CN109293950A - High-hydroscopicity and preparation method thereof - Google Patents

High-hydroscopicity and preparation method thereof Download PDF

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Publication number
CN109293950A
CN109293950A CN201811159852.XA CN201811159852A CN109293950A CN 109293950 A CN109293950 A CN 109293950A CN 201811159852 A CN201811159852 A CN 201811159852A CN 109293950 A CN109293950 A CN 109293950A
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weight
parts
absorbent resin
super absorbent
agent
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卢航
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Guangzhou City Ding Mao New Mstar Technology Ltd
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Guangzhou City Ding Mao New Mstar Technology Ltd
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00Processes of treating or compounding macromolecular substances
    • C08J3/02Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C08J3/075Macromolecular gels
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00Processes of polymerisation
    • C08F2/12Polymerisation in non-solvents
    • C08F2/16Aqueous medium
    • C08F2/22Emulsion polymerisation
    • C08F2/24Emulsion polymerisation with the aid of emulsifying agents
    • C08F2/26Emulsion polymerisation with the aid of emulsifying agents anionic
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00Processes of polymerisation
    • C08F2/12Polymerisation in non-solvents
    • C08F2/16Aqueous medium
    • C08F2/22Emulsion polymerisation
    • C08F2/24Emulsion polymerisation with the aid of emulsifying agents
    • C08F2/30Emulsion polymerisation with the aid of emulsifying agents non-ionic
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04Acids; Metal salts or ammonium salts thereof
    • C08F220/06Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00Processes of treating or compounding macromolecular substances
    • C08J3/24Crosslinking, e.g. vulcanising, of macromolecules
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
    • C08J9/08Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing carbon dioxide
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00Foams characterized by the expanding agent
    • C08J2203/02CO2-releasing, e.g. NaHCO3 and citric acid
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2205/00Foams characterised by their properties
    • C08J2205/02Foams characterised by their properties the finished foam itself being a gel or a gel being temporarily formed when processing the foamable composition
    • C08J2205/022Hydrogel, i.e. a gel containing an aqueous composition
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2333/00Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/02Homopolymers or copolymers of acids; Metal or ammonium salts thereof

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

The invention discloses a kind of super absorbent resins, including following composition: 100 parts by weight of acrylic acid, sodium hydroxide 40-50 parts by weight, first crosslinking agent 1-4 parts by weight, multiple crosslinking agent 0.6-5 parts by weight, antibacterial agent 0-15 parts by weight, oxidant 0.1-1 parts by weight, foaming agent 10-20 parts by weight, reducing agent 0.01-0.1 parts by weight, surfactant 0.01-5 parts by weight, remaining is deionized water.For the present invention using above-mentioned super absorbent resin and preparation method thereof, preparation process is simple, and the reaction time is short, and obtained water-absorbing resins water retention property is preferable, has the effect of bacteriostasis, and deodorization, while can reduce cost, good salt tolerance.

Description

High-hydroscopicity and preparation method thereof
Technical field
The present invention relates to water-absorbing resins technical fields, more particularly, to a kind of super absorbent resin and preparation method thereof.
Background technique
High hydroscopic resin is the general designation with the high molecular polymer of very high water absorbing properties and water retention property, is a kind of New functional macromolecule material with tridimensional network.Its high water absorption ability may be up to hundreds times of sole mass or even do Times, it is pressurizeing and is also being difficult to separate water into out under heating condition.In recent decades, it is contemplated that think with direct body contact and answer With the requirement of performance, the super absorbent resin applied to hygienic material is in biocompatibility, infiltration rate, pressurizing absorption amount, guarantor Water etc. is more demanding.It is hygienic material super absorbent resin that acrylic acid and its copolymer super absorbent resin, which are recognized, Development trend, currently, being applied to the super absorbent resin of the hygienic materials such as sanitary napkin, baby paper diaper greatly mostly from acrylic acid Polymer.The preparation method of acrylic acid series super absorbent resin mainly has inverse suspension method and solution polymerization process, inverse suspension method Due to exist need using organic solvent, production technology is complicated, is difficult to realize the disadvantages of continuous production is difficult to popularize.And solution Polymerization is relatively easily realized, is that current most of manufacturers use this method, but the obtained product of solution polymerization process It can be difficult to compared with inverse suspension method, especially the performances such as infiltration rate required by hygienic material, pressurizing absorption amount, often need It can just meet the requirements after post treatment.Additionally, due to the strongly hydrophilic of acrylic acid, so that prepared by the dry solution polymerization process that becomes The big technical problem of the one of polyacrylic super absorbent resin.And production efficiency is low, and at high cost, obtained water-absorbing resins are resistance to Salt is poor, and soaking effect is poor, and water holding capacity is general, while without antibacterial effect, influence using.For these reasons, one is designed The kind simple super absorbent resin of preparation process is necessary.
Summary of the invention
The object of the present invention is to provide a kind of super absorbent resins and preparation method thereof, and preparation process is simple, the reaction time Short, obtained water-absorbing resins water retention property is preferable, has the effect of bacteriostasis, and deodorization, while can reduce cost, good salt tolerance.
To achieve the above object, the present invention provides a kind of super absorbent resins, including following composition:
100 parts by weight of acrylic acid, sodium hydroxide 40-50 parts by weight, first crosslinking agent 1-4 parts by weight, multiple crosslinking agent 0.6-5 Parts by weight, antibacterial agent 0-15 parts by weight, oxidant 0.1-1 parts by weight, foaming agent 10-20 parts by weight, reducing agent 0.01-0.1 weight Part, surfactant 0.01-5 parts by weight are measured, remaining is deionized water.Preferably, the just crosslinking agent is N, N- di-2-ethylhexylphosphine oxide One of acrylamide, polyethylene glycol 200, butanediol, pentaerythrite, Pehanorm triacrylate are a variety of, institute Stating multiple crosslinking agent is ethers or alcohols.
Preferably, the oxidant is one of sodium peroxydisulfate, potassium peroxydisulfate, ammonium persulfate and hydrogen peroxide or more Kind.
Preferably, the reducing agent is one of sodium sulfite, potassium sulfite, sodium hydrogensulfite and frerrous chloride or more Kind.
Preferably, the foaming agent is sodium bicarbonate or saleratus.
Preferably, the surfactant is anionic surfactant or nonionic surfactant, the anion Surfactant is sulfosuccinic acid fatty alcohol polyoxyethylene ether DNS-628, fast penetrant T or alkali-resistant penetrant OEP-70.
A kind of preparation method of super absorbent resin, comprising the following steps:
A, the acrylic acid of 100 parts by weight is add to deionized water, forms acrylic monomers solution;
B, the sodium hydroxide of 40-50 parts by weight is added to and is neutralized to obtain mixed liquor in acrylic monomers solution, in It is 50-82 DEG C with temperature, degree of neutralization 50-75%;
C, the first crosslinking agent of 1-4 parts by weight is added into above-mentioned mixed liquor, is stirring evenly and then adding into the anti-of 0-15 parts by weight Microbial inoculum continues to be uniformly mixing to obtain acrylates mixed liquor;
D, the multiple crosslinking agent that 0.6-5 parts by weight are added into above-mentioned acrylates mixed liquor is stirred to being completely dissolved, so Oxidant, the foaming agent of 10-20 parts by weight and the reducing agent of 0.01-0.1 parts by weight of 0.1-1 parts by weight are added afterwards, in utilization Polymerization reaction is carried out with heat, forms high water absorbent resin gel;
E, high water absorbent resin gel is granulated, the surfactant that 0.01-5 parts by weight are added after granulation is sprayed Mist processing, is then dried, is crushed, Screening Treatment, obtaining super absorbent resin.
Preferably, it is 20-40% that control mass concentration in deionized water, which is added, in the acrylic acid.
Preferably, the drying temperature in the step E is 80-120 DEG C, and drying time is 8-20 hours.
Preferably, the screening is to be sieving through 60-100 mesh.
Therefore, the present invention is using above-mentioned super absorbent resin and preparation method thereof, and preparation process is simple, and the reaction time is short, Obtained water-absorbing resins water retention property is preferable, has the effect of bacteriostasis, and deodorization, while can reduce cost, good salt tolerance.
Below by embodiment, technical scheme of the present invention will be described in further detail.
Specific embodiment
The present invention provides a kind of super absorbent resins, including following composition:
100 parts by weight of acrylic acid, sodium hydroxide 40-50 parts by weight, first crosslinking agent 1-4 parts by weight, multiple crosslinking agent 0.6-5 Parts by weight, antibacterial agent 0-15 parts by weight, oxidant 0.1-1 parts by weight, foaming agent 10-20 parts by weight, reducing agent 0.01-0.1 weight Part, surfactant 0.01-5 parts by weight are measured, remaining is deionized water, and first crosslinking agent is N, and N- methylene-bisacrylamide gathers One of ethylene glycol 200, butanediol, pentaerythrite, Pehanorm triacrylate are a variety of, and multiple crosslinking agent is ether Class or alcohols, oxidant are one of sodium peroxydisulfate, potassium peroxydisulfate, ammonium persulfate and hydrogen peroxide or a variety of, and reducing agent is One of sodium sulfite, potassium sulfite, sodium hydrogensulfite and frerrous chloride are a variety of, and foaming agent is sodium bicarbonate or bicarbonate Potassium, surfactant are anionic surfactant or nonionic surfactant, and the anionic surfactant is sulfo group Succinic acid fatty alcohol polyoxyethylene ether DNS-628, fast penetrant T or alkali-resistant penetrant OEP-70.
A kind of preparation method of super absorbent resin, comprising the following steps:
A, the acrylic acid of 100 parts by weight is add to deionized water, it is dense that control quality in deionized water is added in acrylic acid Degree is 20-40%, forms acrylic monomers solution;
B, the sodium hydroxide of 40-50 parts by weight is added to and is neutralized to obtain mixed liquor in acrylic monomers solution, in It is 50-82 DEG C with temperature, degree of neutralization 50-75%;
C, the first crosslinking agent of 1-4 parts by weight is added into above-mentioned mixed liquor, is stirring evenly and then adding into the anti-of 0-15 parts by weight Microbial inoculum continues to be uniformly mixing to obtain acrylates mixed liquor;
D, the multiple crosslinking agent that 0.6-5 parts by weight are added into above-mentioned acrylates mixed liquor is stirred to being completely dissolved, so Oxidant, the foaming agent of 10-20 parts by weight and the reducing agent of 0.01-0.1 parts by weight of 0.1-1 parts by weight are added afterwards, in utilization Polymerization reaction is carried out with heat, forms high water absorbent resin gel;
E, high water absorbent resin gel is granulated, the surfactant that 0.01-5 parts by weight are added after granulation is sprayed Mist processing, is then dried, is crushed, Screening Treatment, and drying temperature is 80-120 DEG C, and drying time is 8-20 hours, Screening obtains super absorbent resin to be sieving through 60-100 mesh.
Water absorbent rate refers to the water absorption of the high hydroscopic resin of unit mass within a certain period of time.
Embodiment
A kind of preparation method of super absorbent resin, comprising the following steps:
A, the acrylic acid of 100 parts by weight is add to deionized water, it is dense that control quality in deionized water is added in acrylic acid Degree is 30%, forms acrylic monomers solution;
B, the sodium hydroxide of 45 parts by weight is added in acrylic monomers solution and is neutralized to obtain mixed liquor, neutralize temperature Degree is 80 DEG C, degree of neutralization 60%;
C, the first crosslinking agent of 2 parts by weight is added into above-mentioned mixed liquor, be stirring evenly and then adding into the antibacterial agents of 8 parts by weight after It is continuous to be uniformly mixing to obtain acrylates mixed liquor;
D, the multiple crosslinking agent that 3 parts by weight are added into above-mentioned acrylates mixed liquor is stirred to being completely dissolved, then plus The reducing agent for entering the oxidant of 0.5 parts by weight, the foaming agent of 15 parts by weight and 0.06 parts by weight polymerize using the heat of neutralization anti- It answers, forms high water absorbent resin gel;
E, high water absorbent resin gel is granulated, the surfactant that 4 parts by weight are added after granulation carries out spraying place Reason, is then dried, is crushed, Screening Treatment, and drying temperature is 100 DEG C, and drying time is 10 hours, is screened as screening 80 meshes are crossed, super absorbent resin is obtained.
Therefore, the present invention is using above-mentioned super absorbent resin and preparation method thereof, and preparation process is simple, and the reaction time is short, Obtained water-absorbing resins water retention property is preferable, has the effect of bacteriostasis, and deodorization, while can reduce cost, good salt tolerance.
Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention rather than is limited, Although the present invention is described in detail with reference to preferred embodiments, those skilled in the art should understand that: its according to So can be with modification or equivalent replacement of the technical solution of the present invention are made, and these modifications or equivalent replacement cannot also make to repair Technical solution after changing is detached from the spirit and scope of technical solution of the present invention.

Claims (10)

1. a kind of super absorbent resin, which is characterized in that including following composition:
100 parts by weight of acrylic acid, sodium hydroxide 40-50 parts by weight, first crosslinking agent 1-4 parts by weight, multiple crosslinking agent 0.6-5 weight Part, antibacterial agent 0-15 parts by weight, oxidant 0.1-1 parts by weight, foaming agent 10-20 parts by weight, reducing agent 0.01-0.1 parts by weight, Surfactant 0.01-5 parts by weight, remaining is deionized water.
2. super absorbent resin according to claim 1, it is characterised in that: the just crosslinking agent is N, N- di-2-ethylhexylphosphine oxide third One of acrylamide, polyethylene glycol 200, butanediol, pentaerythrite, Pehanorm triacrylate are a variety of, described Multiple crosslinking agent is ethers or alcohols.
3. super absorbent resin according to claim 1, it is characterised in that: the oxidant is sodium peroxydisulfate, persulfuric acid One of potassium, ammonium persulfate and hydrogen peroxide are a variety of.
4. super absorbent resin according to claim 1, it is characterised in that: the reducing agent is sodium sulfite, sulfurous acid One of potassium, sodium hydrogensulfite and frerrous chloride are a variety of.
5. super absorbent resin according to claim 1, it is characterised in that: the foaming agent is sodium bicarbonate or bicarbonate Potassium.
6. super absorbent resin according to claim 1, it is characterised in that: the surfactant is living for anionic surface Property agent or nonionic surfactant, the anionic surfactant is sulfosuccinic acid fatty alcohol polyoxyethylene ether DNS- 628, fast penetrant T or alkali-resistant penetrant OEP-70.
7. a kind of preparation method of super absorbent resin as claimed in any one of claims 1 to 6, which is characterized in that including following Step:
A, the acrylic acid of 100 parts by weight is add to deionized water, forms acrylic monomers solution;
B, the sodium hydroxide of 40-50 parts by weight is added in acrylic monomers solution and is neutralized to obtain mixed liquor, neutralize temperature Degree is 50-82 DEG C, degree of neutralization 50-75%;
C, the first crosslinking agent of 1-4 parts by weight is added into above-mentioned mixed liquor, is stirring evenly and then adding into the antibacterial agent of 0-15 parts by weight Continue to be uniformly mixing to obtain acrylates mixed liquor;
D, into above-mentioned acrylates mixed liquor be added 0.6-5 parts by weight multiple crosslinking agent stir to being completely dissolved, then plus The reducing agent for entering the oxidant of 0.1-1 parts by weight, the foaming agent of 10-20 parts by weight and 0.01-0.1 parts by weight, utilizes the heat of neutralization Polymerization reaction is carried out, high water absorbent resin gel is formed;
E, high water absorbent resin gel is granulated, the surfactant that 0.01-5 parts by weight are added after granulation carries out spraying place Reason, is then dried, is crushed, Screening Treatment, obtaining super absorbent resin.
8. the preparation method of super absorbent resin according to claim 7, it is characterised in that: acrylic acid addition go from It is 20-40% that mass concentration is controlled in sub- water.
9. the preparation method of super absorbent resin according to claim 7, it is characterised in that: the drying in the step E Temperature is 80-120 DEG C, and drying time is 8-20 hours.
10. the preparation method of super absorbent resin according to claim 7, it is characterised in that: the screening is to be sieving through 60-100 mesh.
CN201811159852.XA 2018-09-30 2018-09-30 High-hydroscopicity and preparation method thereof Pending CN109293950A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110075342A (en) * 2019-03-19 2019-08-02 邦丽达(福建)新材料股份有限公司 A kind of high water-absorbent resin composition of antibacterial and deodouring
CN113350047A (en) * 2021-06-03 2021-09-07 嫒赟(上海)生物科技股份有限公司 Anion sanitary towel

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102516578A (en) * 2011-11-04 2012-06-27 烟台万华聚氨酯股份有限公司 Preparation method of crylic acid resin with high water absorbability
CN105218734A (en) * 2015-04-18 2016-01-06 泉州邦丽达科技实业有限公司 Super absorbent resin of a kind of antibacterial, deodorizing and preparation method thereof
CN107141399A (en) * 2017-06-19 2017-09-08 于天荣 Super absorbent resin preparation method, super absorbent resin and its application
EP3248990A1 (en) * 2015-06-17 2017-11-29 LG Chem, Ltd. Method for manufacturing super absorbent resin

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102516578A (en) * 2011-11-04 2012-06-27 烟台万华聚氨酯股份有限公司 Preparation method of crylic acid resin with high water absorbability
CN105218734A (en) * 2015-04-18 2016-01-06 泉州邦丽达科技实业有限公司 Super absorbent resin of a kind of antibacterial, deodorizing and preparation method thereof
EP3248990A1 (en) * 2015-06-17 2017-11-29 LG Chem, Ltd. Method for manufacturing super absorbent resin
CN107141399A (en) * 2017-06-19 2017-09-08 于天荣 Super absorbent resin preparation method, super absorbent resin and its application

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110075342A (en) * 2019-03-19 2019-08-02 邦丽达(福建)新材料股份有限公司 A kind of high water-absorbent resin composition of antibacterial and deodouring
CN113350047A (en) * 2021-06-03 2021-09-07 嫒赟(上海)生物科技股份有限公司 Anion sanitary towel

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