with in-situ deodorizing function according to claim 1, characterized in that, The oxidant is one of ammonium persulfate, potassium persulfate, hydrogen peroxide, and tert-butyl hydroperoxide.

4. The superabsorbent resin material with in-situ deodorizing function according to claim 1, wherein, The reductant is one of sodium bisulfite, sodium sulfite, and ascorbic acid.

5. A method for preparing a superabsorbent resin material with in-situ deodorizing function according to any one of claims 1-4, characterized in that, It includes the following steps: 1) Add acrylic acid and water to a neutralization kettle, stir evenly, drop in the sodium hydroxide aqueous solution, stir and react after dropping, and naturally cool after the reaction to obtain a neutralized solution; 2) Add the obtained neutralized solution to a polymerization reaction kettle, add zinc ricinoleate under stirring, stir evenly, then drop in the aqueous solution of the initiator, and carry out a polymerization reaction under stirring to obtain a polymer soft colloid; 3) Dry the obtained soft colloid and crush it into granular materials.

6. The preparation method according to claim 5, characterized in that, In step 1), the reaction temperature is lower than 50 °C, and the reaction time is 20 - 30 minutes.

7. The preparation method according to claim 5, characterized in that, In step 2), the polymerization reaction temperature is 20 °C - 40 °C, and the polymerization reaction time is 10 - 20 minutes.

8. The preparation method according to claim 5, characterized in that, In step 3), the drying temperature is 100 °C - 180 °C, and the drying time is 50 - 120 minutes.

9. Application of the superabsorbent resin material with in-situ deodorization function according to any one of claims 1 - 4 in gas deodorization in liquid and space environments.

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