WO2016195376A1 - Résine super-absorbante - Google Patents

Résine super-absorbante Download PDF

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Publication number
WO2016195376A1
WO2016195376A1 PCT/KR2016/005809 KR2016005809W WO2016195376A1 WO 2016195376 A1 WO2016195376 A1 WO 2016195376A1 KR 2016005809 W KR2016005809 W KR 2016005809W WO 2016195376 A1 WO2016195376 A1 WO 2016195376A1
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WIPO (PCT)
Prior art keywords
weight
superabsorbent
super absorbent
polymer
superabsorbent polymer
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PCT/KR2016/005809
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English (en)
Korean (ko)
Inventor
이상기
남혜미
황민호
이수진
장태환
Original Assignee
주식회사 엘지화학
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Priority claimed from KR1020160067426A external-priority patent/KR101871968B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to US15/558,429 priority Critical patent/US11059025B2/en
Priority to CN201680017149.8A priority patent/CN107406562B/zh
Priority to EP16803731.5A priority patent/EP3249001B1/fr
Publication of WO2016195376A1 publication Critical patent/WO2016195376A1/fr

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    • 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
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C08J3/075—Macromolecular gels
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
    • C08J9/08—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing carbon dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes

Definitions

  • the present invention relates to a super absorbent polymer in which re-wetting prevention effect is remarkably improved.
  • Super Absorbent Polymer is a synthetic polymer material capable of absorbing water of 500 to 1,000 times its own weight. Each developer has a super absorbent material (SAM) and an AGKAbsorbent Gel Mater. i al). Such superabsorbent polymers have been put into practical use as sanitary instruments, and now, in addition to hygiene products such as paper diapers and sanitary napkins for children, ' horticulture soil repair, civil engineering, building index materials, seedling sheets, food freshness, etc. It is widely used as a material for agent, and poultice.
  • these superabsorbent polymers are widely used in the field of sanitary products such as diapers and sanitary napkins.
  • the superabsorbent polymers need to exhibit high absorption of moisture and must not escape moisture absorbed by external pressure.
  • it is necessary to maintain good shape even in the state of volume expansion (swelling) by absorbing water, thereby showing excellent permeabi li ty.
  • hygiene materials such as diapers and sanitary napkins may be pressured by the user and weight.
  • the superabsorbent polymer applied to hygiene materials such as diapers or sanitary napkins absorbs the liquid
  • some of the liquid absorbed by the superabsorbent polymer is rewet. This can happen. Therefore, various attempts have been made to improve the absorption capacity and liquid permeability under pressure to suppress such rewetting.
  • the present invention provides a super absorbent polymer which can effectively suppress the rewet phenomenon while showing excellent absorbent physical properties.
  • One embodiment of the invention has the following configuration.
  • Centrifugal water retention (CRC) for physiological saline is 28 to 35 g / g
  • 0.9 psi pressure absorption capacity (AUL) for physiological saline is 14 to 22 g / g
  • free swelling for physiological saline The superabsorbent polymer according to any one of the above (1) to (4), wherein the gel bed transmittance (GBP) is 40 to 100 darcy and the vortex time is 20 to 60 seconds.
  • Another embodiment of the invention has the following configuration.
  • cross-linking a monomer mixture comprising a water-soluble ethylenically unsaturated monomer having a neutralized acidic group, at least a portion thereof, a blowing agent, a bubble accelerator, and a surfactant in the presence of an internal crosslinking agent to form a hydrogel layer; Drying, pulverizing and classifying the hydrogel polymer to form a base resin powder; And in the presence of a surface crosslinking agent, further crosslinking the surface of the base resin powder to form a surface crosslinking layer.
  • the blowing agent is from about 0.05 to about 5.0 weight percent of the total monomer mixture
  • the bubble promoter is from about 0.01 to about 3 weight percent of the total monomer mixture
  • the surfactant is from about 0.001 to the total monomer mixture
  • the superabsorbent polymer according to one embodiment of the present invention may exhibit a fast absorption rate and high gel strength even in a partially swollen state by optimizing the size of the partially swollen gel particles. Accordingly, the use of the super absorbent polymer can effectively prevent rewetting.
  • 1 to 3 are schematic diagrams of exemplary devices for measuring gel bed permeability and components included in the devices.
  • a superabsorbent polymer having an average particle diameter of 300 to 600, a gel obtained by swelling the superabsorbent resin lg in 20 g of 0.9 wt% sodium chloride aqueous solution for 10 minutes is a high particle diameter of 600 to 1000 zm
  • An absorbent resin is provided.
  • the average particle diameter of the gel obtained by partially swelling the super absorbent polymer having an average particle diameter of 300 to 600 kPa under the above conditions is within 600 to 100Oj i, such superabsorbent resin has an optimized pore size and porosity. It was confirmed that the present invention exhibits a rapid absorption rate and excellent liquid permeability. In addition, the superabsorbent polymer exhibits a rapid absorption rate, excellent pressure absorbing ability, and liquid permeability even in a partially swollen state due to such characteristics, thereby rewetting a liquid absorbed into the superabsorbent polymer by external pressure. It was confirmed that can effectively prevent and completed the invention.
  • the superabsorbent polymer may have an average particle diameter of 600 to 1000, 650 to 950 or 700 to 900 mi of the gel obtained by partially swelling under the above conditions.
  • Such a super absorbent polymer may have an optimized pore size and porosity, and thus may exhibit a fast absorption rate and excellent liquid permeability, thereby exhibiting a better rewet prevention effect.
  • the average particle diameter of the gel obtained by the partial swelling can be measured by various methods known in the art using the gel obtained by partially swelling the superabsorbent polymer under the above-described conditions.
  • the superabsorbent polymer lg is put into a plastic bag, and 20 g of 0.9 wt% physiological saline is injected to swell the superabsorbent polymer for 10 minutes to obtain a gel.
  • the vinyl bag any vinyl bag of a material which does not absorb physiological saline may be used.
  • a vinyl bag of PE (polyethylene) material may be used.
  • silica may be added to facilitate the measurement of the average particle diameter of the gel.
  • Silica is wet the surface of the gel can be suppressed to stick to each other in the gel classification process. Since due to the addition of the silica is not distributed is changed, the particle size of the gel, the silica to have a hydrophobic or hydrophilic silica may be used if all possible to suppress the developer adhering to each other during the classification process of the gel. In addition, since the particle size distribution of the gel is not affected by the addition content of silica, silica can be used in an appropriate content. As a non-limiting example, in order to reproducibly obtain the same particle size distribution, layered silica may be applied to the gel surface to measure the particle size of the gel.
  • the average particle diameter of the gel can be measured through various methods known in the art.
  • the average particle diameter of the gel may be measured according to the European Di Sposables and Nonwovens Associ at ion (EDANA) standard EDANA WSP 220.2 method.
  • EDANA European Di Sposables and Nonwovens Associ at ion
  • the room temperature may mean a temperature of about 1 to 3 (rC, about 5 to 30 ° C or about 15 to 25 ° C as a natural temperature that is not warmed or reduced.
  • the superabsorbent polymer having the average particle diameter of the gel obtained by partial swelling under the above-described conditions satisfying the above-described range may exhibit a uniform particle size distribution.
  • the super absorbent polymer of the embodiment may include 45 to 85 wt% of particles having a bib diameter of 300 / rni to 600. Accordingly, the superabsorbent polymer has a fast absorption rate and excellent gel even after partial swelling. It can show strength.
  • the super absorbent polymer according to the embodiment may include 15 to 25% by weight of particles having a particle size of more than 0 300 / m or less.
  • the superabsorbent polymer is partially swollen to easily form a gel having a uniform particle size distribution, it is possible to provide gel particles having a small particle size from the superabsorbent polymer having a small particle size. Accordingly, the super absorbent polymer exhibiting the particle size distribution may exhibit an improved anti-wetting effect.
  • the superabsorbent polymer may include 45 to 85 wt% of particles having a particle size of 300 to 600 kPa, and 15 to 25 wt% of particles having a particle size of greater than 0 to 300 zm or less.
  • the super absorbent polymer may include particles having a particle size of more than 600 of the remaining amount. Superabsorbent polymers having such particle size distributions can exhibit improved absorption rates and gel strength in the partially swollen state.
  • the superabsorbent polymer according to one embodiment may be a fraction of the gel having a particle diameter of more than 0 and less than 600 is 5% to 30% by weight or 5% to 20% by weight. At this time, the gel is obtained by partially swelling the superabsorbent polymer under the above-described conditions.
  • Such superabsorbent resins may exhibit faster absorption rates and higher gel strengths, due to small particle size gel particles even in some swollen conditions. Accordingly, the super absorbent polymer may exhibit a remarkably improved rewet prevention effect.
  • the fraction of the gel having a particle size of more than 0 and 600 or less may satisfy the above-mentioned range.
  • the superabsorbent polymer according to the embodiment in which the average particle diameter of the gel obtained by partially swelling the superabsorbent polymer under the above-described conditions satisfies the above-described range has excellent porosity and porosity, and thus exhibits excellent absorption and overall performance. Can be.
  • the super absorbent polymer has a centrifugal water retention (CRC) of physiological saline of 28 g / g to 35 g / g, 28.5 g / g to 34 g / g Or 29 g / g to 33 g / g, and a 0.9 ps i pressurized absorption capacity (AUL) for physiological saline is 14 g / g to 22 g / g, 15 g / g to 21 g / g, 16 g / g To 20 g / g or 18 g / g to 20 g / g, free swelling gel bed permeability (GBP) for physiological saline is 40 to 100 darcy, 45 to 90 darcy or 50 to 80 darcy, vortex time 20 It may exhibit a property of seconds to 60 seconds, 25 to 55 seconds, or 30 to 50 seconds.
  • CRC centrifugal water retention
  • AUL 0.9 ps i press
  • the superabsorbent polymer according to the embodiment exhibiting such characteristics not only has excellent basic absorbent performance, but also shows a remarkably improved anti-wetting effect, so that it can be applied to various hygiene products such as diapers to exhibit very excellent overall physical properties. Can be.
  • the superabsorbent polymer according to the embodiment exhibiting such characteristics includes particles having a particle size of 300 to 600 m as 45 to 85 weight 3 ⁇ 4> or 15 to 25 weight particles having a particle size of more than 0 and 300 or less. If the content of the gel is included as 3 ⁇ 4, the fraction of the gel having a particle diameter of more than 0 and less than 600 or less than 5% by weight to 30% by weight, or two or more of these conditions are satisfied, the basic physical properties of the superabsorbent polymer are excellent. Even in some swelled state, it shows excellent absorption rate and gel strength, and can show remarkably improved anti-wetting effect and high drying efficiency.
  • the centrifugal water retention capacity (CRC) for the physiological saline can be measured according to the method of the EDANA method WSP 241.2. More specifically, the water retention capacity is prepared by classifying the super absorbent polymer to prepare a super absorbent polymer having a particle size of 300 to 600, absorbed in physiological saline over 30 minutes, and calculated by the following formula Can be:
  • W 0 (g) is the initial weight (g) of the superabsorbent polymer having a particle size of 300 to 600
  • Kg) is a device measured after dehydration at 250G for 3 minutes using a centrifuge without using a superabsorbent polymer Weight
  • W 2 (g) has a particle diameter of 300 ⁇ 600 ⁇ in 0.9 wt% of normal saline at room temperature
  • the superabsorbent polymer was immersed in water for 30 minutes, absorbed therein, and then dehydrated at 250 G for 3 minutes using a centrifuge. The weight of the superabsorbent polymer was measured.
  • the pressure absorption capacity (AUL) of 0.9 psi can be measured according to the method of EDANA method WSP 242.2. More specifically, the pressure-absorbing capacity may be calculated according to the following formula 2 after absorbing the superabsorbent polymer in physiological saline under a pressure of about 0.9 psi over 1 hour:
  • AUL (g / g) [W 4 (g)-W 3 (g)] / W 0 (g)
  • W 0 (g) is the superabsorbent polymer's .
  • Initial weight (g) is the sum of the weight of the superabsorbent resin and the weight of the device capable of loading the superabsorbent resin
  • W 4 (g) is 1 hour under load (0.9 psi) After absorbing physiological saline to the superabsorbent polymer, the sum of the weight of the superabsorbent polymer and the weight of the device capable of applying a load to the superabsorbent polymer.
  • W 0 (g) described in Formulas 1 to 2 corresponds to an initial weight (g) before absorbing the superabsorbent polymer in physiological saline, and may be the same or different.
  • GBP Gel bed permeability for the physiological saline
  • Idarcy means that a liquid with a viscosity of lcP flows 1 cm 2 per second through 1 cm 2 under a pressure gradient of 1 atmosphere per cm.
  • Gel bed permeability has the same units as area Idarcy are as 0.98692 x 10- 12 m 2 or 0.98692 X 10- 8 cm 2.
  • GBP is the permeability (or transmittance) of the swollen gel layer (or bed) under the free swell state of 0 ps i (Gel Bed Permeabi 1 i ty (GBP) Under Opsi Swel Pressure Test), and the GBP may be measured using the apparatus shown in FIGS. 1 to 3.
  • an apparatus 500 for measuring GBP Test device assembly 528 includes a sample container 530 and a plunger 536.
  • the plunger includes a shaft 538 having a cylinder hole drilled down the longitudinal axis and a head 550 positioned at the bottom of the shaft.
  • the diameter of the shaft hole 562 is about
  • the plunger head is attached to the shaft by an adhesive, for example. Twelve holes 544 are drilled in the radial axis of the shaft, and the diameter of three holes located every 90 ° is about 6.4 mm.
  • the shaft 538 is machined from a LEXAN rod or equivalent material and has an outer diameter of about 2.2 cm and an inner diameter of about 16 mm 3.
  • Plunger head 550 has seven inner holes 560 and fourteen outer holes 554, all of which have a diameter of about 8.8 mm. In addition, a hole of about 16 mm is aligned with the shaft.
  • the plunger head 550 is machined from a LEXAN rod or equivalent material and is about 16 mm in height and has a minimum wall clearance (wal l cl earance) that fits snugly inside the cylinder 534 but still moves freely. It is made in size.
  • the total length of the plunger head 550 and shaft 538 is about 8.25 cm, but can be machined at the top of the shaft to obtain the desired size of the plunger 536.
  • the plunger 536 is biaxially stretched and includes a 100 mesh stainless steel cloth screen 564 attached to the bottom of the plunger 536. Attach the screen to the plunger head 550 using a suitable solvent that will securely attach the screen to the plunger head 550.
  • the sample vessel 530 includes a cylinder 534 and a 400 mesh stainless steel cloth screen 566 which is biaxially stretched and taut and attached to the bottom of the cylinder 534.
  • the screen is attached to the cylinder using a suitable solvent to securely adhere to the cylinder. Care must be taken to avoid excess solvent moving into the openings of the screen, reducing the pore area for liquid flow.
  • Acrylic solvent Weld-on 4 from IPS Corporat ion place of business, Gardena, California, USA
  • the gel particle sample (swelled superabsorbent resin), indicated at 568 in FIG. 2, is supported on the screen 566 inside the cylinder 534 during the test.
  • the cylinder 534 may be drilled in a transparent LEXAN rod or even material, or cut into a LEXAN tubing or even material, having an inner diameter of about 6 cm (e.g., a cross section of about 28.27 cm 2 ) and a wall thickness. It may be manufactured to about 0.5 cm and about 7.95 cm in height.
  • the step may be formed by machining the outer diameter of the cylinder 534 such that the portion 534a having an outer diameter of 66 mm is present at the bottom 31 mm of the cylinder 534.
  • An o-ring 540 may be placed at the top of the step to match the diameter of the region 534a.
  • the annul ar weight 548 has counter-bored holes about 2.2 cm in diameter and 1.3 cm in depth, so it freely slides onto the shaft 538.
  • the annular weight also has a thru-bore 548a of about 16 mm 3.
  • the annular weight 548 can be made of stainless steel or other suitable material that can resist corrosion by physiological saline (aqueous sodium chloride solution) of 0.9 weight 3 ⁇ 4>.
  • sample 568 is applied pressure over a sample area of about 28.27cm about 2 or about 0.3ps i 20.7dyne / cm which is the the sangung to the 2 (2.07kPa).
  • the sample vessel 530 is generally placed on a weir 600.
  • the purpose of the weir is to divert the overflowing liquid at the top of the sample vessel 530, which is diverted to a separate collection device 601.
  • the weir may be positioned above the bottom 602 where the beaker 603 is placed to collect physiological saline passing through the swollen sample 568.
  • a plunger 536 equipped with a weight 548 is placed in an empty sample vessel 530 and a weight of 548 up to 0.01 mm with a suitable gauge. The height from the top of the c) to the bottom of the sample vessel 530 is measured. The force exerted by the thickness gauge during the measurement should be as small as possible, preferably less than about 0.74 N.
  • the base on which the sample container 530 is placed is flat, and the surface of the weight 548 is preferably parallel to the bottom surface of the sample container 530.
  • a test sample is prepared from a superabsorbent resin having a particle size of about 300 to about 600 i that passes through a US standard 30 mesh screen and is maintained on a US standard 50 mesh screen.
  • About 2.0 g of sample is placed in sample vessel 530 and spread evenly over the bottom of the sample vessel.
  • the vessel containing 2.0 grams of sample without plunger 536 and weight 548 is immersed in 0.9 weight 3 ⁇ 4 saline for about 60 minutes to allow the sample to swell under pressure.
  • the sample container 530 is placed on a mesh located in the liquid reservoir so that the sample container 530 is slightly below the bottom of the liquid reservoir.
  • the mesh may be any one that does not affect the movement of physiological saline to the sample container 530.
  • Such mesh may be part number 7308 from Eagle Sup ly and Plast ic, Appleton, Wisconsin, USA.
  • the height of physiological saline during saturation can be adjusted such that the surface in the sample container is defined by the sample, not physiological saline.
  • the assembly of the plunger 536 and weight 548 is placed on the saturated sample 568 in the sample container 530 and then the sample container 530, plunger 536, weight 548. And sample 568 is taken out of solution.
  • the sample vessel 530, plunger 536, weight 548 and sample 568 are then left on a flat, large grid, uniform thickness, non-deformation plate for about 30 seconds, prior to GBP measurements.
  • the plate will prevent liquid in the sample vessel from releasing onto a flat surface due to surface tension.
  • the plate has a total dimension of 7.6 cm x 7.6 cm and each grid dimension may be 1.59 cm long by 1.59 cm wide by 1.12 cm deep.
  • a suitable plate material is a parabolic diffuser plate, catalog number 1624K27, available from McMaster Carr Supply Company, Chicago, Illinois, USA, which can be cut and used to the appropriate dimensions. '
  • the height from the top of the weight 548 to the bottom of the sample vessel 530 is measured again using the same thickness gauge as previously used. Height measurements should be made as soon as possible after the thickness gauge is fitted. Inside empty sample container 530 The height measurement of the empty assembly where the plunger 536 and weight 548 are located should be subtracted from the height measurement obtained after saturating the sample 568. The resulting value is the thickness or height of the saturated sample 568. In addition, if a plate is included in the assembly including the saturated sample 568, the height, including the plate should be measured when measuring the height of the empty assembly.
  • the GBP measurement begins with delivering 0.9% physiological saline into the sample vessel 530 containing the saturated sample 568, plunger 536 and weight 548. Adjust the f low rate of physiological formula water into the vessel so that the physiological saline overflows to the top of the cylinder 534, thereby resulting in a consistent head pressure equivalent to the height of the sample vessel 530.
  • Physiological saline may be added by any means sufficient to ensure a small but consistent amount of overflow from the top of the cylinder with instrument pump 604 or the like.
  • the overflow liquid is diverted into a separate collection device 601. Using the balance 602 and the beaker 603, the amount versus time of the solution passing through the sample 568 is measured gravimetrically.
  • the flow rate Q through the swollen sample 568 is in g / sec by the linear least-square fit of liquid (g) versus time (sec) passing through the sample 568. Decide on
  • the GBP (cm 2 ) can be calculated according to the following Equation 3 to confirm the gel bed transmittance.
  • ⁇ is the gel bed transmission (cm 2 )
  • H is the height (cm) of the swollen sample
  • ⁇ is an (viscosity of the test solution is from about lcP used for this "test), the liquid viscosity ( ⁇ ), A is the cross-sectional area for the liquid flow (28.27 ciif for the sample vessel used in this test)
  • p is the liquid density (g / cm 3 ) (about 1 g / cm 3 for the test solution used in this test),
  • P is the hydrostatic pressure (dyne / cm 2) (normally approximately 7, 797dyne / cm 2).
  • the vortex time can be measured in seconds according to the method described in International Publication No. 1987-003208. More specifically, the vortex time may be calculated by adding 2 g of superabsorbent resin to 50 mL of physiological saline and stirring at 600 rpm to measure the time until the vortex disappears in seconds.
  • the superabsorbent polymer of the embodiment in which the average particle diameter of the partially swollen gel under the aforementioned conditions is in the above-described range, may be provided by appropriately adjusting the structure or physical properties of various kinds of superabsorbent polymers known in the art. More specifically, the superabsorbent polymer of the above embodiment basically includes a crosslinked polymer crosslinked with a water-soluble ethylenically unsaturated monomer as a base resin powder, as in the previous superabsorbent resin, and on the base resin powder The formed surface crosslinking layer may be included. In addition, the superabsorbent polymer of the embodiment may include a component black which is adjusted so that the gel obtained by partial swelling under the above-described conditions has an average particle diameter in the above-described range.
  • the superabsorbent polymer of one embodiment may have an increased absorption area compared to the existing one so that the gel partially swollen under the above-described conditions may exhibit an average particle diameter in the above-described range.
  • gels partially swollen under the above-mentioned conditions using a foaming agent capable of generating bubbles during polymerization of the base resin powder, a foaming accelerator for promoting bubble generation, and a surfactant for stable foaming have an average particle diameter in the above-described range. It is possible to provide a superabsorbent polymer exhibiting.
  • the superabsorbent polymer of one embodiment is a hydrogel polymer by crosslinking and polymerizing a monomer mixture comprising a water-soluble ethylenically unsaturated monomer, a blowing agent, a bubble accelerator, and a surfactant having at least a portion of neutralized acid groups in the presence of an internal crosslinking agent.
  • a monomer mixture comprising a water-soluble ethylenically unsaturated monomer, a blowing agent, a bubble accelerator, and a surfactant having at least a portion of neutralized acid groups in the presence of an internal crosslinking agent.
  • the water-soluble ethylenically unsaturated monomer acrylic acid, methacrylic acid, maleic anhydride, fumaric acid, crotonic acid, itaconic acid, 2-acryloylethane sulfonic acid, 2-methacryloylethanesulfonic acid, 2 Anionic monomers of (meth) acryloylpropanesulfonic acid, or 2- (meth) acrylamide-2-methyl propane sulfonic acid and salts thereof; (Meth) acrylamide, N-substituted (meth) acrylamide, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, hydroxypolyethylene glycol (meth) acrylate or polyethylene glycol ( Nonionic hydrophilic-containing monomers of meth) acrylate; And an amino group-containing unsaturated monomer of ( ⁇ , ⁇ ) -dimethylaminoethyl (meth)
  • alkali metal salts such as acrylic acid or salts thereof, for example, acrylic acid and / or sodium salts of which at least a portion of acrylic acid is neutralized may be used, and the preparation of superabsorbent polymers having superior physical properties using such monomers may be used.
  • acrylic acid may be neutralized with a basic compound such as caustic soda (NaOH).
  • NaOH caustic soda
  • the degree of neutralization of the water-soluble ethylenically unsaturated monomer may be adjusted to about 50 to 95% black to about 70 to 85%, to provide a superabsorbent polymer having excellent water retention capability without fear of precipitation during neutralization within this range.
  • the concentration of the water-soluble ethylenically unsaturated monomer is about 20 to about 60% by weight relative to the total monomer mixture including each of the raw materials and the solvent described below, or It may be about 40 to about 50% by weight, and may be in an appropriate concentration in consideration of polymerization time and reaction conditions.
  • concentration of the monomer is too low, the yield of the superabsorbent polymer may be low and there may be a problem in economics.
  • the concentration is too high, a part of the monomer may precipitate or the grinding efficiency of the polymerized hydrogel polymer may be low. Etc. may cause problems in the process and may decrease the physical properties of the super absorbent polymer.
  • the bubble generation may be promoted by the foaming accelerator, and carbonates capable of stable foaming by the surfactant may be used.
  • Such carbonates include magnesium carbonate, calcium carbonate, sodium bicarbonate, sodium carbonate, potassium bicarbonate and potassium carbonate ( potassium carbonate) and one or more selected from the group consisting of.
  • an inorganic acid aluminum salt such as aluminum sulfate, aluminum chloride, or the like, or an organic acid aluminum salt such as aluminum lactate, aluminum oxalic acid, aluminum citric acid, aluminum uric acid, or the like may be used.
  • the average particle diameter of the partially swollen gel is It is out of range.
  • Silicone-based surfactants may be used as the surfactant for inducing stable bubble generation due to the blowing agent and the bubble promoter. These silicone-based surfactants have good water retention and proper porosity. It exhibits a pressure-absorbing capacity, and has an appropriate density, which can greatly contribute to providing a super absorbent polymer which is easy to handle in processes such as classification.
  • silicone-based surfactant polysiloxane including polyether as a side chain may be used.
  • poly (ethylene oxide) in the polydimethyl si loxane skeleton Alternatively, a silicone-based surfactant having a structure in which polyether side chains such as poly (propylene oxide) are bonded may be used.
  • examples of such surfactants include OFX-0190 Fluid (PEG / PPG-18 / 18 Dimethi cone), 0FX-0193 Fluid (PEG-12 Dimethi cone), OFX-5220 Fluid (PEG / PPG-17 by Xi ameter (R). / 18 Dimethi cone), OFX-5324 Fluid (PEG-12 Dimethicone).
  • the concentration of the blowing agent may be about 0.05 to about 5.0% by weight, or about 0.01 to about 3% by weight, based on the total monomer mixture.
  • the concentration of the bubble promoter may be about 0.01 to about 3 weight percent, or about 0.5 to about 2 weight percent, based on the total monomer mixture, and the concentration of the surfactant is about 0.001 to about the total monomer mixture.
  • black can be from about 0.01 to about 0.5.
  • bubble accelerator and surfactant in this range can significantly improve the absorption surface area by optimizing the pore size and porosity of the superabsorbent polymer, thereby improving the absorption rate and rewetting prevention effect.
  • a large amount of bubbles generated by using the foaming agent bubble accelerator and the surfactant is contained in the hydrogel polymer, so that the plurality of pores contained in the hydrogel polymer can be stably maintained in the subsequent process
  • a hydroxy group-containing compound can be used.
  • a hydroxy group-containing compound when used in the step of forming the hydrogel polymer, it is possible to shorten the gelation time by improving the viscosity of the polymerization solution during the crosslinking polymerization of the monomer mixture including a water-soluble ethylenically unsaturated monomer and the like. This effectively prevents the large amount of bubbles formed by the blowing agent or the like from escaping from the polymerization liquid so that the large amount of bubbles are contained in the hydrogel polymer.
  • the hydroxyl group-containing compound may be included in the resulting super absorbent polymer to improve the wettability of the super absorbent polymer. Accordingly, the pressureless and pressurized absorption rate of the super absorbent polymer can be further increased.
  • hydroxy group-containing compound a compound such as polyvinyl alcohol or a polyalkylene glycol such as polyethylene glycol may be used.
  • concentration of such hydroxy group containing compound can be used at about 0.01 to 1% by weight based on the total monomer mixture. In this content range, the absorption area and the wettability of the superabsorbent polymer can be effectively increased.
  • any internal crosslinking agent having a crosslinkable functional group which has been conventionally used in the production of superabsorbent polymers, can be used without particular limitation.
  • a multifunctional acrylate compound having a plurality of ethylene oxide groups may be used as the internal crosslinking agent.
  • Such internal crosslinking agents include polyethylene glycol diacrylate (PEGDA), glycerin diacrylate, glycerin triacrylate, unmodified or ethylated trimethylolpropane triacrylate (TMPTA), nucleic acid diol diacrylate, And triethyleneglycol diacrylate.
  • PEGDA polyethylene glycol diacrylate
  • TMPTA ethylated trimethylolpropane triacrylate
  • nucleic acid diol diacrylate ethylated trimethylolpropane triacrylate
  • triethyleneglycol diacrylate ethylated trimethylolpropane triacrylate
  • the monomer mixture may further include a polymerization initiator generally used for preparing a super absorbent polymer.
  • the polymerization initiator may use a thermal polymerization initiator or a photopolymerization initiator according to UV irradiation depending on the polymerization method.
  • a thermal polymerization initiator may further include a thermal polymerization initiator.
  • the photopolymerization posting agent may be used without limitation in the configuration as long as it is a compound capable of forming radicals by light such as ultraviolet rays.
  • photocharge initiator for example, benzoin ether, dialkyl acetophenone, hydroxyl alkylketone, phenylglyoxylate, One or more selected from the group consisting of benzyl dimethyl ketal, acyl phosphine and alpha-aminoketone can be used.
  • acylphosphine commercially available lucirin TP0, that is, 2,4,6-trimethyl-benzoyl-trimethyl phosphine oxide (2,4,6-t rimethyl -benzoyl -trimethyl phosphine oxide) can be used.
  • lucirin TP0 that is, 2,4,6-trimethyl-benzoyl-trimethyl phosphine oxide (2,4,6-t rimethyl -benzoyl -trimethyl phosphine oxide) can be used.
  • a wider variety of photoinitiators are well specified in Reinhold Schwalm lm "UV Coatings: Basics, Recent Developments and
  • the photopolymerization initiator may be included in a concentration of about 0.01 wt% to about 1.0 wt% based on the monomer mixture. When the concentration of the photopolymerization initiator is too low, the polymerization rate may be slow. When the concentration of the photopolymerization initiator is too high, the molecular weight of the superabsorbent polymer may be low and the physical properties may be uneven.
  • the thermal polymerization initiator may be used at least one selected from the group consisting of persulfate initiator, azo initiator, hydrogen peroxide and ascorbic acid.
  • persulfate-based initiators include sodium persulfate (Na 2 S 2 0 8 ), potassium persulfate (K 2 S 23 ⁇ 4), ammonium persulfate (NH 4 ) 2 S 2 0 8 ), and examples of azo initiators include 2,2-azobis— (2—amidinopropane) dihydrochloride (2,2_azobis (2— amidinopropane) dihydrochlor ide) and 2,2 azo.
  • the thermal polymerization initiator is about 0.001 to about the monomer mixture. It may be included at a concentration of about 0.5% by weight. When the concentration of the thermal polymerization initiator is too low, additional thermal polymerization hardly occurs, so that the effect of the addition of the thermal polymerization initiator may be insignificant. When the concentration of the thermal polymerization initiator is too high, the molecular weight of the superabsorbent polymer may be low and the physical properties may be uneven. have. .
  • the monomer mixture may further include additives such as thickeners, plasticizers, preservative stabilizers, and antioxidants.
  • Raw materials such as the above-mentioned water-soluble ethylenically unsaturated monomers, blowing agents, foam accelerators, surfactants, photopolymerization initiators, thermal polymerization initiators, internal crosslinking agents and additives may be prepared in the form of a monomer mixture solution dissolved in a solvent.
  • the solvent that can be used at this time can be used without limitation in the configuration as long as it can dissolve the above components, for example, water, ethanol, ethylene glycol, diethylene glycol, triethylene glycol, 1,4-butanediol, Propylene glycol, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl ethyl ketone, acetone, methyl amyl ketone, cyclonucleanone, cyclopentanone, diethylene glycol monomethyl ether, diethylene glycol Ethyl ether, toluene, xylene, butyrolactone, carby, methyl cellosolve acetate, and one or more selected from ⁇ , ⁇ -dimethylacetamide and the like can be used in combination.
  • the solvent may be included in the remaining amount except for the above-described components with respect to the total content of the monomer mixture.
  • the method of forming a hydrogel polymer by thermal polymerization or photopolymerization of such a monomer mixture may be carried out in a reactor having a stirring shaft, such as kneader (kneader) to promote the generation of bubbles.
  • a stirring shaft such as kneader (kneader) to promote the generation of bubbles.
  • the hydrogel polymer discharged to the reaction vessel outlet by supplying a polymerization energy source such as heat or light to a reaction vessel such as a kneader having a stirring shaft may be formed according to the shape of the stirring shaft provided in the reaction vessel. It may be in the form of centimeters to several millimeters. Specifically, the size of the hydrogel polymer obtained may vary depending on the concentration and the injection speed of the monomer mixture to be injected, usually a hydrogel having a weight average particle diameter of about 2 to 50 mm 3 Polymers can be obtained.
  • the normal water content of the hydrogel polymer obtained by the above method is about
  • water content is the amount of water to the total weight of the hydrogel gel polymer means the weight of the hydrogel polymer minus the weight of the dry polymer. It is defined as a value calculated by measuring the weight loss due to moisture evaporation in the polymer during drying by raising the temperature of the polymer, in which drying conditions are increased by raising the temperature from room temperature to about 180 ° C and maintaining the temperature at 18 CTC. The drying time is set to 20 minutes, including the temperature rise step 5 minutes, to measure the moisture content.
  • a base resin powder through a process such as drying, grinding and classification, the base resin powder and the super absorbent polymer obtained therefrom through such a process such as grinding and classification Suitably manufactured and provided to have a particle diameter of about 150 to 850. More specifically, at least about 95% by weight or more of the base resin powder and the superabsorbent polymer obtained therefrom will have a particle size of about 150 to 850 / mm 3, and the fine powder having a particle size of less than about 150 will be less than about 3% by weight. Can be.
  • the superabsorbent resin finally prepared may exhibit excellent absorption properties.
  • the pulverizer used is not limited in configuration, and specifically, a vertical pulverizer, a turbo cutter, a turbo grinder, a rotary cutter mill, a cutting machine Cutter mill, Disc mill, Shred crusher, Crusher, Chopper and Disc cutter It may include any one selected from the group of grinding devices consisting of a cutter), but is not limited to the above-described example.
  • the coarse grinding step may be pulverized so that the particle size of the hydrogel polymer is about 2 to about 10 ⁇ .
  • drying is carried out for the polymerization—the hydrous gel polymer immediately after the coarse grinding or the black without the coarse grinding step.
  • the drying temperature of the drying step may be about 50 to about 250 ° C.
  • the drying temperature is less than about 50 ° C, the drying time may be too long and the physical properties of the final superabsorbent polymer may be lowered.
  • the drying temperature exceeds about 250 ° C, only the polymer surface is dried excessively. It may result in further comprising milling step sseseo differential, "there is a high possibility that the physical properties of the water absorbent resin reduced to be finally formed.
  • drying time may be performed for about 20 minutes to about 15 hours, in consideration of process efficiency and the like, but is not limited thereto.
  • the drying method of the drying step is also commonly used as a drying step of the hydrogel polymer, it can be selected and used without limitation. Specifically, the drying step may be performed by hot air supply, infrared irradiation, microwave irradiation, or ultraviolet irradiation.
  • the water content of the polymer after the drying step may be about 0.1 to about 10% by weight.
  • the polymer powder obtained after the grinding step may have a particle diameter of about 150 to about 850 zm. Mills used to grind to such particle diameters are specifically pin mills, hammer mills, screw mills, mills, disc mills or jogs. A jog mill or the like may be used, but is not limited to the example described above.
  • a separate process of classifying the polymer powder obtained after grinding according to the particle size may be performed.
  • the polymer having a particle size of about 150 to about 850 may be classified and commercialized only through the surface crosslinking reaction step for the polymer powder having such a particle size. Since the particle size distribution of the base resin powder obtained through this process has already been described above, a detailed description thereof will be omitted.
  • the surface of the base resin powder in the presence of a surface crosslinking agent, can be further crosslinked to form a surface crosslinking layer, thereby producing a super absorbent polymer.
  • the surface crosslinking layer may be formed using a surface crosslinking agent that has been used for the production of superabsorbent polymers.
  • a surface crosslinking agent all known in the art may be used without any particular limitation. More specific examples thereof include ethylene glycol, propylene glycol, 1, 4-butanediol, 1,6-nucleic acid diol, 1, 2-nucleic acid di, 1, 3-nucleic acid di, 2-methyl-1, 3-propanedi, 2, 5- nucleic acid di, 2-methyl-1, 3-pentanediol, 2-methyl-2, 4-pentanediol, tripropylene glycol, glycerol, one or more selected from the group consisting of ethylene carbonate and propylene carbonate Can be mentioned.
  • Such surface crosslinking agents may be used in an amount of about 0.01 to 3% by weight based on the total weight of the base resin powder.
  • at least one inorganic material selected from the group consisting of silica (si li ca), clay (cl ay), alumina, silica-alumina composite, titania, zinc oxide and aluminum sulfate in addition to the surface crosslinking agent Further crosslinking reaction may be performed by further adding a substance or the like.
  • the inorganic material may be used in powder form or in liquid form, and in particular, may be used as alumina powder, silica-alumina powder, titania powder, or nano silica solution.
  • the inorganic material may be used in an amount of about 0.05 to about 2% by weight based on the total weight of the base resin powder.
  • the surface crosslinked structure of the super absorbent polymer can be further optimized. This is expected because this metal cation can further reduce the crosslinking distance by forming a chelate with the carboxyl group (C00H) of the superabsorbent resin.
  • the structure of the surface crosslinking agent and, if necessary, the method of adding the inorganic substance and / or the polyvalent metal transition silver to the base resin powder are not limited.
  • a surface crosslinking agent and a base resin powder are mixed in a semi-permanent mixture, or a surface crosslinking agent or the like is sprayed onto the base resin powder, or a base resin powder and a surface crosslinking agent are continuously supplied to a mixer which is continuously operated. Method and the like can be used.
  • water and methanol may be added in combination together.
  • water and methanol are added, there is an advantage that the surface crosslinking agent can be evenly dispersed in the base ' resin powder.
  • the amount of water and methanol added may be appropriately adjusted to induce even dispersion of the surface crosslinking agent, prevent aggregation of the base resin powder, and at the same time optimize the surface penetration depth of the surface crosslinking agent.
  • the surface crosslinking reaction may be performed by heating the base resin powder to which the surface crosslinking agent is added at about ioo ° C or more for about 20 minutes or more.
  • the surface cross-linking process conditions may be adjusted to a maximum reaction temperature of about 100 to 250 ° C. in order to prepare a super absorbent polymer to more appropriately striking the physical properties according to one embodiment.
  • the holding time at the maximum reaction temperature can be adjusted in a condition of about 20 minutes or more and black or more and about 20 minutes or more and 1 hour or less.
  • a temperature at the start of the initial reaction for example, at a temperature of about 100 ° C.
  • the temperature raising time up to the maximum reaction temperature can be controlled to about 10 minutes or more, and black to about 10 minutes to 1 hour or less. have.
  • the temperature raising means for surface crosslinking reaction is not specifically limited. It can be heated by supplying a heat medium or by directly supplying a heat source. In this case, as the type of heat medium that can be used, a heated fluid such as steam, hot air, or hot oil may be used. Consideration can be made as appropriate. On the other hand, as a heat source directly supplied, electric heating, Although a heating method through a gas is mentioned, it is not limited to the above-mentioned example.
  • the superabsorbent polymer obtained according to the above-mentioned manufacturing method is partially swollen under the above-mentioned conditions to easily form a gel having a uniform particle size distribution, and thus the partially swollen gel can exhibit an average particle diameter in the above-described range. That is, the superabsorbent polymer obtained according to the above-described manufacturing method is optimized by pore size and porosity due to the use of a blowing agent, bubble accelerator and surfactant, and shows excellent absorption rate and high gel strength even in a partially swollen state. The phenomenon can be effectively prevented.
  • the operation and effect of the invention will be described in more detail with reference to specific examples. However, this is presented as an example of the invention, whereby the scope of the invention is not limited in any sense.
  • IRGACURE 819 initiator llg 110 ppi for monomer composition
  • 26 g of polyethyleneglycol diacrylate (PEGDA, molecular weight 400) diluted 5% in acrylic acid were prepared to prepare a solution (A solution) mixed with 0.5% in acrylic acid. .
  • the mixed solution prepared above was poured into a Vat-shaped tray equipped with a light irradiation device on the top and installed inside a square polymerizer preheated to 80 ° C. Thereafter, the mixed solution was irradiated with light. It was confirmed that a gel was formed on the surface after about 20 seconds from the light irradiation, and polymerization reaction occurred simultaneously with foaming after about 30 seconds from the light irradiation. Thereafter, the polymerization reaction was further performed for 2 minutes, and the polymerized sheet was taken out and cut into a size of 3 cm X 3 cm. The cut sheet was then made into a powder through a chopping process using a meat chopper.
  • the crump was then dried in an oven capable of transferring air volume up and down.
  • the hot ai r at 180 ° C. was flowed downwards upwards for 15 minutes, and then flowed upwards and downwards for 15 minutes so that the water content of the dried powders was about 2% or less.
  • the dried powder was pulverized with a grinder and then classified to obtain a base resin having a size of 150 to 8500.
  • the water solubility of the base resin thus prepared was 36.5 g / g, and the content of water-soluble component was 14.2 wt%.
  • Water retention was measured according to the method of EDANA method WSP 241.2, and the content of water-soluble components was measured according to the method of EDANA method WSP 270.2.
  • Example 2 Preparation of Super Absorbent Polymer A base resin was prepared in the same manner as in Example 1, except that 15 g was added instead of 34 g of the D solution in Example 1.
  • the water retention capacity of the prepared base resin was 35.2 g / g, and the content of water-soluble component was 13.9 wt%. Then, the surface-crosslinked superabsorbent polymer having a particle size of 150 to 850 was obtained in the same manner as in Example 1 using the prepared base resin.
  • Example 3 Preparation of Super Absorbent Polymer
  • a base resin was prepared in the same manner as in Example 1, except that 0.8 g of aluminum sulfate (E-2 solution) was dissolved in 28 g of sodium persulfate solution diluted in 4% in water instead of the E-1 solution. Prepared.
  • the water retention capacity of the prepared base resin was 37.4 g / g, and the content of water-soluble component was 15. 1 wt%.
  • the surface-crosslinked superabsorbent polymer having a particle size of 150 to 850 was obtained in the same manner as in Example 1 using the prepared base resin.
  • Example 5 Preparation of Super Absorbent Polymer
  • a solution was prepared, which was a mixture of IRGAC® 819 initiator llg (110 ppm for monomer composition) and 26 g of polyethylene glycol diacrylate (PEGDA, molecular weight 400) dilute in acrylic acid at 0.5% in acrylic acid. It was.
  • D solution a solution of 0.8 g of aluminum sulfate dissolved in 28 g of sodium persulfate solution (4% dilute in water) (E-2 solution) and 0FX-0193 (XIAMETER (R)) solution diluted to 1> in water (F Solution). And 34g of D solution and 2.8g of F solution were mixed.
  • the mixed solution of D and F prepared in advance was injected into the mixed solution, and the E-2 solution was injected at the same time.
  • the mixed solution prepared above was poured into a Vat-shaped tray (15 cm long by 15 cm wide) equipped with a light irradiation apparatus on the top and installed in a square polymerizer preheated to 80 ° C. Thereafter, the mixed solution was irradiated with light. It was confirmed that a gel was formed on the surface after about 20 seconds from the light irradiation, and polymerization reaction occurred simultaneously with foaming after about 30 seconds from the light irradiation.
  • the polymerization reaction was further performed for 2 minutes, and the polymerized sheet was taken out and cut into a size of 3 cm X 3 cm. Then using a meat chopper . The cut sheet was made into a powder through a chopping process.
  • the crump was dried in an oven capable of transferring air volume up and down.
  • the crump was dried uniformly by flowing hot air of 18 CTC for 15 minutes from below to upward, and again from above for 15 minutes so that the dried powder had a water content of about 23 ⁇ 4 or less.
  • the dried powder was pulverized with a grinder and then classified to obtain a base resin having a size of 150 to 850 zm.
  • the water holding capacity of the base resin thus prepared was 35.8 g / g, and the content of water-soluble component was 13.7 wt%.
  • Example 5 Base resin was prepared in the same manner as. The water retention capacity of the prepared base resin was 39.3 g / g, and the content of water-soluble component was 19.3 wt%. Then, using the prepared base resin in the same manner as in Example 5 to obtain a surface-crosslinked superabsorbent polymer having a particle diameter of 150 to 850 Pa. Comparative Example 2: Preparation of Super Absorbent Polymer
  • Comparative Example 1 34 g of a sodium bicarbonate (D solution) diluted with 53 ⁇ 4 was added to the mixed solution before adding the E-0 solution.
  • Base resin was prepared by the method. The water retention capacity of the prepared base resin was 34.2 g / g, and the content of water-soluble component was 13.1% by weight. Then, using the prepared base resin in the same manner as in Comparative Example 1 to obtain a surface-crosslinked superabsorbent water particles having a particle diameter of 150 to 850 Pa. Comparative Example 3: Preparation of Super Absorbent Polymer
  • a base resin was prepared in the same manner as in Example 1, except that 0FX-0193 (XIAMETER (R)) solution diluted with 13 ⁇ 4 in acrylic acid was not used as the surfactant in Example 1.
  • the water holding capacity of the prepared base resin was 35.22 g / g .
  • the surface-crosslinked superabsorbent polymer having a particle size of 150 to 850 was obtained in the same manner as in Example 1 using the prepared base resin. Comparative Example 4: Preparation of Super Absorbent Polymer
  • the average particle diameters of the superabsorbent polymers prepared in Examples 1 to 5 and Comparative Examples 1 to 4 were measured according to the method of EDANA WSP 220.2 (European Di sposabl es and Nonwovens Assoc on at EDANA) standard.
  • the superabsorbent polymer lg was placed in a plastic bag of PE material, and 20 g of 0.9 wt% physiological saline was injected to swell the superabsorbent polymer for 10 minutes. Thereafter, the obtained gel (partially swollen superabsorbent resin) was O. lg hydrophobic silica (trade name: DM-30S, manufactured by Tokuyama) was added, and the plastic pack was shaken to evenly apply the silica to the swollen superabsorbent resin.
  • the hydrophobic silica was added to prevent the gel from sticking together while measuring the average particle diameter of the gel, and several experiments confirmed that the particle size of the gel did not change due to the addition and the amount of the hydrophobic silica.
  • the average particle diameter of the obtained gel was measured according to the European Di sposables and Nonwovens Associ at ion (EDANA) standard EDANA WSP 220.2 method.
  • EDANA European Di sposables and Nonwovens Associ at ion
  • WSP 220.2 method 3.
  • Centrifugal water retention capacity (CRC) Centrifugal water retention capacity (CRC) of the superabsorbent polymers of Examples 1 to 5 and Comparative Examples 1 to 4 with respect to physiological saline is EDANA method WSP 241.2 It was measured according to the method.
  • a super absorbent polymer having a particle size of 300 to 600 which passed through the US standard 30 mesh screen and maintained on the US standard 50 mesh screen, was prepared among the superabsorbent polymers to be measured for centrifugal water retention.
  • the superabsorbent polymer W 0 (g, about 0.2 g) having a particle size of 300 to 600 mm was uniformly placed in a nonwoven fabric bag and sealed. Then, the envelope was immersed in 0.9% by weight of saline solution at room temperature. After 30 minutes, the envelope was dehydrated at 250 G for 3 minutes using a centrifuge, and then the weight W 2 (g) of the envelope was measured. On the other hand, the same operation was performed using the empty bag which does not contain superabsorbent polymer, and the weight Wg) at that time was measured.
  • W 0 (g) is the initial weight (g) of the super absorbent polymer having a particle diameter of 300 to 600
  • Wg) is the weight of the device after dehydration at 250G for 3 minutes using a centrifuge without using the super absorbent polymer ego
  • W 2 (g) is a device measured by submerging the superabsorbent polymer in physiological saline of 0.9 wt.> At room temperature for 30 minutes and then dehydrating it at 250 G for 3 minutes using a centrifuge. It is weight.
  • AUL Absorbency under Load
  • the pressure-absorbing capacity (AUL) of 0.9 ps i with respect to physiological saline of the superabsorbent resins of Examples 1 to 5 and Comparative Examples 1 to 4 was measured according to the method of EDANA method WSP 242.2.
  • a stainless steel 400 mesh screen was mounted on the bottom of the plastic cylinder having an inner diameter of 25 mm 3. Then, the superabsorbent polymer W 0 (g, about 0.16 g), which is to be measured under pressure at room temperature and 50> humidity, was uniformly sprayed on the screen. Subsequently, a piston was added to the superabsorbent polymer to uniformly impart a load of 6.3 kPa (0.9 psi). At this time, the outer diameter of the piston is slightly smaller than 25mm, the inner wall of the cylinder has no name, and was used to move freely up and down. Then, the weight W 3 (g) of the device thus prepared was measured.
  • a glass filter having a diameter of 90 mm and a thickness of 5 mm was placed inside a 150 mm diameter petri dish, and 0.9 wt% of physiological saline was poured into the petri dish. At this time, physiological saline was poured until the surface of physiological saline became horizontal with the upper surface of the glass filter. Then, a sheet of 90 mm diameter filter paper was placed on the glass filter. '
  • the prepared device was placed on the filter paper so that the superabsorbent resin in the device was swollen by physiological saline under load. After 1 hour, the weight W 4 (g) of the device containing the swollen superabsorbent resin was measured.
  • AUL (g / g) [W 4 (g)-W 3 (g)] / Wo (g)
  • W 0 (g) is the initial weight (g) of the superabsorbent polymer
  • W 3 (g) is the sum of the weight of the superabsorbent polymer and the weight of the device capable of applying a load to the superabsorbent polymer
  • W 4 (g ) Is the sum of the weight of the superabsorbent resin and the weight of the device capable of applying a load to the superabsorbent resin after absorbing physiological saline to the superabsorbent resin for 1 hour under a load (0.9 psi).
  • the free swelling gel bed permeability (GBP) of the superabsorbent resins of Examples 1 to 5 and Comparative Examples 1 to 4 to physiological saline was measured according to the following method described in Patent Application No. 2014-7018005.
  • a plunger 536 equipped with a weight 548 is placed in an empty sample container 530, and with a suitable gauge to an accuracy of 0.01 mm, from the top of the weight 548 to the bottom of the sample container 530. The height was measured. During the measurement, the force applied by the thickness gauge was adjusted to less than about 0.74 N.
  • the super absorbent resin passed through the US standard 30 mesh screen and retained on the US standard 50 mesh screen was selected to obtain a super absorbent resin having a particle size of 300 to 600.
  • the super absorbent polymer thus classified was placed in the sample container 530 and evenly spread on the bottom of the sample container.
  • This vessel without plunger 536 and weight 548 was then immersed in 0.9% physiological saline for about 60 minutes to swell the superabsorbent resin under no pressure.
  • the sample vessel 530 was placed on the mesh located in the liquid reservoir so that the sample vessel 530 is slightly above the bottom of the fluid reservoir, and the mesh does not affect the movement of physiological saline to the sample vessel 530. Not used.
  • the height of physiological saline was adjusted such that the surface in the sample vessel was defined by the swollen superabsorbent resin, not physiological saline.
  • the assembly of the plunger 536 and the weight 548 is laid down on the swollen superabsorbent resin 568 in the sample container 530, and then the sample container 530, plunger 536, weight ( 548) and the swollen superabsorbent resin 568 were removed from the solution.
  • the sample vessel 530, plunger 536, weight 548 and swollen superabsorbent resin 568 are then placed on a flat, large grid, uniform thickness, non-deformation plate, prior to GBP measurements. Leave it on for a while. Then, using the same thickness gauge as used previously, the height from the top of the weight 548 to the bottom of the sample vessel 530 is again used. Measured.
  • the flow rate Q through the swollen superabsorbent resin 568 is the linear least-squares fit of the fluid (g) versus time (sec) through the swollen superabsorbent resin 568. It was determined in g / sec unit by.
  • the GBP (cm 2 ) was calculated according to the following equation 3 using the data values thus obtained.
  • ⁇ is the gel bed transmission (cm 2 )
  • H is the height (cm) of the swollen superabsorbent resin
  • ⁇ is the liquid viscosity ( ⁇ ) (the viscosity of the physiological saline used in this test is about lcP),
  • A is the cross-sectional area for the liquid flow (28.27 cm 2 for the sample vessel used in this test),
  • p is the liquid density (g / cm 3 ) (about 1 g / cm 3 for the saline solution used in this test),
  • P is the hydrostatic pressure (dyne / cm 2) (normally approximately 7, 797dyne / cm 2).
  • the absorption rate (or vortex time) was calculated by adding 2 g of superabsorbent resin to 50 mL of physiological saline, stirring at 600 rpm, and measuring the time until the vortex disappeared in seconds.
  • a superabsorbent resin-enhanced US standard 30 mesh screen for evaluating the rewet characteristics was prepared, and a super absorbent polymer having a particle diameter of 300 to 600 / im was prepared on the US standard 50 mesh screen.
  • test assembly was prepared by uniformly spreading the superabsorbent polymer W 0 (g 0.1 g) prepared in advance on the screen at room temperature and 50% humidity.
  • test assembly was placed on a 80 mm diameter PE dish with a 25 mm diameter crab 1 filter paper. Thereafter, 4 g of 0.9 wt% physiological saline was injected around the test assembly to allow the superabsorbent resin to absorb physiological saline in the unpressurized state. Once all of the physiological saline is absorbed by the superabsorbent polymer, the superabsorbent polymer It was left for 10 minutes to swell.
  • a piston was added which was able to uniformly impart a load of 5. 1 kPa (0.7 psi) on the swollen superabsorbent resin. At this time, the outer diameter of the piston is slightly smaller than 25mm, there is no gap with the inner wall of the cylinder, was used to be able to move freely up and down.
  • test assembly to which the piston was added was mounted on the previously prepared 2nd filter paper. After 2 minutes, after lifting and removing the test assembly to which the piston was added, the weight W 6 (g) of the second filter paper was measured again.
  • Rewet amount (g / g) [W 6 (g)-W 5 (g)] / W 0 (g)
  • W 0 (g) is the initial weight (g) of the superabsorbent polymer
  • W 5 (g) is the initial weight of the second filter paper
  • W 6 (g) is the initial weight of the superabsorbent polymer under pressureless time. After absorbing 25 times the physiological saline solution of the superabsorbent resin, the weight of the second filter paper which absorbed the liquid oozed from the swollen superabsorbent resin for 2 minutes under load (0.7 psi).
  • Example 1 and the water-absorbent resin (2) to measure the mean diameter of the gel and, for high swelling portion in the same way that part swell the water-absorbent resin produced in, was added to the same silica in the resulting gel in the same content.
  • the gel obtained above was classified by several meshes (Mesh # 14, Mesh # 18, Mesh # 20, Mesh # 30). First, the gel was separated into particles having a particle size greater than 1400 and particles having a particle size of 1400 or less by a mesh of Mesh # 14. Particles having a particle size of 1400 or less were separated into particles having a particle size of more than 1000 and 1400 or less and particles having a particle size of 1000 or less by a mesh of Mesh # 18.
  • Particles with a particle size of 1000 or less were separated by a mesh of Mesh # 20 into particles having a particle diameter of more than 850 mm and less than 1000 and bibs having a particle size of less than 850 mm. Finally, particles with a particle size of 850 or less were separated into particles with a particle size of more than 600 and less than 800 m and particles with a particle size of 600 or less by the mesh of Mesh # 30. At this time, the classification conditions were adjusted to 1.0 AMP, 2 minutes. The gel was classified as described above to obtain the weight and fraction of the gel belonging to the particle size range shown in Table 2 below, and the results are shown in Table 2.

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Abstract

La présente invention concerne une résine super-absorbante, ladite résine super-absorbante pouvant présenter un taux d'absorption rapide et une force en gel élevée, même à l'état partiellement gonflé grâce à l'optimisation de la taille des particules de gel partiellement gonflées. Par conséquent, l'utilisation de la résine super-absorbante permet d'empêcher efficacement un phénomène de remouillage.
PCT/KR2016/005809 2015-06-01 2016-06-01 Résine super-absorbante WO2016195376A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
US15/558,429 US11059025B2 (en) 2015-06-01 2016-06-01 Super absorbent resin
CN201680017149.8A CN107406562B (zh) 2015-06-01 2016-06-01 超吸收性树脂
EP16803731.5A EP3249001B1 (fr) 2015-06-01 2016-06-01 Résine super-absorbante

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR10-2015-0077534 2015-06-01
KR20150077534 2015-06-01
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US11384208B2 (en) 2016-12-27 2022-07-12 Lg Chem, Ltd. Super absorbent polymer and method for producing same

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US11020725B2 (en) 2016-12-20 2021-06-01 Lg Chem, Ltd. Method of preparing superabsorbent polymer
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