CN111732685A - Water-absorbent resin composition, water-absorbent resin and process for producing the same - Google Patents
Water-absorbent resin composition, water-absorbent resin and process for producing the same Download PDFInfo
- Publication number
- CN111732685A CN111732685A CN202010629391.9A CN202010629391A CN111732685A CN 111732685 A CN111732685 A CN 111732685A CN 202010629391 A CN202010629391 A CN 202010629391A CN 111732685 A CN111732685 A CN 111732685A
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- Prior art keywords
- water
- group
- absorbent resin
- crosslinking agent
- internal
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- 239000011347 resin Substances 0.000 title claims abstract description 111
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- 239000011342 resin composition Substances 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 title claims description 21
- 230000008569 process Effects 0.000 title description 6
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- 238000006386 neutralization reaction Methods 0.000 claims abstract description 13
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- 235000013312 flour Nutrition 0.000 description 1
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- 229920002824 gallotannin Polymers 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid group Chemical group C(\C=C/C(=O)O)(=O)O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
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- 230000000813 microbial effect Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- BONNRKLSQRLNHV-UHFFFAOYSA-N n-methylmethanamine;prop-2-enamide Chemical compound CNC.NC(=O)C=C BONNRKLSQRLNHV-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
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- 230000035699 permeability Effects 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- QVKOLZOAOSNSHQ-UHFFFAOYSA-N prop-1-ene;prop-2-enoic acid Chemical compound CC=C.OC(=O)C=C QVKOLZOAOSNSHQ-UHFFFAOYSA-N 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
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- 150000003839 salts Chemical class 0.000 description 1
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
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- 239000011780 sodium chloride Substances 0.000 description 1
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920001864 tannin Polymers 0.000 description 1
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- 239000004753 textile Substances 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- OTRQTVHWMPQPOJ-UHFFFAOYSA-N trimethyl-(prop-2-enoylamino)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)NC(=O)C=C OTRQTVHWMPQPOJ-UHFFFAOYSA-N 0.000 description 1
- YFHICDDUDORKJB-UHFFFAOYSA-N trimethylene carbonate Chemical compound O=C1OCCCO1 YFHICDDUDORKJB-UHFFFAOYSA-N 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K31/00—Medicinal preparations containing organic active ingredients
- A61K31/74—Synthetic polymeric materials
- A61K31/765—Polymers containing oxygen
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P31/00—Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
- A61P31/02—Local antiseptics
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P31/00—Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
- A61P31/04—Antibacterial agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
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- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Medicinal Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Veterinary Medicine (AREA)
- Public Health (AREA)
- Pharmacology & Pharmacy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Communicable Diseases (AREA)
- Oncology (AREA)
- General Chemical & Material Sciences (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Epidemiology (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Absorbent Articles And Supports Therefor (AREA)
Abstract
The invention relates to a water-absorbent resin composition, a water-absorbent resin and a manufacturing method thereof. Water-absorbent resinThe composition comprises: the neutralization degree of the acid group-containing monomer aqueous solution is 45 mol percent to 85 mol percent; the first internal crosslinking agent of the internal crosslinking agent comprises an ester compound having a structure represented by formula (I):
wherein X represents a linear or branched alkenyl group with the carbon number of 3 to 5, and one end of X far away from Y is of a double bond structure; n represents 8 to 15; a plurality of Y's each independently represent an ethylene glycol group or a propylene glycol group, and the oxygen atoms of the ethylene glycol group and the propylene glycol group are bonded to X; z represents a substituted saturated linear chain carboxyl with the carbon number of 3 to 7, one end of Z far away from the carbon atom is in a carboxyl structure, the substituent of the saturated linear chain carboxyl comprises hydroxyl, and the number of the hydroxyl is 1 to 3; a polymerization initiator; and a surface cross-linking agent. The water-absorbent resin obtained by the production method of the present invention has good antibacterial properties and long-lasting absorption capacity.
Description
Technical Field
The present invention relates to a water-absorbent resin composition, a water-absorbent resin and a method for producing the same, and more particularly to a water-absorbent resin composition having both excellent antibacterial ability and long-term absorption ability, a water-absorbent resin and a method for producing the same.
Background
Water-absorbent resins are widely used in water-retaining agents for agricultural or horticultural fields, dew condensation preventing agents for building materials, materials for removing water from petroleum, water-proof coating agents for outer layers of electric cables, and sanitary goods. Such as diapers, feminine hygiene products, disposable wipes, and the like, with diapers being the largest among others.
At present, functional diapers are the main development direction, and in particular adult diapers. In addition to emphasizing the absorption capacity and dryness, the development is directed toward antibacterial ability. Based on the demand for antibacterial ability, various studies are actively being conducted to develop a water-absorbent resin having characteristics of antibacterial ability and long-lasting absorption ability.
With the global rise of raw materials, the price of pulp is rapidly rising, and the tendency of replacing pulp with water-absorbent resin is more and more obvious. In addition to the long-term absorption properties, it is also necessary to have antimicrobial properties to prevent the growth of bacteria and the resulting red rash on the user's skin during extended periods of use.
In order to make the water-absorbent resin meet the above-mentioned requirements, it is a conventional practice in the art to increase the water-absorbing capacity by increasing the degree of neutralization. Another way is to add copolymers to increase the water absorption capacity, for example: a copolymer of acrylic acid and acrylamide is used, and the polymerization temperature is controlled in the range of 50 to 110 ℃ (U.S. patent publication No. 5496890), but residual acrylamide is harmful to human body when used.
In addition, the water absorption capacity of the water-absorbent resin is improved by graft polymerization, for example, a super absorbent resin made by adding konjaku flour (Chinese patent publication No. 1410463A) and starch and cellulose (Chinese patent application No. 200410050060.0) has advantages of high absorption capacity and high absorption speed. However, after water absorption, the gel strength of the graft type water-absorbent resin is low, which easily causes dissolution loss and affects the water retention capacity. Furthermore, starch chains are also vulnerable to microbial damage, resulting in loss of water retention and reduced service life.
In addition, world patent publication No. WO2003028778 mentions a method for preparing a water-absorbent resin having antibacterial ability by lowering the pH of the water-absorbent resin. Further, U.S. patent publication No. 20010053807 mentions that the addition of glycine reduces the occurrence of malodor. However, the water-absorbent resin obtained by the above method is inferior in urine resistance under pressure.
A water-absorbent resin having deodorizing ability can be produced by mixing tannin (Gallotannin) (U.S. patent publication No. 8658146) or its derivative with a water-absorbent resin, but the water-absorbent resin has a problem of turning yellow or brown under high-temperature and high-humidity conditions at high cost, and is not suitable for long-term storage.
In addition, the use of activated carbon, nano silver ions or zeolite surface-coated with silver ions can also reduce the occurrence of odor or bacterial growth (U.S. patent publication No. 6663949, european patent publication No. 1404385 and U.S. patent publication No. 7868075). European patent publication No. 1275404 mentions that mixing cyclodextrin or its derivative with a water-absorbent resin can reduce the occurrence of odor. Further, the generation of odor can be reduced by heat-treating 1, 2-decanediol with a water-absorbent resin (U.S. patent publication No. 20150306272). However, none of these patents can provide both antibacterial and deodorizing abilities, and only have a good ability to suppress ammonia gas.
Further, U.S. patent publication No. 8647317 mentions that silane derivatives can improve the long-term absorption of water-absorbent resins, but silane derivatives have disadvantages of high price and poor stability.
In view of the above, it is desirable to develop a water-absorbent resin composition, a water-absorbent resin and a method for producing the same, which have both good antibacterial ability and long-term absorption ability, so as to overcome the above-mentioned disadvantages of the conventional water-absorbent resin.
Disclosure of Invention
Accordingly, an object of the present invention is to provide a water-absorbent resin composition in which a water-absorbent resin having both excellent antibacterial properties and long-lasting absorption capacity is obtained by using a first internal crosslinking agent having a specific structure.
Another object of the present invention is to provide a process for producing a water-absorbent resin, which comprises using the above-mentioned water-absorbent resin composition to produce the water-absorbent resin of the present invention.
It is still another object of the present invention to provide a water-absorbent resin. The water-absorbent resin is produced by the above-mentioned production method, and the water-absorbent resin has an organic acid ester bond. When the ester bond of the organic acid is hydrolyzed, the generated hydroxyl and the released organic acid can respectively provide long-acting absorption capacity and good antibacterial property.
According to an object of the present invention, a water-absorbent resin composition is provided. The water-absorbent resin composition comprises an aqueous solution of an acid-group-containing monomer, an internal crosslinking agent, a polymerization initiator and a surface crosslinking agent. The neutralization degree of the aqueous acid group-containing monomer solution is 45 mol% to 85 mol%. The internal crosslinking agent comprises a first internal crosslinking agent, wherein the first internal crosslinking agent comprises an ester compound having a structure represented by formula (I):
in the formula (I), X represents a linear or branched alkenyl group with 3 to 5 carbon atoms, and one end of X far away from Y is a double bond structure; n represents 8 to 15; a plurality of Y's each independently represent an ethylene glycol group or a propylene glycol group, and the oxygen atoms of the ethylene glycol group and the propylene glycol group are bonded to X; z represents a saturated linear carboxyl group with the carbon number of 3-7 and substituted, one end of Z far away from the carbon atom is in a carboxyl structure, the substituent of the saturated linear carboxyl group comprises hydroxyl, and the number of the hydroxyl is 1-3.
According to an embodiment of the present invention, the aqueous solution containing an acid-group-containing monomer contains a neutralized acid-group-containing monomer, and the amount of the neutralized acid-group-containing monomer used is 20 to 55 parts by weight based on 100 parts by weight of the aqueous solution containing an acid-group-containing monomer.
According to another embodiment of the present invention, the internal crosslinking agent is used in an amount of 0.001 to 5 parts by weight, based on 100 parts by weight of the total amount of the neutralized acid group-containing monomer, the internal crosslinking agent and the polymerization initiator.
According to another embodiment of the present invention, the internal cross-linking agent optionally comprises a second internal cross-linking agent, and the second internal cross-linking agent is selected from the group consisting of amines having an acryl group, esters having an acrylic acid group, ethers having at least two ethylene oxides, and any combination thereof.
According to still another embodiment of the present invention, the first internal crosslinking agent is used in an amount of not less than 20 weight percent based on 100 weight percent of the internal crosslinking agent.
Another object of the present invention is to provide a process for producing a water-absorbent resin. The method for producing the water-absorbent resin is to provide an aqueous acid group-containing monomer solution, wherein the degree of neutralization of the aqueous acid group-containing monomer solution is 45 to 85 mole percent. And then mixing an internal cross-linking agent, a polymerization initiator and an acid group-containing monomer aqueous solution to perform free radical polymerization reaction to prepare a hydrogel, wherein the internal cross-linking agent comprises a first internal cross-linking agent, and the first internal cross-linking agent comprises an ester compound with a structure shown in a formula (I):
in the formula (I), X represents a linear or branched alkenyl group with 3 to 5 carbon atoms, and one end of X far away from Y is a double bond structure; n represents 8 to 15; a plurality of Y's each independently represent an ethylene glycol group or a propylene glycol group, and the oxygen atoms of the ethylene glycol group and the propylene glycol group are bonded to X; z represents a saturated linear carboxyl group with the carbon number of 3-7 and substituted, one end of Z far away from the carbon atom is in a carboxyl structure, the substituent of the saturated linear carboxyl group comprises hydroxyl, and the number of the hydroxyl is 1-3. Then, the hydrogel is subjected to a surface crosslinking reaction using a surface crosslinking agent to obtain a water-absorbent resin.
According to an embodiment of the present invention, the internal crosslinking agent is used in an amount of 0.001 to 5 parts by weight based on 100 parts by weight of the total amount of the neutralized acid group-containing monomer, the internal crosslinking agent and the polymerization initiator contained in the aqueous acid group-containing monomer solution.
According to another embodiment of the present invention, the internal cross-linking agent optionally comprises a second internal cross-linking agent selected from the group consisting of amines having an acryl group, esters having an acrylic acid group, ethers having at least two ethylene oxides, and any combination thereof.
According to still another embodiment of the present invention, the first internal crosslinking agent is used in an amount of not less than 20 weight percent based on 100 weight percent of the internal crosslinking agent.
It is still another object of the present invention to provide a water-absorbent resin. The water-absorbent resin is produced by the above-mentioned method for producing a water-absorbent resin having an organic acid ester bond.
The water-absorbent resin composition and the method for producing the water-absorbent resin, provided by the invention, have good absorption capacity for synthetic urine and excellent antibacterial function through the specific structure and the specific using amount of the first internal cross-linking agent. Furthermore, in the case of the water-absorbent resin of the present invention, the particles do not leak into the production equipment or even suspend in the air of the factory building, and harm the respiratory tract of the people.
Drawings
For a more complete understanding of the embodiments of the present invention and the advantages thereof, reference is now made to the following descriptions taken in conjunction with the accompanying drawings. It must be emphasized that the various features are not drawn to scale and are for illustrative purposes only. The content of the related figures is explained as follows:
FIG. 1 is a flow chart showing a method for producing a water-absorbent resin according to an embodiment of the present invention.
Description of the main reference numerals:
100-method; 110,120, 130-operation.
Detailed Description
The making and using of embodiments of the present invention are discussed in detail below. It should be appreciated, however, that the embodiments provide many applicable inventive concepts that can be embodied in a wide variety of specific contexts. The specific embodiments discussed are merely illustrative and do not limit the scope of the invention.
The water-absorbent resin composition of the present invention comprises an aqueous solution of an acid-group-containing monomer, an internal crosslinking agent, a polymerization initiator and a surface crosslinking agent. The aqueous acid group-containing monomer solution contains water as a solvent and an acid group-containing monomer as a solute, wherein the acid group-containing monomer is a water-soluble unsaturated monomer. In some embodiments, the acid group-containing monomer may include, but is not limited to, acrylic compounds, other suitable acid group-containing unsaturated monomer compounds, or any combination of the foregoing. In some embodiments, the acrylic compound may include, but is not limited to, acrylic acid, methacrylic acid, and acrylic compounds such as 2-allylamine-2-methylpropanesulfonic acid. In other embodiments, other suitable unsaturated monomer compounds containing acid groups can include, but are not limited to, unsaturated compounds containing acid groups such as maleic acid, maleic anhydride, fumaric acid, and fumaric anhydride.
In other embodiments, the acid group-containing monomer may optionally contain other hydrophilic monomer compounds having an unsaturated double bond. In some embodiments, other hydrophilic monomer compounds having an unsaturated double bond may include, but are not limited to, compounds having an unsaturated double bond such as acrylamide, methacrylamide, 2-carboxyethyl acrylate, 2-carboxyethyl methacrylate, methyl acrylate, ethyl acrylate, dimethylamine acrylamide, and acrylamidotrimethylammonium chloride. However, it is understood that the amount of the unsaturated monomer compound containing an acid group is not limited to the amount that does not deteriorate the physical properties of the water-absorbent resin.
In addition, neutralization of the carboxyl groups of the acid-group-containing monomer can adjust the pH of the aqueous solution of the acid-group-containing monomer. In some embodiments, the pH of the aqueous acid group-containing monomer solution is equal to or greater than 5.5, and preferably 5.6 to 6.5. The foregoing neutralization can be accomplished using a neutralizing agent. When the neutralization degree of the aqueous solution containing the acid-based monomer is less than 45 mol%, the pH value of the aqueous solution containing the acid-based monomer is less than 5.5, and the content of residual monomers in the hydrogel after polymerization is too high, so that the physical properties of the water-absorbent resin are poor, and the long-acting absorption capacity of the absorber is influenced.
In some embodiments, the neutralizing agent may include, but is not limited to, hydroxides of alkali metal or alkali earth elements, carbonic acid compounds, or combinations thereof, and/or other suitable basic compounds. In one embodiment, the neutralizing agent may include, but is not limited to, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, ammonia, or combinations thereof. The neutralizing agent may be used singly or in combination of plural kinds.
After the acid group-containing monomer is neutralized by the neutralizing agent, the acid group of the acid group-containing monomer may form a salt such as a sodium salt, a potassium salt or an ammonium salt to provide a water-absorbent resin having a pH value suitable for skin contact. In some embodiments, the neutralization degree of the aqueous acid group-containing monomer solution may be 45 to 85 mole percent, and preferably may be 50 to 75 mole percent. When the degree of neutralization of the aqueous solution of the acid-group-containing monomer is less than 45 mol%, the pH of the resultant water-absorbent resin tends to be low (i.e., pH less than 5.5). When the degree of neutralization of the aqueous solution containing the acid-group-containing monomer is more than 85 mol%, the pH of the resultant water-absorbent resin tends to be high (pH is more than 6.5). In the case where the pH of the finished water-absorbent resin product is slightly acidic (i.e., pH 5.5) to neutral (i.e., pH 7), the finished water-absorbent resin product is suitable for human contact and is also safe.
In some embodiments, the amount of acid group-containing monomer used in the present invention is not particularly limited. In other embodiments, the acid-group-containing monomer is used in an amount of 20 to 55 parts by weight, and preferably 30 to 45 parts by weight, based on 100 parts by weight of the acid-group-containing monomer aqueous solution. When the amount of the acid group-containing monomer used is less than 20 parts by weight, the hydrogel after polymerization is too soft and sticky to be machined. When the amount of the acid-group-containing monomer used is more than 55 parts by weight, the concentration of the aqueous solution containing the acid-group-containing monomer approaches a saturated concentration and is not easy to prepare, and the polymerization reaction is too fast to control the reaction heat.
In some embodiments, the aqueous solution of the acid-group-containing monomer may optionally contain a water-soluble polymer to reduce costs. In these embodiments, the water-soluble polymer may include, but is not limited to, partially saponified or fully saponified polyvinyl alcohol, polyethylene glycol, polyacrylic acid, polyacrylamide, starch, and/or starch derivatives. In some embodiments, the starch and/or starch derivatives may include, but are not limited to, polymers such as methyl cellulose, methyl cellulose acrylate, and ethyl cellulose.
The molecular weight of the water-soluble polymer is not particularly limited. Preferably, the water-soluble polymer may be starch, partially saponified polyvinyl alcohol, fully saponified polyvinyl alcohol, and any combination thereof. The water-soluble polymer may be used in an amount of 0 to 20 parts by weight, preferably 0 to 10 parts by weight, and more preferably 0 to 5 parts by weight, based on 100 parts by weight of the aqueous solution of the acid group-containing monomer. When the amount of the water-soluble polymer used is more than 20 parts by weight, the water-soluble polymer affects the physical properties of the water-absorbent resin and deteriorates the physical properties.
In the water-absorbent resin composition of the present invention, the internal-crosslinking agent comprises a first internal-crosslinking agent, and the first internal-crosslinking agent comprises an ester compound having a structure represented by the formula (I):
in formula (I), X represents a linear or branched alkenyl group having 3 to 5 carbon atoms, and preferably represents a linear alkenyl group having 3 carbon atoms or a branched alkenyl group having 4 carbon atoms, wherein one end of X away from Y is a double bond structure. The double bond structure is used for crosslinking with the acid group-containing monomer. When the alkenyl group represented by X does not have a terminal alkenyl group, the first internal crosslinking agent cannot crosslink with the acid group-containing monomer.
In the above formula (I), n represents 8 to 15, and preferably 9 to 12. When n is less than 8, the first internal crosslinking agent has poor water solubility, and poor water solubility results in poor reactivity of the first internal crosslinking agent. When n is more than 15, the first internal crosslinking agent is expensive and not economically advantageous.
Further, each of Y independently represents an ethylene glycol group or a propylene glycol group, and preferably an ethylene glycol group in which the oxygen atoms of the ethylene glycol group and the propylene glycol group are bonded to X.
In addition, Z represents a substituted saturated linear carboxyl group with the carbon number of 3 to 7, one end of Z far away from the carbon atom is in a carboxyl structure, wherein the substituent of the saturated linear carboxyl group comprises a hydroxyl group, and the number of the hydroxyl groups is 1 to 3. In some embodiments, the number of hydroxyl groups is 1. The hydroxyl group in the saturated linear carboxyl group can be used for carrying out a crosslinking reaction with the carboxyl group of the acid group-containing monomer to form an ester bond. In some embodiments, the substituent of the saturated linear carboxyl group optionally includes a carboxyl group, and preferably, the number of the carboxyl groups is 1 to 3. In other embodiments, the number of hydroxyl groups is 1 and the number of carboxyl groups is 0 or 1.
Further, the first internal crosslinking agent of the present invention is an unsaturated double-bond acid ester compound (i.e., an ester compound having a structure represented by the above formula (I)) formed by reacting an unsaturated double-bond compound having a hydroxyl Group in the structure with an organic acid having antibacterial ability, using the concept of a Protecting Group (Protecting Group) in organic synthesis.
In some embodiments, specific examples of the unsaturated double bond compound having a hydroxyl group may include, but are not limited to, ethers such as polyethylene glycol propylene ether, polyethylene glycol methyl propylene ether, polypropylene glycol propylene ether, or polypropylene glycol methyl propylene ether. The organic acid compound having antibacterial ability may include, but is not limited to, a hydroxy diacid compound or a hydroxy triacid compound. Specific examples of the hydroxy diacid compound include 2, 3-dihydroxybutanedioic acid (tartaric acid) and 2-hydroxybutanedioic acid (malic acid). A specific example of the hydroxytricarboxylic acid compound may be 3-hydroxy-3-carboxyglutaric acid (citric acid).
In other embodiments, the ester compound may be a commercially available product. Specific examples of the ester compound may include, but are not limited to, polyethylene glycol allyl ether 2-hydroxysuccinate (n ═ 9) (manufactured by doksi, and having a trade name of DK450, a structure shown by formula (I-1)), polyethylene glycol allyl ether 3-hydroxy-3-carboxyglutarate (n ═ 9) (manufactured by doksi, and having a trade name of DK455, a structure shown by formula (I-2)), polyethylene glycol propylene ether 2-hydroxysuccinate (n ═ 12) (manufactured by doksi under the trade name DK600 or LM6012 under the trade name of formula (I-3)), polyethylene glycol propylene ether 2-hydroxysuccinate (n ═ 10) (manufactured by lugsi under the trade name LM4510 under the trade name of formula (I-4)).
In other embodiments, the internal crosslinking agent optionally comprises a second internal crosslinking agent, wherein the second internal crosslinking agent is selected from the group consisting of amines having an acryl group, esters having an acrylic acid, ethers having at least two ethylene oxides, and any combination thereof.
In some embodiments, the amines having an allyl group may include, but are not limited to, amines such as N, N ' -bis (2-propenyl) amine, N ' -methylenebisacrylamide, N ' -methylenebismethacrylamide, and N, N-tris (2-propenyl) amine. Esters with acrylic acid may include, but are not limited to, esters such as propylene acrylate, ethylene glycol diacrylate, polyethylene glycol diacrylate, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, glycerol triacrylate, glycerol trimethacrylate, glycerol ethylene oxide-appended triacrylate or trimethacrylate, trimethylolpropane triacrylate, ethylene glycol diacrylate, polyoxyethylene glycerol triacrylate, diethylpolyoxyethylene glycerol triacrylate, and triethylene glycol diacrylate. The ethers having at least two ethylene oxides may include, but are not limited to, sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, diglycerol polyglycidyl ether, and the like.
In some embodiments, the internal crosslinking agent is used in an amount of 0.001 to 5 parts by weight, and preferably 0.01 to 3 parts by weight, based on 100 parts by weight of the total amount of the neutralized acid group-containing monomer, the internal crosslinking agent, and the polymerization initiator. When the internal crosslinking agent is used in an amount of 0.001 to 5 parts by weight, the polymerized hydrogel body is not sticky and is easy to machine, and has good water absorption property, thereby improving the properties of the water-absorbent resin.
In some embodiments, the first internal crosslinking agent is used in an amount of not less than 20 weight percent, and preferably equal to or greater than 50 weight percent, based on 100 weight percent of the internal crosslinking agent. When the amount of the first internal crosslinking agent used is not less than 20 weight percent, the first internal crosslinking agent can improve the antibacterial property and long-lasting water absorbability of the water-absorbent resin.
Specifically, after the water-absorbent resin absorbs a liquid, the water-absorbent resin exhibits weak acidity, and this weak acidity causes hydrolysis of the ester bond of the first internal crosslinking agent to generate a hydroxyl group (i.e., the hydroxyl group of the unsaturated double bond compound) and a carboxyl group (i.e., the carboxyl group of the organic acid having antibacterial ability). The hydroxyl group and water molecule generate hydrogen bond, thereby improving the absorption capacity of the water-absorbent resin. Further, an ester bond formed between a saturated linear carboxyl group hydroxyl group represented by Z and a carboxyl group of an acid group-containing monomer can be cleaved by hydrolysis with the aforementioned weak acidity. Thereby releasing the organic acid to provide the water-absorbent resin with antibacterial property.
Although the ester with acrylic acid (such as polyethylene glycol diacrylate) in the second internal cross-linking agent also has ester bond, the first internal cross-linking agent has more hydroxyl and carboxyl, so compared with the ester with acrylic acid, the first internal cross-linking agent can greatly improve the long-acting water absorption capacity and the antibacterial property of the water-absorbent resin.
In the water-absorbent resin composition of the present invention, the polymerization initiator is used to generate radicals to induce polymerization. The polymerization initiator may include, but is not limited to, a thermal decomposition type initiator, a redox type initiator, or a combination thereof. In the case where the above-mentioned redox initiator is used in combination with a thermal decomposition type initiator, the redox initiator is first reacted to generate a radical, and then the radical is transferred to a monomer having an acid group to induce a first stage of radical polymerization. The radical polymerization reaction in the first stage releases a great deal of heat, and the high temperature caused by the heat induces the decomposition of the thermal decomposition type initiator, and further induces the radical polymerization reaction in the second stage, thereby increasing the completeness of the radical polymerization reaction.
In some embodiments, the thermal decomposition type initiator may include, but is not limited to, peroxides and/or azo compounds. In some embodiments, the peroxide may include, but is not limited to, peroxides such as hydrogen peroxide, di-tertiary butyl peroxide, peroxyamides or persulfates (ammonium or alkali metal salts). In other embodiments, the azo compound may include, but is not limited to, azo compounds such as 2.2 '-azobis (2-amidinopropane) dihydrochloride or 2.2' -azobis (N, N-dimethyleneisobutyramidine) dihydrochloride. In other embodiments, the redox initiator may include, but is not limited to, acid sulfite, thiosulfate, ascorbic acid, or ferrous salt initiators.
In some embodiments, the polymerization initiator may be used in an amount of 0.001 to 10 weight percent, and preferably 0.1 to 5 weight percent, based on 100 weight percent of the weight of the acrylate salt (i.e., the amount of neutralized acid group-containing monomer used). When the polymerization initiator is used in an amount of 0.001 to 10% by weight, the radical polymerization reaction rate is moderate, economic efficiency is good, and it is easy to control the reaction heat so that the degree of polymerization is not easily too high without forming a gel-like solid.
In the water-absorbent resin composition of the present invention, the surface cross-linking agent is used to perform a surface cross-linking reaction on the surface of the hydrogel body to form an external cross-linked structure on the surface of the hydrogel body, thereby obtaining the water-absorbent resin. The surface cross-linking agent may include, but is not limited to, polyols, polyamines, compounds having at least two epoxy groups, alkylene carbonates, and any combination thereof.
Specific examples of the aforementioned polyols include, but are not limited to, polyols such as glycerol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, and propylene glycol. Specific examples of the aforementioned polyamines include, but are not limited to, polyamines such as ethylenediamine, diethylenediamine, or triethylenediamine. Specific examples of the aforementioned compound having at least two epoxy groups include, but are not limited to, glycidyl ethers such as sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, and diglycerol polyglycidyl ether.
Specific examples of the aforementioned alkylene carbonate may include, but are not limited to, ethylene glycol carbonate, 4-methyl-1, 3-dioxolan-2-one, 4, 5-dimethyl-1, 3-dioxolan-2-one, 4-dimethyl-1, 3-dioxolan-2-one, 4-ethyl-1, 3-dioxolan-2-one, 1, 3-dioxan-2-one, 4, 6-dimethyl-1, 3-dioxan-2-one, and 1, 3-dioxacycloheptan-2-one, and the like.
The surface cross-linking agent is used in an amount of 0.001 to 10 parts by weight, and preferably 0.005 to 5 parts by weight, based on 100 parts by weight of the hydrogel body obtained by polymerization. When the surface-crosslinking agent is used in an amount of 0.001 to 10 parts by weight, the crosslinking effect on the surface of the water-absorbent resin is remarkable, and the water absorption of the water-absorbent resin is improved to improve the performance of the water-absorbent resin.
The addition of the surface cross-linking agent may be either direct or formulated into a cross-linking solution, depending on the type of the surface cross-linking agent. Among them, the crosslinking solution may be water or a hydrophilic organic solvent, such as: methanol, ethanol, propanol, isobutanol, acetone, methyl ether or ethyl ether and the like. In some embodiments, the hydrophilic organic solvent may preferably be methanol or ethanol. As shown in the disclosure of U.S. patent publication No. 6849665.
Referring to FIG. 1, a flow chart of a method for producing a water-absorbent resin according to an embodiment of the present invention is shown. In the method 100, the aqueous solution of the acid-based monomer is provided as described above, and the neutralization degree of the aqueous solution of the acid-based monomer is 45 mol% to 85 mol%, as shown in operation 110.
Next, the internal crosslinking agent, the polymerization initiator, and the aqueous acid group-containing monomer solution are mixed to perform a radical polymerization reaction, thereby obtaining a hydrogel body, as shown in operation 120. The internal cross-linking agent comprises a first internal cross-linking agent, and the first internal cross-linking agent comprises an ester compound having a structure shown in the formula (I).
The free radical polymerization reaction described above can be carried out in conventional batch reaction vessels or on a conveyor belt reactor. The hydrogel body obtained by the reaction can be cut into hydrogel body particles with the particle size of less than or equal to 20mm by a mincing machine, and the particle size of the hydrogel body particles is preferably less than or equal to 10 mm. Then, screening was performed.
The screening is to screen out hydrogel particles having a fixed particle size of 2.00mm or less, preferably 0.05 to 1.5 mm. If the particle size of the hydrogel particles is larger than 2.00mm, the hydrogel particles are returned to the reactor and cut up again. When the particle diameter of the hydrogel particles is less than 0.05mm, the amount of fine powder of the water-absorbent resin is easily increased after the drying and pulverizing treatment. When the particle size of the hydrogel particles is larger than 2.00mm, the hydrogel particles are liable to have a poor heat conduction effect during drying, which results in a disadvantage that the residual monomer content of the water-absorbent resin is high and the physical properties thereof are not good. According to the invention, the narrower the particle size distribution of the hydrogel particles, the more the physical properties of the dried hydrogel particles can reach the optimal state, and the drying time and temperature can be controlled.
And screening the hydrogel particles, and drying, wherein the drying temperature can be 100-180 ℃. When the drying temperature is less than 100 ℃, the drying time is too long, and the economic benefit is not obtained. When the drying temperature is higher than 180 ℃, the internal cross-linking agent will undergo a cross-linking reaction in advance, and in the subsequent drying process, the residual monomer cannot be effectively removed due to an excessively high degree of cross-linking, so that the effect of reducing the residual monomer cannot be achieved.
After drying, the hydrogel particles are crushed and screened to a fixed particle size. Then, a surface cross-linking agent coating process is performed to perform a surface cross-linking reaction on the dried hydrogel particles to produce a water-absorbent resin, as shown in operation 130. The fixed particle size for screening is 0.06 to 1.00mm, and preferably 0.10 to 0.85 mm. When the fixed particle diameter is less than 0.06mm, the fine powdery hydrogel particles give rise to increased dust of the finished water-absorbent resin. When the particle diameter of the hydrogel particles is larger than 1.00mm, the hydrogel particles slow down the water absorption rate of the finished water-absorbent resin. According to the present invention, the narrower the particle size distribution of the hydrogel body particles, the better.
As mentioned above, the dried hydrogel particles have a low water content (e.g., a water content of 5% or less based on the total weight of the hydrogel particles: 100%) and therefore have water-absorbing properties, and thus may be referred to as primary water-absorbent resin particles, which have a uniform cross-linked bridge structure inside and are insoluble hydrophilic polymers. In order to further improve the absorption rate, the gel strength, the blocking resistance, the liquid permeability and other water absorption characteristics of the water-absorbent resin, the water-absorbent resin can be selectively subjected to a surface cross-linking treatment process, so as to obtain the water-absorbent resin of the present invention, wherein the surface cross-linking agent used in the surface cross-linking treatment process is as described above and is not described herein again.
There are many patent documents disclosing the way of surface cross-linking treatment, for example: surface crosslinking treatment is carried out by dispersing the preliminary water-absorbent resin and ｃA crosslinking agent in an organic solvent (JP-A-56-131608, JP-A-57-44627, JP-A-58-42602, JP-A58-117222); ｃA surface crosslinking treatment is carried out by directly mixing ｃA crosslinking agent and ｃA crosslinking agent solution into ｃA water-absorbent resin using an inorganic powder (JP-A-60-163956, JP-A-60-255814); after the addition of the crosslinking agent, it is treated with steam (JP-A-1-113406); surface treatment using an organic solvent, water and ｃA polyol (JP-A-1-292004, U.S. Pat. No. 6346569); an organic solution, water, ｃA compound such as ether (JP-A-2-153903) or the like is used. These surface crosslinking methods can increase the absorption rate and the water absorption capacity under pressure, but have the undesirable effect of decreasing the holding power too much, thereby reducing the performance in practical use. However, the method of surface crosslinking treatment of the present invention does not suffer from the above-mentioned disadvantages.
The water-absorbent resin produced by the method of the present invention has an organic acid ester bond. These organic acid ester bonds are ester bonds derived from the internal crosslinker structure. After the water-absorbent resin absorbs the liquid, the water-absorbent resin exhibits weak acidity, which causes these organic acid ester bonds to be hydrolyzed and broken. The water absorption capacity of the water-absorbent resin is improved by breaking the organic acid ester bonds, and the water-absorbent resin is provided with antibacterial properties.
Further, when the method for producing a water-absorbent resin of the present invention is maintained in an inert gas atmosphere, a water-absorbent resin having more excellent physical properties can be obtained.
In some embodiments, the water-absorbent resin prepared by the present invention can be applied to sanitary products such as paper diapers (e.g., low-concentration pulp diapers (using a large amount of water-absorbent resin) or adult paper diapers), so that the paper diapers have the characteristics of good antibacterial property and long-term absorption capacity.
In some application examples, the absorbent body of the present invention is formed by molding a water-absorbent resin and hydrophilic fibers to form a sheet-like absorbent body, and the absorbent body is composed of a liquid-impermeable Polyethylene (PE) film and a liquid-permeable nonwoven fabric as a top sheet thereunder; or fixing the water-absorbent resin on pulp fiber material (Airlaid) and/or nonwoven fabric, wherein the pulp fiber is pulverized wood pulp, crosslinked cellulose fiber, cotton, wool, or vinyl acetate fiber.
The content (core concentration) of the water-absorbent resin is equal to or more than 20 weight percent and less than 100 weight percent, preferably equal to or more than 40 weight percent and less than 100 weight percent, and more preferably equal to or more than 50 weight percent and less than 100 weight percent, based on 100 weight percent of the weight of the absorbent body. The use of such a high water-absorbent resin content in the core concentration enables the antibacterial property and long-lasting absorption ability of the present invention to be more remarkably exhibited.
In general, the basis weight (weight per unit area) of the absorbent body of the present invention may be 0.01g/cm2To 0.30g/cm2And the thickness of the absorber is not more than 30 mm.
The following examples are provided to illustrate the present invention, but not to limit the invention, and those skilled in the art can make various changes and modifications without departing from the spirit and scope of the invention.
Preparation of polyethylene glycol allyl ether 3-hydroxy-3-carboxyl glutarate
99.6 g (0.2 mol) of polyethylene glycol allyl ether (n ═ 9) (manufactured by kyoto corporation and having a trade name of P3009) was added to an aqueous solution of 42.3 g (0.22 mol) of 3-hydroxy-3-carboxyglutaric acid, and refluxed at 120 ℃ for 1 hour to perform an esterification reaction. After cooling to room temperature, 30mL of saturated aqueous sodium bicarbonate solution was added to extract out the reaction. The organic phase obtained by extraction was concentrated using a separatory funnel with 30mL of ethyl acetate, and then using a rotary concentrator, to obtain 115 g of polyethylene glycol propenyl ether 3-hydroxy-3-carboxyglutarate represented by the aforementioned formula (I-2).
Preparation of Water-absorbent resin
Example 1
In a 2000 ml conical flask, 583.2 g of water and 540 g of acrylic acid were placed, and after stirring and dissolution, 437.5 g of a 48% aqueous sodium hydroxide solution was further dropped for 2 hours at a dropping ratio of sodium hydroxide to acrylic acid of 0.85 to 0.95 while maintaining the temperature at 15 ℃ to 40 ℃ to obtain an aqueous sodium acrylate solution having a monomer concentration of 42 parts by weight in which 70 mol% of acrylic acid was partially neutralized to sodium acrylate.
2.3 grams of 3-hydroxy-3-carboxyglutarate polyethylene glycol allyl ether (n ═ 10) was added to the aqueous sodium acrylate solution described above, and the temperature was maintained at about 20 ℃. Then, 0.3 g of hydrogen peroxide, 3.6 g of sodium hydrogen sulfite, and 3.6 g of a polymerization initiator of ammonium persulfate were added to carry out a radical polymerization reaction. And then, cutting the hydrogel generated after the reaction by using a cutting type grinder, and screening out hydrogel particles with the diameter being equal to or less than 2mm according to the particle size.
After drying at 130 ℃ for 2 hours, it was sieved using a sieve of fixed particle size of 0.1mm to 0.85mm to obtain dried hydrogel body particles (i.e., primary water-absorbent resin particles). Then, tests were carried out by the method for evaluating holding power described later, and the results are shown in table 1.
A volume ratio of ethylene glycol (manufactured by Sigma-Aldrich) to methanol was prepared to be 1.5: 0.5 g of the mixed solution, and 5g of the mixed solution was added to 200 g of the primary water-absorbent resin particles, and heat-treated at 150 ℃ for 1 hour. Then, the resultant was cooled to obtain a water-absorbent resin of example 1. Then, the test was performed using the following evaluation method, and the results thereof are shown in table 2 below.
Examples 2 to 7 and comparative examples 1 to 5
Examples 2 to 7 and comparative examples 1 to 5 were all prepared using the same method as in example 1. Except that the kinds and the amounts of the internal-crosslinking agents of examples 2 to 7 and comparative examples 1 to 5 were different from those of example 1. In example 2, polyethylene glycol allyl ether 3-hydroxy-3-carboxyglutarate (n ═ 10) was used in an amount of 1.2 g, and the internal crosslinking agent further contained 1.0 g of polyethylene glycol diacrylate (n ═ 9) (manufactured by changxing chemical company, and having a molecular weight of 523g/mol under the trade name EM 226). The polyoxypropylene ether 3-hydroxy-3-carboxyglutarate was used in an amount of 54.5 weight percent based on 100 weight percent of the internal cross-linking agent.
In example 3, polyethylene glycol propenyl ether 3-hydroxy-3-carboxyglutarate (n ═ 10) was substituted with polyethylene glycol propenyl ether 2-hydroxysuccinate (n ═ 12) (manufactured by long mao corporation and sold under the trade name LM 6012).
In example 4, instead of polyethylene glycol propenyl ether 3-hydroxy-3-carboxyglutarate (n ═ 10), polyethylene glycol propenyl ether 3-hydroxy-3-carboxyglutarate (n ═ 9) (manufactured by doksi, inc., and under the trade name DK455) was used in an amount of 1.2 g, and the internal crosslinking agent further contained 1.0 g of polyethylene glycol diacrylate (n ═ 9) (manufactured by changxing chemical company, under the trade name EM226, having a molecular weight of 523 g/mol). The polyoxypropylene ether 3-hydroxy-3-carboxyglutarate was used in an amount of 54.5 weight percent based on 100 weight percent of the internal cross-linking agent.
In example 5, polyethylene glycol allyl ether 3-hydroxy-3-carboxyglutarate (n ═ 10) was used in an amount of 1.2 g, and the internal crosslinking agent further contained 1.0 g of polyethylene glycol diglycidyl ether (n ═ 9) (manufactured by Nagase corporation and having a molecular weight of 586g/mol, trade name EX 830). The polyoxypropylene ether 3-hydroxy-3-carboxyglutarate was used in an amount of 54.5 weight percent based on 100 weight percent of the internal cross-linking agent.
In example 6, polyoxypropylene ether 3-hydroxy-3-carboxyglutarate (n ═ 10) was used in an amount of 1.2 g.
In example 7, polyethylene glycol allyl ether 3-hydroxy-3-carboxyglutarate (n ═ 10) was used in an amount of 1.1 g, and the internal crosslinking agent further contained 1.0 g of polyethylene glycol diacrylate (n ═ 9) (manufactured by changxing chemical company, and having a molecular weight of 523g/mol under the trade name EM 226). The polyoxypropylene ether 3-hydroxy-3-carboxyglutarate was used in an amount of 52.4 weight percent based on 100 weight percent of the internal cross-linking agent.
In comparative example 1, polyethylene glycol allyl ether (n ═ 10) (manufactured by kyoto corporation and sold under the trade name P3009) was used in place of polyethylene glycol allyl ether 3-hydroxy-3-carboxyglutarate (n ═ 10), and the amount used was 2.5 g.
In comparative example 2, polyethylene glycol propenyl ether 3-hydroxy-3-carboxyglutarate (n ═ 10) was not used, and only 1.0 g of polyethylene glycol diacrylate (n ═ 9) (manufactured by changxing chemical company, and having a molecular weight of 523g/mol, under the trade name EM 226) was used.
In comparative example 3, polyethylene glycol allyl ether 3-hydroxy-3-carboxyglutarate (n ═ 10) was not used, and only 1.0 g of polyethylene glycol diglycidyl ether (n ═ 9) (manufactured by Nagase, inc., and having a molecular weight of 586g/mol, under the trade name EX 830) was used.
In comparative example 4, polyethylene glycol diglycidyl ether (n ═ 9) (manufactured by Nagase corporation and having a molecular weight of 586g/mol) was used in an amount of 1.2 g in place of polyethylene glycol propenyl ether 3-hydroxy-3-carboxyglutarate (n ═ 10), and the internal crosslinking agent further contained 1.0 g of polyethylene glycol diacrylate (n ═ 9) (manufactured by changxing chemical corporation and having a molecular weight of 523g/mol) manufactured under a trade name of EM226
In comparative example 5, polyethylene glycol allyl ether 3-hydroxy-3-carboxyglutarate (n ═ 10) was used in an amount of 0.3 g, and the internal crosslinking agent further contained 2.0 g of polyethylene glycol diacrylate (n ═ 9) (manufactured by changxing chemical company, and having a molecular weight of 523g/mol under the trade name EM 226). The polyoxypropylene ether 3-hydroxy-3-carboxyglutarate was used in an amount of 13.0 weight percent based on 100 weight percent of the internal cross-linking agent. The evaluation results for examples 2 to 7 and comparative examples 1 to 5 are shown in table 1.
TABLE 1
TABLE 1 (continuation)
Production of absorbent body
Application example 1
First, 10.0g of the water-absorbent resin of example 1 was mixed with 10.0g of pulverized wood pulp using an absorber-forming machine to form a metal mesh having a mesh size of 400 mesh (38 μm) and an absorber area of 160 cm (8 cm × 20 cm) in square, and then, the formed absorber was placed over a PE film and a nonwoven fabric was placed on the absorber, followed by application of 18.39kPa (area 160 square centimeters, weight 30 Kg). After pressing for 5 minutes, the sheet was adhered with a white glue for four weeks to obtain an absorbent body of application example 1, wherein the absorbent body of application example 1 had a basis weight of 0.08g/cm2And a thickness of 17 mm.
Application examples 2 to 7 and comparative application examples 1 to 5
Application examples 2 to 7 and comparative application examples 1 to 5 were prepared in the same manner as in application example 1. Except that the water-absorbent resins of examples 2 to 7 and comparative examples 1 to 5 were used in accordance with the respective application examples 2 to 7 and comparative examples 1 to 5. Further, the basis weights and thicknesses of the water-absorbent resins relating to application examples 2 to 7 and comparative application examples 1 to 5 are shown in table 2, and the evaluation results are also shown in table 2.
Evaluation method
In each evaluation mode described below, unless otherwise specified, it was carried out at room temperature (23. + -. 2 ℃ C.) and a relative air humidity of 45. + -. 10%.
1. Retention force
The Retention Capacity (CRC) was tested according to the ERT441.3(10) determination method specified by the European nonwoven society (European Disposities and Nonwovens Association; EDANA).
2. Core retention
The Core Retention Capacity (CCRC) was measured according to ERT441.3(10) specified by EDANA, but the test time was extended to 240 minutes.
3. Water absorption capacity under pressure
The water Absorption capacity under Pressure (AAP) was measured according to the method of measuring ERT442.2(5) specified by EDANA. The water absorption capacity of the water-absorbent resin with respect to a 0.9% aqueous solution of sodium chloride was measured under a pressure of 4.9kPa for a test time of 60 minutes. The water absorption capacity under pressure is preferably more than 15g/g, and more preferably 20 to 30 g/g.
4. Free absorption Rate
Free Swell Capacity (FSC) was measured according to the method of ERT440.3(10) specified by EDANA.
5. Core free absorption Capacity
The Core Free absorption Capacity (CFSC) was measured according to the test method of ERT440.3(10) specified by EDANA, but the test time was extended to 240 minutes.
6. Absorption index
The Absorption Index (AI) is calculated by the following formula (II):
wherein the core retention, core free absorbent capacity, retention and free absorbent capacity are as defined above.
7. Residual monomer
Residual Monomers (RAA) were tested according to EDANA specified ERT 410.3 (10).
8. Antibacterial test
The antibacterial test was conducted by analyzing the antibacterial ability of a water-absorbent resin or an absorbent containing a water-absorbent resin against Escherichia coli using a method specified by AATCC100 of the American society for textile chemistry. When the test group of the water-absorbent resin or the absorbent body containing the water-absorbent resin had a smaller amount of E.coli growth than the control group, the water-absorbent resin was judged to have antibacterial ability, and the evaluation result is indicated by ". smallcircle". On the other hand, when the test group of the water-absorbent resin or the absorbent material containing the water-absorbent resin had the same or more amount of E.coli growth as the control group, the water-absorbent resin was judged to have no antibacterial ability, and the evaluation result was represented by "gamma".
9. Amount of reverse osmosis
The Rewet (i.e., dryness) was measured by placing a weight of 4.8kPa (160 square centimeters in area and 7.8Kg in weight) on the test absorbent and uniformly pressing the weight against the test absorbent. Synthetic urine (according to Jayco synthetic urine described in U.S. patent publication No. 20040106745) was then added in three portions at the center point and added to the absorbent body at a frequency of 30 minutes per compartment, wherein the total amount of synthetic urine was 180 milliliters. After the synthetic urine was added and after 30 minutes, the weight above the test absorber was removed, and 30 sheets of filter paper (8 cm. times.20 cm.) having a total weight (W1(g)) measured in advance were placed on the test absorber, and immediately after that, a weight of 4.8kPa was placed on the test absorber for 5 minutes to allow the filter paper to absorb the rewet liquid, and then the weight of the 30 sheets of filter paper (W2(g)) was measured, wherein the rewet amount (g) of the synthetic urine of the absorber was a weight value obtained by subtracting W1 from W2. The lower the rewet amount is, the more excellent the dryness of the water-absorbent resin is.
TABLE 2
Referring to Table 1, according to the results of the core free absorption capacity, absorption index and antibacterial test, the water-absorbent resins of the examples have higher core free absorption capacity and absorption index and better antibacterial property than those of comparative example 1 in which the first internal crosslinking agent is not used and comparative examples 2 to 4 in which only the second internal crosslinking agent is used. In addition, in comparative example 5, the amount of the first internal crosslinking agent used was 13.0 wt% based on 100 wt% of the amount of the internal crosslinking agent used, and since comparative example 5 used an excessively low amount of the first internal crosslinking agent (less than 20 wt%), the water-absorbent resin of comparative example 5 had a lower free core absorption capacity and absorption index and a poorer antibacterial property than those of examples. This shows that the water-absorbent resin obtained by using the first internal crosslinking agent having a specific structure and a specific amount of the first internal crosslinking agent has excellent antibacterial properties and long-lasting absorption ability.
Referring to table 2, according to the results of the antibacterial test, the absorbent body of each application example has better antibacterial properties than comparative application example 1 in which the first internal crosslinking agent is not used and comparative application examples 2 to 4 in which only the second internal crosslinking agent is used. In addition, in comparative application example 5, similarly to the above, since comparative application example 5 used the first internal crosslinking agent which was too low, the absorbent body of comparative application example 5 had inferior antibacterial properties compared to each application example. This shows that the absorber obtained by the specific structure and the specific amount of the first internal crosslinking agent has a good antibacterial property.
The water-absorbent resin composition and the method for producing the water-absorbent resin of the present invention are applied, wherein the water-absorbent resin has good antibacterial property and long-lasting absorption capacity by the specific structure and the specific usage amount of the first internal cross-linking agent.
Although the present invention has been described with reference to the above embodiments, it should be understood that various changes and modifications may be made therein by those skilled in the art without departing from the spirit and scope of the invention.
Claims (10)
1. A water-absorbent resin composition, comprising:
an aqueous acid group-containing monomer solution, wherein the degree of neutralization of the aqueous acid group-containing monomer solution is from 45 mole percent to 85 mole percent;
an internal crosslinking agent comprising a first internal crosslinking agent, wherein the first internal crosslinking agent comprises an ester compound having a structure represented by formula (I):
wherein X represents a linear or branched alkenyl group with the carbon number of 3 to 5, and one end of X far away from Y is of a double bond structure; n represents 8 to 15; a plurality of Y's each independently represent an ethylene glycol group or a propylene glycol group, and the oxygen atoms of the ethylene glycol group and the propylene glycol group are bonded to X; z represents a substituted saturated linear chain carboxyl with the carbon number of 3-7, one end of Z far away from the carbon atom is in a carboxyl structure, the substituent of the saturated linear chain carboxyl comprises hydroxyl, and the number of the hydroxyl is 1-3;
a polymerization initiator; and
a surface cross-linking agent.
2. The water-absorbent resin composition according to claim 1, wherein the aqueous acid group-containing monomer solution contains a neutralized acid group-containing monomer, and the neutralized acid group-containing monomer is used in an amount of 20 to 55 parts by weight based on 100 parts by weight of the aqueous acid group-containing monomer solution.
3. The water-absorbent resin composition according to claim 2, wherein the internal-crosslinking agent is used in an amount of 0.001 to 5 parts by weight based on 100 parts by weight of the total amount of the neutralized acid group-containing monomer, the internal-crosslinking agent and the polymerization initiator.
4. The water-absorbent resin composition according to claim 1, wherein the internal-crosslinking agent further comprises a second internal-crosslinking agent, and the second internal-crosslinking agent is selected from the group consisting of amines having an acryl group, esters having an acrylic acid group, ethers having at least two ethylene oxides, and any combination thereof.
5. The water-absorbent resin composition according to claim 1 or 4, wherein the first internal-crosslinking agent is used in an amount of not less than 20% by weight based on 100% by weight of the internal-crosslinking agent.
6. A method for producing a water-absorbent resin, comprising:
providing an aqueous acid-group-containing monomer solution, wherein the degree of neutralization of the aqueous acid-group-containing monomer solution is from 45 mole percent to 85 mole percent;
mixing an internal cross-linking agent, a polymerization initiator and the acid group-containing monomer aqueous solution to perform free radical polymerization reaction to prepare a hydrogel body, wherein the internal cross-linking agent comprises a first internal cross-linking agent, and the first internal cross-linking agent comprises an ester compound with a structure shown in a formula (I):
wherein X represents a linear or branched alkenyl group with the carbon number of 3 to 5, and one end of X far away from Y is of a double bond structure; n represents 8 to 15; a plurality of Y's each independently represent an ethylene glycol group or a propylene glycol group, and the oxygen atoms of the ethylene glycol group and the propylene glycol group are bonded to X; z represents a substituted saturated linear chain carboxyl with the carbon number of 3-7, one end of Z far away from the carbon atom is in a carboxyl structure, the substituent of the saturated linear chain carboxyl comprises hydroxyl, and the number of the hydroxyl is 1-3; and
and carrying out surface crosslinking reaction on the hydrogel by using a surface crosslinking agent to prepare the water-absorbent resin.
7. The method for producing a water-absorbent resin according to claim 6, wherein the amount of the internal crosslinking agent used is 0.001 to 5 parts by weight based on 100 parts by weight of the total amount of the neutralized acid-group-containing monomer, the internal crosslinking agent and the polymerization initiator contained in the aqueous solution of acid-group-containing monomer.
8. The method according to claim 6, wherein the internal-crosslinking agent further comprises a second internal-crosslinking agent, and the second internal-crosslinking agent is selected from the group consisting of amines having an acryl group, esters having an acrylic acid, ethers having at least two ethylene oxides, and any combination thereof.
9. The method according to claim 8, wherein the first internal-crosslinking agent is used in an amount of not less than 20% by weight based on 100% by weight of the internal-crosslinking agent.
10. A water-absorbent resin obtained by the method for producing a water-absorbent resin according to any one of claims 6 to 9, wherein the water-absorbent resin has an organic acid ester bond.
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|---|---|---|---|---|
| US20100093917A1 (en) * | 2007-03-16 | 2010-04-15 | Nippon Shokubai Co., Ltd. | Water Absorbent Resin Production Method, Water Absorbent Resin, and Usage Thereof |
| CN101768237A (en) * | 2008-12-30 | 2010-07-07 | 台湾塑胶工业股份有限公司 | Manufacturing method of super absorbent resin |
| CN108659434A (en) * | 2017-03-31 | 2018-10-16 | 台湾塑胶工业股份有限公司 | Water-absorbent resin and method for producing same |
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| WO2001094459A1 (en) * | 2000-06-05 | 2001-12-13 | Nagase Chemtex Corporation | Crosslinking agent for water-absorbing resin and water-absorbing material obtained with the same |
| DE10053858A1 (en) * | 2000-10-30 | 2002-05-08 | Stockhausen Chem Fab Gmbh | Absorbent structure with improved blocking properties |
| TWI449731B (en) * | 2009-04-30 | 2014-08-21 | Formosa Plastics Corp | Production efficiency of superabsorbent polymer |
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| US20100093917A1 (en) * | 2007-03-16 | 2010-04-15 | Nippon Shokubai Co., Ltd. | Water Absorbent Resin Production Method, Water Absorbent Resin, and Usage Thereof |
| CN101768237A (en) * | 2008-12-30 | 2010-07-07 | 台湾塑胶工业股份有限公司 | Manufacturing method of super absorbent resin |
| CN108659434A (en) * | 2017-03-31 | 2018-10-16 | 台湾塑胶工业股份有限公司 | Water-absorbent resin and method for producing same |
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