WO2005023877A1 - Resine hydroabsorbante et son procede de production - Google Patents

Resine hydroabsorbante et son procede de production Download PDF

Info

Publication number
WO2005023877A1
WO2005023877A1 PCT/JP2003/011245 JP0311245W WO2005023877A1 WO 2005023877 A1 WO2005023877 A1 WO 2005023877A1 JP 0311245 W JP0311245 W JP 0311245W WO 2005023877 A1 WO2005023877 A1 WO 2005023877A1
Authority
WO
WIPO (PCT)
Prior art keywords
water
monomer
network structure
gel
absorbent resin
Prior art date
Application number
PCT/JP2003/011245
Other languages
English (en)
Japanese (ja)
Inventor
Yoshihito Osada
Jian Ping Gong
Original Assignee
Hokkaido Technology Licensing Office Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hokkaido Technology Licensing Office Co., Ltd. filed Critical Hokkaido Technology Licensing Office Co., Ltd.
Priority to PCT/JP2003/011245 priority Critical patent/WO2005023877A1/fr
Priority to AU2003261904A priority patent/AU2003261904A1/en
Publication of WO2005023877A1 publication Critical patent/WO2005023877A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/04—Polymerisation in solution
    • C08F2/10—Aqueous solvent

Definitions

  • the present invention relates to a water-absorbent resin having excellent mechanical strength and a method for producing the same.
  • water-absorbing resins have been used as various water-absorbing materials such as diapers, sanitary products, soil water retention agents, sealants and the like.
  • the first problem of the conventional water-absorbent resin is weak mechanical strength.
  • a water-absorbent resin having a nonionic hydrophilic segment for example, a crosslinked polybutyl alcohol-modified product (Japanese Patent Laid-Open No. 54-20993), a polyethylene oxide partially cross-linked product (Japanese Patent Application Laid-Open No. No. 30, 324) tend to have properties such as low gel strength, low water absorption rate, and low absolute value of absorption capacity.
  • the second problem with the conventional water-absorbent resin is that the absorption capacity varies greatly depending on the type of liquid to be absorbed.
  • a water-absorbing resin having an electrolyte structure such as a carboxy group ⁇ for example, a crosslinked body of an acrylic acid (salt) polymer (Japanese Patent Application Laid-Open No.
  • the absorption rate changes due to a change in the salt concentration in urine, leading to quality fluctuation.
  • the swelling volume changes depending on the salt concentration, which may limit its use in the fields of agriculture and horticulture and the field of waterproofing agents.
  • the present invention is intended to provide a material having excellent mechanical strength, and It is an object of the present invention to provide a water-absorbent resin excellent in water resistance and a method for producing the same. Disclosure of the invention
  • the present invention (1) provides a first network by polymerizing and crosslinking a first monomer component (here, at least 10 mol% of the component is a charged unsaturated monomer) in the presence of a solvent.
  • a first step of forming a structure
  • the second monomer component After introducing a second monomer component (where at least 60 mol% of the component is an electrically neutral unsaturated monomer) into the first network structure, the second monomer component is A step of forming a polymer in the first network by polymerizing in the presence of a solvent, or a second step of forming a second network in the first network by optionally further crosslinking. (Here, when the second monomer component is polymerized and cross-linked, the degree of cross-linking is set smaller than when the first monomer component is polymerized and cross-linked);
  • a water-absorbent resin having a semi-interpenetrating network structure or an interpenetrating network structure (where the amount of the first monomer component: the amount of the second monomer component in the water-absorbing resin is 1: 2 to 1 in molar ratio) : 100).
  • the present invention (2) is the production method according to the above invention (1), wherein the charged unsaturated monomer is an unsaturated monomer having an acidic group and / or a basic group.
  • the present invention (3) is the process according to the invention (2), wherein the acidic group is selected from the group consisting of a carboxyl group, a phosphoric acid group and a sulfonic acid group.
  • the present invention (4) is the process according to the invention (3), wherein the unsaturated monomer having an acidic group is 2-acrylamide 2-methylpropanesulfonic acid, acrylic acid, methacrylic acid or a salt thereof. is there.
  • the present invention (5) is characterized in that the electrically neutral unsaturated monomer is acrylamide, N-isopropylpropylacrylamide, butylpyridine, styrene, methyl methacrylate, fluorine-containing unsaturated monomer (for example, Trifluoroacetic acid atalylate), hydroxyxetyl atalylate or biel acetate.
  • the present invention (6) further comprises a metal source that generates a metal ion when the resin comes into contact with water, and at least a part of the first monomer component and the second monomer component is complexed with the metal ion.
  • the production method according to any one of the inventions (1) to (5) which is a monomer having a group capable of forming
  • the crosslinking agent is used in an amount of 0.1 to 50 mol% with respect to the first monomer component, and the crosslinking agent is used in an amount of 0.001 to 20 mol% with respect to the second monomer component.
  • the invention (8) is the production method according to any one of the inventions (1) to (7), wherein the polymerization and / or crosslinking in the first step and / or the second step is performed in an aqueous solution.
  • the present invention (9) is the production method according to any one of the inventions (1) to (8), further comprising a fourth step of crushing and sieving the water-absorbent resin obtained in the third step. .
  • the present invention (10) is the production method according to any one of the inventions (1) to (9), wherein the absorbent resin has salt resistance.
  • the present invention (11) is the production method according to any one of the inventions (1) to (10), wherein the water absorbing resin has an absorption capacity (water) of 2 to 1000%.
  • any one of the above inventions (1) to (12), wherein a compressive rupture stress of a hide mouth gel formed when the absorbent resin absorbs water is 0.1 to 10 OMPa.
  • the present invention is the production method according to any one of the inventions (1) to (14), wherein the gel at the hide opening formed when the absorbent resin absorbs water exhibits stress dispersibility.
  • the present invention (16) is a water-absorbent resin obtained by the production method according to any one of the inventions (1) to (15).
  • the present invention (17) is a sanitary article, agricultural or horticultural product containing the water-absorbent resin of the invention (16). It is a product selected from the group consisting of:, sealant, lubricant for propulsion method, prevention of sludge loss in ground excavation, fixing agent for muddy water, carpet underlay, and agricultural coating agent.
  • Figure 1 shows the network structure formed by polymerizing and crosslinking the first monomer component.
  • a mutual intrusion network structure in which the first network structure and a network structure (second network structure) formed by polymerizing and crosslinking the second monomer component are physically entangled with each other via a network. It is a water-absorbing resin of the network type.
  • A indicates the first network structure
  • B indicates the second network structure
  • 1 and 2 indicate cross-linking points.
  • Figure 2 shows the water absorption of a semi-interpenetrating network structure (double network type) in which linear polymers formed by polymerizing the first network structure and the second monomer component are physically entangled with each other via the network.
  • C indicates the first network structure
  • D indicates a linear polymer
  • 3 indicates a crosslinking point.
  • FIG. 3 shows the dependency of the compressive rupture stress and the rupture strain in 1PAMPS4-XPAAmO. 1 DN gel on the concentration of the monomer constituting the second network structure.
  • the second monomer concentration on the horizontal axis means the second monomer concentration used in the polymerization, and X in “1 PAMP S—XPAAmO. 1” corresponds to this.
  • FIG. 4 shows the dependence of the compressive rupture stress in the 1PAMPS4-lPAAmX DN gel on the bridging degree in the second network structure.
  • Figure 5 shows an experimental system for taking a photoelastic image photograph when the gel is subjected to stress deformation.
  • 4 is a light source
  • 5 is a polarizer
  • 6 and 8 are 1/4 plates
  • 7 is a sample
  • 9 is an analyzer
  • 10 is a CCD camera
  • 11 is a computer.
  • Figure 6 is a photoelastic image showing the stress diffusion state of various gels when subjected to stress deformation.
  • A Force S 1 PAMPS 4-1 PAAm 0.1 DN gel
  • B Force S 1 PAMPS 4 One lPAAm2DN gel.
  • “mouth” has a distortion of 6.670%
  • V shows the case where the distortion is 13.33%
  • ⁇ shows the case where the distortion is 20.00%
  • ⁇ shows the case where the distortion is 26.67%.
  • FIG. 9 shows the relationship between intensity (vertical axis) and strain (%) when various lPAMPS4-XPAAm0.1 DN gels having different AAm concentrations were subjected to stress deformation.
  • the “interpenetrating network structure” refers to a state in which another network structure is uniformly entangled as a whole with the base network structure, and as a result, a plurality of network structures are formed inside.
  • this type of resin is composed of a first network structure ⁇ having a plurality of crosslinking points 1 and a second network structure B having a plurality of crosslinking points 2.
  • the first network structure A and the second network structure B are physically intertwined with each other via the network.
  • This figure is a conceptual diagram of a gel containing a solvent (water) in a network structure, which is obtained as a result of absorbing water by a water-absorbing resin.
  • “Semi-interpenetrating network structure” refers to a state in which a linear polymer is uniformly entangled as a whole with a base network structure, and as a result, a plurality of network structures are formed inside.
  • this type of resin is composed of a first network structure C having a plurality of crosslinking points 3 and a linear polymer D. Polymers D are physically entangled with each other via a network.
  • the first network structures A and C are drawn thicker than the second network structure B and the linear polymer D, but are drawn by changing the thickness for convenience. Things.
  • the “interpenetrating network structure” and “semi-interpenetrating network structure” are concepts that include not only a double network type but also a mode having a triple or quadruple or more network structure.
  • Crosslinking degree refers to a value expressed as a percentage of a molar concentration of a crosslinking agent to a molar concentration of a charged monomer. Actually, there may be a few monomers that did not participate in the polymerization and some crosslinking agents that did not participate in the crosslinking, but in this case, the degree of crosslinking of the gel in this specification is as described above. .
  • Water-insoluble monomer refers to a monomer that dissolves at most 0.1 g at a temperature of 1 g in 100 ml of water at normal temperature and pressure.
  • water-soluble monomer refers to a monomer that exceeds the above-mentioned value at normal temperature and normal pressure.
  • the first feature of the present invention 1 0 mole 0/0 or more first monomer component is an unsaturated monomer having an electric charge, 6 0 mole 0/0 or more second monomer component, electrical In that it is a neutral unsaturated monomer. That is, by adopting such a configuration, the first network structure ⁇ a charged group (for example, a carboxyl group) formed by polymerizing and crosslinking the first monomer component is present in an amount not less than a certain amount. Large amounts of electrically neutral unsaturated monomers can be introduced into the network. That is, the type and amount of the monomer used and the order of use are very important.
  • the unsaturated monomer having a charge preferably, an unsaturated monomer having an acidic group (for example, a carboxyl group, a phosphate group and a sulfonic acid group) or a basic group (for example, an amino group) is used.
  • an acidic group for example, a carboxyl group, a phosphate group and a sulfonic acid group
  • a basic group for example, an amino group
  • 2-acrylamide-1-methylpropanesulfonic acid, acrylic acid, methacrylic acid or salts thereof can be mentioned.
  • the electrically neutral unsaturated monomer include acrylamide, N-isopropylacrylamide, bierpyridine, styrene, methyl methacrylate, and a fluorine-containing unsaturated monomer (for example, trifluoroethyl acrylate).
  • the amount of unsaturated monomer having an electric charge of the first monomer component is a first monomer component with respect to 1 0 mol 0/0 or more, preferably 1 0 0 mole 0/0.
  • the amount of unsaturated monomer that does not charge the second monomer component is a second monomer component to 1 0 mol 0/0 or more, preferably 1 0 0 mole 0/0.
  • a second feature of the present invention is that the amount of the first monomer component: the amount of the second monomer component in the water-absorbent resin is 1: 2 to 1: 100 (preferably 1: 3) in a molar ratio. To 1:50, more preferably 1: 3 to 1:30).
  • the amount of the first monomer component is 1: 2 to 1: 100 (preferably 1: 3) in a molar ratio. To 1:50, more preferably 1: 3 to 1:30).
  • the amount of monomer in the resin is determined by elemental analysis when each network structure is composed of one type of monomer. In the case of two or more types, it may not be possible to determine them due to the complexity of elemental analysis. In such a case, the amount is determined, for example, by subtracting the amount of non-polymerized monomer from the amount of monomer used in the production.
  • a third feature of the present invention is that the degree of crosslinking is set to be smaller when polymerizing and crosslinking the second monomer component than when polymerizing and crosslinking the first monomer component. That is, the degree of crosslinking of the second network structure (the network structure formed by polymerizing and crosslinking the second monomer component) is smaller than that of the first network structure.
  • An extreme example is the form of a water-absorbent resin having a semi-interpenetrating network structure in which the degree of crosslinking of the second network structure is 0 (that is, when the second monomer component is polymerized but not cross-linked).
  • the present invention is epoch-making in that the mechanical strength is greatly improved only by reversing the relationship between the degree of crosslinking of the first network structure and the degree of crosslinking of the second network structure. Specifically, the amount of the cross-linking agent used to form the first network structure and the amount of the cross-linking agent used to form the second network structure are determined based on the amount of the raw material monomer of each network structure. Make appropriate adjustments in association with them.
  • the degree of cross-linking of the first network structure is 0.:! To 50 mol%, and the degree of cross-linking of the second network structure is 0.001 to 20 mol%.
  • the first network structure has a degree of crosslinking of 1 to 20 mol%
  • the second network structure has a degree of crosslinking of 0.01 to 5 mol%.
  • the degree of crosslinking of the first network structure is 2 to 10 mol%
  • the degree of crosslinking of the second network structure is 0.05 to 1 mol%.
  • both crosslinking degrees are required. Should be raised.
  • the first monomer component is not particularly limited as long as it contains 10% by mole or more of a charged unsaturated monomer.
  • the first monomer component is used as an electrically neutral neutral monomer. Certain unsaturated monomers may be used.
  • the second monomer component is not particularly limited as long as it contains 60% by mole or more of an electrically neutral unsaturated monomer.
  • the charge, which is essentially used as the first monomer component may be reduced. May be used.
  • AMPS 2-acrylamide-12-methylpropanesulfonic acid
  • AAm acrylamide
  • acrylic acid AA
  • methacrylic acid N-isopropylacrylamide
  • bulpyridine hydroxylethyl atari And butyl acetate
  • dimethinolesiloxane St
  • MMA methyl methacrylate
  • TFE trifluoroethyl acrylate
  • polysaccharides such as dielan, hyaluronic acid, carrageenan, chitin and alginic acid, and proteins such as gelatin and collagen may be used.
  • the organic monomer used is composed of a first network structure, a second network structure (a water-absorbent resin having an interpenetrating network structure) and a linear polymer (a water-absorbing resin having a semi-interpenetrating network structure). They may be the same or different. However, if different raw materials are used, the hydrated mouth gel obtained after water absorption will have higher mechanical properties. It is preferable to use both a water-insoluble monomer and a water-soluble monomer as the raw material organic monomer. This is based on the new finding that excellent mechanical strength is achieved when a water-insoluble monomer is partially used.
  • the second network structure water-absorbing resin having an interpenetrating network structure
  • the linear polymer water absorbing resin having a semi-interpenetrating network structure
  • the ratio of the water-insoluble monomer to the water-soluble monomer is preferably from 9.9: 0.1 to 0.1: 9.9.
  • water-soluble monomer: water-insoluble monomer 0: 100 to 1:99
  • water-soluble monomer: water-insoluble monomer 0: 100 It is more preferable to set to ⁇ 10: 90.
  • the content of the hydrophobic monomer may be increased.
  • Water-insoluble monomers include, for example, fluorine-containing monomers such as 2,2,2-trifluoroethyl acrylate, 2,2,3,3,3-pentafluoropropyl methacrylate, 3- Butyl) — 2-hydroxypropyl methacrylate, 1H, 1 H, 9H— to Xadecafluorononi methacrylate, 2, 2, 2-trifluorethyl acrylate, 2, 3, 4, 5, 6— Pentafluorostyrene, vinylidene fluoride and the like can be mentioned.
  • fluorine-containing monomers such as 2,2,2-trifluoroethyl acrylate, 2,2,3,3,3-pentafluoropropyl methacrylate, 3- Butyl) — 2-hydroxypropyl methacrylate, 1H, 1 H, 9H— to Xadecafluorononi methacrylate, 2, 2, 2-trifluorethyl acrylate, 2, 3, 4, 5, 6— Pentafluor
  • a monomer having a group capable of forming a complex with a metal ion is used as an organic monomer as a raw material, and the metal ion is introduced into a gel (a gel at a mouth opening obtained by absorbing water).
  • a gel a gel at a mouth opening obtained by absorbing water.
  • the second network structure (a water-absorbing resin having an interpenetrating network structure) or a linear polymer is used.
  • Polymer si-interpenetrating network (Aqueous resin) or both.
  • a preferred embodiment is one in which a complex is formed with a metal ion in the first network structure.
  • the metal content is preferably 0.03 mol / 1 to: 1 mol / 1, and 0.01 mol / !! ⁇ 0.3 mol / 1 is more preferred.
  • the content of the monomer having a group capable of forming a complex is 10 to 10% with respect to the total amount of the monomers constituting the first network structure.
  • the ratio of the monomer having a group capable of forming a complex with the metal ion is preferably from 1: 1 to 1: 100, more preferably from 1:10 to 1: 10,000. is there.
  • the metal ion is not particularly limited as long as it is a metal ion capable of forming a complex, and examples thereof include a zinc ion, an iron ion, a nickel ion, a cobalt ion, and a chromium ion.
  • the metal source include a water-soluble metal salt which generates a metal ion when dissolved in water.
  • the group capable of forming a complex with a metal ion refers to a group capable of forming a complex with a selected metal ion.
  • a polyvalent metal such as zinc, iron, nickel, cobalt, or chromium is selected as the metal ion.
  • a carboxyl group, a sulfonic acid group, and a phosphoric acid group can be exemplified.
  • the monomer containing a group capable of forming a complex with a metal ion include acrylic acid, methacrylic acid, itaconic acid, styrenesulfonic acid, and burric acid.
  • the water absorption ratio (water, physiological saline, urine) of the water absorbent resin is preferably 2 to 20, more preferably 4 to 15.
  • the particle size is not particularly limited. For example, when used as a material for ommu, 90 to 100% by weight of L :! ⁇ 1 4 9 ⁇ , especially :! It preferably has a particle size of ⁇ 74 ⁇ ⁇ . Further, the water content is not particularly limited, but is preferably 0 to 10%.
  • the shear modulus of the gel is preferably from 0.01 to 10 MPa, more preferably from 0.03 to 3 MPa, and most preferably from 0.1 to 1.0 OMPa.
  • the compressive rupture stress of the gel is preferably 0.1 to 10 OMPa, more preferably:! To 5 OMPa, and most preferably 3 to 4 OMPa.
  • the tensile breaking stress of this gel is preferably 0.1 to 10 OMPa, more preferably 0.1 to 10 OMPa. 50 MPa, most preferably 0.5 to 5 MPa.
  • the gel preferably has a water content of at least 10% (more preferably at least 50%, more preferably at least 85%).
  • the water-absorbent resin according to the present invention has a high absorption ability and is suitable as a water-absorbent material.
  • the upper limit of the water content is not particularly limited, but is usually 99.9% or less, preferably 99% or less, more preferably 95% or less, for reasons such as maintaining the mechanical strength of the gel. is there.
  • a water absorbent resin contains a second monomer component (containing at least 60 mol% of an electrically neutral unsaturated monomer) and a polymerization initiator (and a crosslinking agent in the case of an interpenetrating network hydrid gel).
  • a gel having a first network structure ⁇ a single network gel formed by polymerizing and crosslinking a first monomer component (containing at least 10 mol% of a charged unsaturated monomer) ⁇ is used as the solution.
  • the second monomer component and the polymerization initiator (and, in the case of an interpenetrating network hydrogel, also a crosslinking agent) are allowed to diffuse into the gel.
  • the gel is taken out of the solution, and the second monomer component in the gel is polymerized (and in the case of an interpenetrating network hydrogel, also crosslinked) to be entangled in the network of the first network.
  • a gel having a double network structure is produced as a result of formation of a second network structure (in the case of an interpenetrating network hydrated gel) or a linear polymer (in the case of a semi-interpenetrating network hydrated gel). be able to.
  • a gel having a multi-network structure instead of the single-network gel in the same manner as the above procedure, it is possible to produce a triple or more interpenetrating network gel.
  • the aqueous solution polymerization is carried out under stirring and mixing in order to uniformly disperse the second monomer component in the first network structure and efficiently perform the reaction for forming the second network structure and the polymer. It is preferred to do so.
  • a kneader is used as a reaction vessel having a plurality of rotary stirring shafts. Most preferably, it is used.
  • the gel obtained at this time may be dried, crushed and, if necessary, sieved to adjust to a desired particle size (range).
  • the polymerization initiator used to form the first network structure, the second network structure (for interpenetrating network gel), and the linear polymer (for semi-interpenetrating network gel) is particularly preferable.
  • various types are selected according to the organic monomer to be polymerized.
  • thermally polymerizing AMPS, A Am, or AA as an organic monomer use a water-soluble thermal catalyst such as persulfuric acid rim, or a redox initiator such as persulfuric acid urea-sodium thiosulfate.
  • 2-oxodaltaric acid can be used as a photosensitizer.
  • the crosslinking agent used to form the first network structure or the second network structure is not particularly limited. Things are selected. For example, AMPS, A as organic monomers
  • N, ⁇ '-methylenebisacrylamide can be used, and when St is used as the organic monomer, ethylene dalicol dimethacrylate can be used.
  • the solvent of the solution in which the gel having the first network structure is immersed As for the solvent of the solution in which the gel having the first network structure is immersed, the adverse effect on the gel immersed in the solution is prevented, and the double network structure (interpenetrating network structure hide mouth gel) is used.
  • the polymer having the first network structure with the linear polymer (semi-interpenetrating network structure mouth gel) in the first network structure Preferably, they are the same.
  • the embodiment in which metal ions are introduced into the gel is carried out by drying the obtained (semi-) interpenetrating network hydrogel in vacuum and then immersing it in this metal salt solution. According to this operation, it is possible to efficiently form a complex with a metal ion by minimizing the distance between the networks.
  • the polymerization reaction of the first monomer component diffused into the gel having the first network structure is carried out by heating or by using ultraviolet light. Such irradiation can be performed by any of the above methods. This polymerization reaction is performed under conditions that do not destroy the first network structure of the gel.
  • a predetermined concentration of a cross-linking agent and a reaction initiator are mixed together with a second monomer component in a solvent and diffused into a gel having a first network structure.
  • the gel having the first network structure is immersed in a second monomer solution containing a crosslinking agent, and is diffused at a low temperature for 24 hours.
  • the temperature is preferably lower than room temperature and around 4 ° C.
  • the water-absorbent resin according to the present invention has such a property that a hydrogel formed after absorbing water has strong gel strength, chemical resistance, flexibility, material permeability, and impact resistance. Specifically, the hydrogel formed after water absorption has a strength of at least 10 MPa, which is ideal for absorbent materials (eg, diapers and civil engineering materials), despite a solvent content of at least 10%. From the viewpoint that the water-absorbent resin according to the present invention can be used, the utility is great. In addition, the water absorbent resin according to the present invention can have excellent salt resistance.
  • Salt resistance salt absorption capacity of physiological saline / pure water (Deionized water).
  • Gel strength 2 compression rupture stress / compression rupture strain: A swollen gel is cut into a disk having a diameter of 9 mm and a thickness of 5 mm, and the gel is sandwiched between two flat plate plates, and a TENSILON TM tensile tester ( 0 Compress using the RIENTEC model: RTC-1310A) (compression speed is 10% / min).
  • the “compression rupture stress” is calculated by the formula of (force at compression rupture / original cross-sectional area), and “compression rupture strain” is (original length minus length at compression rupture) / Original length X The value calculated by the formula of 100%.
  • Gel strength 3 (Tensile rupture stress ⁇ Tensile rupture strain): Cut the swollen gel into a strip of 5cm in length, 5ram in width, and 3 rows in thickness, and use a special jig (chuck) to sandwich both ends of the gel. The test is performed using a TENSILON TM tensile tester (model: 1310 A, manufactured by 0RIENTEC), and the stress at the time of fracture is defined as the tensile fracture stress ⁇ . The tensile speed is 10% 0min.
  • tensile rupture stress is calculated by the formula (force at tensile rupture ⁇ original cross-sectional area), and “tensile rupture strain” is (length at tensile rupture one-dimensional length) ⁇ ⁇ The value calculated by the formula of original length X 100%.
  • a frame with an outer edge length of 80 mm ⁇ 80 thighs and a width of 5 mm was cut out from a silicon plate having an area of 1 O OmmX l 00 mm and a thickness of 2 with a force cutter, and a 3 mm groove was made at one place of the frame.
  • the silicone frame was sandwiched between two 100 thighs x 10 Omm and a glass plate of 3 corrupt thickness to assemble a polymerization container.
  • the deoxygenated aqueous solution was poured into an opening of a silicon plate placed on one glass plate of the polymerization vessel, and the other glass plate was overlaid on the silicon plate to seal around the opening.
  • UV light 22 W, 0.34 A
  • UV light was used to irradiate with ultraviolet light at room temperature for 6 hours to polymerize, thereby producing an AMPS gel (first network structure) with a degree of crosslinking of 4 mol%.
  • the calculation of the degree of crosslinking is as follows:
  • the gel was taken out of the immersion liquid, cut into a suitable size, and then sandwiched between two glass plates with a width of 10 OmmX, a length of 10 OmmX, and a thickness of 3 mm to prevent air bubbles from entering. .
  • ultraviolet light was irradiated for 6 hours at room temperature using a 365 nm wavelength UV lamp (22 W, 0.34 A).
  • the AAm monomer diffused in the gel was polymerized to obtain a double network type gel.
  • the degree of crosslinking of the second network structure of this double network type gel was 0.1 mol%. The calculation of the degree of cross-linking is as follows: ⁇ ( ⁇ .
  • the obtained double network type gel was dried with hot air on a wire mesh at 150 ° C. for 2 hours.
  • the dried product was pulverized using a hammer mill to obtain a water absorbent resin.
  • the deoxygenated aqueous solution was poured into an opening of a silicon plate placed on one glass plate of the same polymerization vessel as in Example 1, and the other glass plate was overlaid on the silicon plate to cover the periphery of the opening.
  • a UV lamp with a wavelength of 365 nm 22 W, 0.34 A was irradiated with ultraviolet rays at room temperature for 6 hours to polymerize, thereby producing a gel having a degree of crosslinking of 111101%.
  • the immersion solution and 4 g of the single network type gel were placed in a sealed container having a sufficiently larger capacity than the gel.
  • the container was placed in a refrigerator at 4 ° C. for 24 hours, and the monomer, crosslinking agent and initiator in the immersion solution were diffused and permeated into the gel. In this process, the container was occasionally gently shaken in order to equalize the concentration of the immersion liquid.
  • the gel was taken out of the immersion liquid, cut into an appropriate size, and then sandwiched between two glass plates having a width of 10 OmmX, a length of 10 OmmX, and a thickness of 3 mm so as not to mix bubbles.
  • ultraviolet light was irradiated for 6 hours at room temperature using a 365 nm wavelength UV lamp (22 W, 0.34 A).
  • the AAm monomer diffused in the gel was polymerized to obtain a double network gel.
  • the degree of cross-linking of the second network structure of this double-net gel is 0.1 mol. /. Met.
  • the obtained double network type gel was dried with hot air on a wire mesh at 150 ° C. for 2 hours.
  • the dried product was pulverized using a hammer mill to obtain a water-absorbing resin.
  • the first network structure is PAMPS with a monomer concentration of 1 M and a degree of crosslinking of 4 mol%
  • the second network structure is a double network type gel with a monomer concentration of 1 M and a degree of crosslinking of 0.1 mol% PAAm. Is expressed as 1 P AMP S 4_1 PAAmO.1.
  • the monomer concentration here is the concentration at the time of manufacture and is different from the final monomer amount in the gel. That is, for example, when the first monomer concentration and the second monomer concentration are both 1M, the molar ratio of these in the finally obtained hydrogel is not 1: 1.
  • a hide mouth gel was prepared by introducing various metal ions into the double network type gel of 1 P AMP S 4 — 1 P AAmO. 1 obtained in Example 3.
  • a pure, equilibrium-swelled double network gel was cut out to an appropriate size and then vacuum-dried once. Then, aqueous solutions of various metal salts were adjusted to 20 times the gel volume at the time of equilibrium swelling, and the gel was immersed for about one week. The concentration of the aqueous solution is, for Z n S0 4, 0. 0 1M ( Example 5-1),
  • Example 5 0. 1M (Example 5-2), three kinds of 1M (Example 5-3), with respect to the F e C l 3, 0. 0 1M ( Example 5 4), 0. 1 M (Example 5 — 5) and 0.3 M (Examples 5-6) were prepared. After the metal ions were introduced into the hide-mouth gel in this way, the gel was dried and ground by the procedure described in Example 1 to obtain a water-absorbent resin.
  • Test Example 1 Physical properties of water absorbent resin
  • Table 3 shows the degree of crosslinking, the water content and the monomer ratio of the first and second network structures in the water-absorbent resins obtained in Examples 1 to 5.
  • Figure 5 shows the test system used this time.
  • a He—Ne laser (model 127, Spectra-Physics Laser, Inc.) was used as the light source 4.
  • the axis of the polarizer 5 was arranged vertically, and the axis of the analyzer 9 was arranged parallel.
  • the fast axes of the two 1/4 plates 68 were set at ⁇ / 4 and 1 ⁇ / 4 radians, respectively, with respect to the polarizer 5 and analyzer 9 axes.
  • Photoelastic images were recorded with a cooledC CD camera (C4742-95, Hamamatsu Co., Japan) connected to a personal computer 11 (all image areas included 1280 x 1024 pixels).
  • Figure 6 shows an image diagram showing the degree of stress dispersion taken by this CCD camera.
  • the discolored area means that stress is concentrated.
  • P AMP S- P AAm Hyde opening image (a) of the gel (the degree of crosslinking of PAAm is 0.1 mol 0/0)
  • P AMP S- PAAm Hyde port gel (P Degree of crosslinking of A Am 2 mol 0/0) compared to the image (b) and this the color transition range is small seen in the.
  • the hydrated gel according to the present invention with optimized mechanical strength has excellent stress dispersibility.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Absorbent Articles And Supports Therefor (AREA)

Abstract

L'invention concerne un procédé destiné à produire une résine hydroabsorbante possédant une structure de réseau à intrusion mutuelle ou une structure de réseau à intrusion semi-mutuelle. Ce procédé comprend une première étape consistant à polymériser un monomère insaturé possédant une charge électrique tout en réticulant le polymère résultant en présence d'un solvant de manière à former une première structure de réseau, et une seconde étape consistant à introduire un monomère insaturé électriquement neutre dans la première structure de réseau et à polymériser le second monomère en présence d'un solvant de sorte à former un second polymère dans la première structure de réseau, ou éventuellement à encore réticuler le second polymère de façon à former une seconde structure de réseau à l'intérieur de la première structure de réseau. Lorsqu'il est polymérisé et réticulé, le second polymère présente un degré de réticulation inférieur à celui du premier polymère. La résine hydroabsorbante contient le premier constituant monomère et le second constituant monomère dans un rapport molaire du premier constituant au second constituant compris entre 1:2 et 1:100. Une résine hydroabsorbante produite au moyen de ce procédé peut être utilisée comme matière absorbante dans un article tel qu'une couche-culotte.
PCT/JP2003/011245 2003-09-03 2003-09-03 Resine hydroabsorbante et son procede de production WO2005023877A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PCT/JP2003/011245 WO2005023877A1 (fr) 2003-09-03 2003-09-03 Resine hydroabsorbante et son procede de production
AU2003261904A AU2003261904A1 (en) 2003-09-03 2003-09-03 Water-absorbing resin and method for manufacturing the same

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP2003/011245 WO2005023877A1 (fr) 2003-09-03 2003-09-03 Resine hydroabsorbante et son procede de production

Publications (1)

Publication Number Publication Date
WO2005023877A1 true WO2005023877A1 (fr) 2005-03-17

Family

ID=34260121

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2003/011245 WO2005023877A1 (fr) 2003-09-03 2003-09-03 Resine hydroabsorbante et son procede de production

Country Status (2)

Country Link
AU (1) AU2003261904A1 (fr)
WO (1) WO2005023877A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102604609A (zh) * 2012-02-07 2012-07-25 中国石油天然气股份有限公司 异部交联堵水调剖凝胶剂及其制备方法
WO2019235108A1 (fr) * 2018-06-06 2019-12-12 富士フイルム株式会社 Modificateur, composition, film de revêtement dur, articule pourvu du film de revêtement dur et dispositif d'affichage d'image
EP3795633A1 (fr) * 2019-09-23 2021-03-24 Vito NV Procédé de production d'un hydrogel

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63186712A (ja) * 1987-01-29 1988-08-02 Mitsubishi Petrochem Co Ltd スポンジの吸水性改良法
JPH05320270A (ja) * 1992-05-27 1993-12-03 Nippon Kayaku Co Ltd 吸水性ポリマーの製造法
JPH09249812A (ja) * 1996-03-17 1997-09-22 Miyuki Mitsuda 金属粒子・イオンおよびキレート形成 分子網目の構築および利用方法
JPH11130968A (ja) * 1997-10-29 1999-05-18 Mitsubishi Chemical Corp 吸水性樹脂及びその製造方法
WO2001037660A1 (fr) * 1999-11-19 2001-05-31 Nof Corporation Preparation du type dispersion aqueuse a liberation prolongee, et procede de production correspondant
JP2002105344A (ja) * 2000-09-28 2002-04-10 Fuji Xerox Co Ltd 高分子ゲル組成物およびその製造方法、並びにそれを用いた光学素子

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63186712A (ja) * 1987-01-29 1988-08-02 Mitsubishi Petrochem Co Ltd スポンジの吸水性改良法
JPH05320270A (ja) * 1992-05-27 1993-12-03 Nippon Kayaku Co Ltd 吸水性ポリマーの製造法
JPH09249812A (ja) * 1996-03-17 1997-09-22 Miyuki Mitsuda 金属粒子・イオンおよびキレート形成 分子網目の構築および利用方法
JPH11130968A (ja) * 1997-10-29 1999-05-18 Mitsubishi Chemical Corp 吸水性樹脂及びその製造方法
WO2001037660A1 (fr) * 1999-11-19 2001-05-31 Nof Corporation Preparation du type dispersion aqueuse a liberation prolongee, et procede de production correspondant
JP2002105344A (ja) * 2000-09-28 2002-04-10 Fuji Xerox Co Ltd 高分子ゲル組成物およびその製造方法、並びにそれを用いた光学素子

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102604609A (zh) * 2012-02-07 2012-07-25 中国石油天然气股份有限公司 异部交联堵水调剖凝胶剂及其制备方法
CN102604609B (zh) * 2012-02-07 2014-11-19 中国石油天然气股份有限公司 异部交联堵水调剖凝胶剂及其制备方法
WO2019235108A1 (fr) * 2018-06-06 2019-12-12 富士フイルム株式会社 Modificateur, composition, film de revêtement dur, articule pourvu du film de revêtement dur et dispositif d'affichage d'image
CN112004838A (zh) * 2018-06-06 2020-11-27 富士胶片株式会社 改性剂、组合物、硬涂膜、具备硬涂膜的物品及图像显示装置
JPWO2019235108A1 (ja) * 2018-06-06 2021-04-22 富士フイルム株式会社 改質剤、組成物、ハードコートフィルム、ハードコートフィルムを備えた物品、及び画像表示装置
EP3795633A1 (fr) * 2019-09-23 2021-03-24 Vito NV Procédé de production d'un hydrogel

Also Published As

Publication number Publication date
AU2003261904A1 (en) 2005-03-29

Similar Documents

Publication Publication Date Title
KR101002147B1 (ko) (세미)상호침입 메쉬 구조 하이드로겔 및 그의 제조 방법
Dai et al. Synthesis and response of pineapple peel carboxymethyl cellulose-g-poly (acrylic acid-co-acrylamide)/graphene oxide hydrogels
Bahram et al. An introduction to hydrogels and some recent applications
Zhao et al. Mechanically strong and thermosensitive macromolecular microsphere composite poly (N-isopropylacrylamide) hydrogels
CN104448161B (zh) 一种改性明胶纳米微球交联的有机复合水凝胶及其制备方法
CN103145920B (zh) 一种温度、pH、紫外光多刺激响应半互穿网络纳米复合水凝胶的制备方法
CN103145914B (zh) 一种高强度pH、温度快速双响应纳米复合水凝胶的制备方法
Omidian et al. Swelling and mechanical properties of modified HEMA-based superporous hydrogels
Cheng et al. Recent advances in tough and self-healing nanocomposite hydrogels for shape morphing and soft actuators
Puig et al. Microstructured polyacrylamide hydrogels prepared via inverse microemulsion polymerization
Zhang et al. Multi-responsive, tough and reversible hydrogels with tunable swelling property
JPH0577453B2 (fr)
CN113024732B (zh) 一种近红外光响应n-异丙基丙烯酰胺基水凝胶及其制备方法、应用
Kumru et al. Tough high modulus hydrogels derived from carbon-nitride via an ethylene glycol co-solvent route
KR101068499B1 (ko) 온도 및 ｐＨ 감응형 하이드로젤의 제조방법
Ghazinezhad et al. A review of frontal polymerization in the chemical industry
CN110724283B (zh) 一种紫外光辅助自修复的高强度离子凝胶、制备方法及修复方法
JP5939796B2 (ja) キチンまたはキトサンと合成高分子との複合体およびその製造方法
JP2006213868A (ja) ゲルおよびその製造方法
CN103333294B (zh) 一种高强度的抗蛋白质吸附水凝胶及其制备方法和应用
Patil et al. CdS quantum dots doped tuning of deswelling kinetics of thermoresponsive hydrogels based on poly (2-(2-methoxyethoxy) ethyl methacrylate)
JP5285839B2 (ja) 高分子複合ゲルの製造方法
WO2005023877A1 (fr) Resine hydroabsorbante et son procede de production
JP2004292592A (ja) 高強度含水ゲルおよびその製造方法
US11786884B2 (en) Superabsorbent polymers based on copolymers of charged monomers and neutral monomers

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: JP

WWW Wipo information: withdrawn in national office

Country of ref document: JP