COMPOSITION OF PARTICULATED SUPERABSORBENT POLYMER, PROCESS FOR THE PRODUCTION OF A PARTICULATED SUP

专利摘要:
particulate superabsorbent polymer composition, process for producing a particulate superabsorbent polymer composition and absorbent article the present invention relates to a particulate superabsorbent polymer composition that absorbs water, aqueous liquids, and blood, and a process for making superabsorbent polymers, wherein a superabsorbent polymer is the surface treated with a neutralized multivalent metal salt solution having a pH value similar to that of human skin. the present invention also relates to the particulate superabsorbent polymeric composition having high gel permeability and high absorbency under load.
公开号:BR112013024336B1
申请号:R112013024336-8
申请日:2012-03-28
公开日:2020-02-11
发明作者:Yaru Shi；Gonglu Tian；Mark C. Joy；Geoffrey W. Black；Bernfried Andreas Messner；Scott Smith
申请人:Evonik Corporation；
IPC主号:

专利说明:

COMPOSITION OF PARTICULATED SUPERABSORBENT POLYMER, PROCESS FOR THE PRODUCTION OF A PARTICULATED SUPERABSORBENT POLYMER COMPOSITION AND ABSORBENT ARTICLE
FIELD OF THE INVENTION [0001] The present invention relates to particulate superabsorbent polymer compositions that absorb water, aqueous liquids, and blood, and a method for making the superabsorbent polymer compositions. In particular, the present invention relates to superabsorbent polymer compositions with high permeability, which are produced by contacting a superabsorbent polymer with a neutralized multivalent metal salt solution having a pH value close to that of human skin. The present invention also relates to particulate superabsorbent polymer compositions having high gel bed permeability and high absorption capacity under load.
BACKGROUND OF THE INVENTION [0002] A superabsorbent polymer, or material, in general, refers to a water-expandable polymer, insoluble in water, or a material, capable of absorbing at least about 10 times its weight, and up to about 30 times or more by weight in an aqueous solution containing 0.9 weight percent sodium chloride solution in water. Examples of superabsorbent polymer may include a partially neutralized cross-linked polymer, including cross-linked polyacrylic acids or cross-linked starch-acrylic acid polymers, which are capable of absorbing large amounts of aqueous liquids and body fluids, such as
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2/80 blood or urine, with swelling and the formation of superabsorbent hydrogel, and to retain aqueous liquids, under certain pressure, according to the general definition of the superabsorbent polymer.
[0003] Superabsorbent polymer hydrogel can be formed into particles, generally referred to as superabsorbent polymer particles, in which the particulate superabsorbent polymer can be post-treated with surface crosslinking, surface treatment, and other forms of surface treatment for form particulate superabsorbent polymer compositions. The acronym PSA (SAP in English) can be used in place of the superabsorbent polymer, the superabsorbent polymer composition, particulate superabsorbent polymer compositions, or variations thereof. A primary use of superabsorbent polymer and superabsorbent polymer compositions is in sanitary articles, such as baby diapers, incontinence products, or sanitary napkins. Extensive research on superabsorbent polymers, and their use and manufacture, is given in FL Buchholz and AT Graham (editors), in Modern Superabsorbent Polymer Technology, Wiley-VCR, New York, 1998.
[0004] Sanitary articles, such as diapers, generally include an absorbent core that includes about 30-50% cellulose fibers and about 50-70% of the particulate superabsorbent polymer composition. It is an objective of future sanitary articles to make them smaller and thinner, for fit, comfort and aesthetic reasons and environmental aspects. One way to achieve this goal is to reduce the amount of fiber material
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3/80 and increase the amount of particulate superabsorbent polymer composition, where there may be less than about 30%, or less than about 20%, or less than about 10% of the fibrous material in the absorbent core. The particulate superabsorbent polymer composition of these next generation of diaper constructions must have sufficiently high stability and permeability in a swollen state, so that the liquid can be transported through the swollen gel. In addition, the components of the sanitary articles must be compatible for the user, where the components must have properties, such as a pH compatible with the baby's skin, which has a pH of about 7.
[0005] Superabsorbent polymers can be prepared, initially, by neutralizing unsaturated carboxylic acids or their derivatives, such as acrylic acid, alkali metal (eg sodium and / or potassium) or ammonium salts of acrylic acid, alkyl acrylates , and the like, in the presence of a caustic treatment, such as sodium hydroxide, and then polymerization of the product with relatively small amounts of an internal cross-linking agent, or monomer, such as di- or polyfunctional monomers. The di- or poly-functional monomer materials can serve as internal covalent crosslinking agents slightly to crosslink the polymeric chains, thus making them insoluble in water, however, expandable with water. These slightly crosslinked superabsorbent polymers contain a multiplicity of carboxyl groups attached to the main structure of the polymer. These carboxyl groups generate an osmotic driving force for the absorption of body fluids by the polymer network
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4/80 cross-linked. The particulate superabsorbent polymer can be surface treated with surface crosslinking and surface treatment to improve the properties of the particulate polymer. [0006] Superabsorbent polymers and particulate superabsorbent polymeric compositions, useful as absorbents in absorbent articles such as disposable diapers, must have adequate high adsorption capacity, as well as sufficiently high gel strength. Absorption capacity must be high enough to allow the absorbent polymer to absorb significant amounts of aqueous body fluids found during the use of the absorbent article. The strength of the gel refers to the tendency of the swollen polymer particles to resist deformation under an applied stress, and it must be such that the particles do not deform under pressure, and fill the empty capillary spaces of the absorbent element, or of the article, to an unacceptable degree, which is generally called gel blocking, thereby inhibiting the rate of fluid absorption, or the distribution of fluid, by a limb or article. After the gel blockage occurs, it can substantially prevent the distribution of fluids to relatively dry areas or regions in the absorbent article, and leakage of the absorbent article can occur long before the particles of the absorbent polymer in the absorbent article are completely saturated, or before the liquid may diffuse or pass through the block.
[0007] Permeability is a measure of the effective bonding of a porous structure, be it a fiber mat from a foam slab or, in the case of this application, the particulate superabsorbent polymer and
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5/80 the particulate superabsorbent polymer composition generally refers to the particulate superabsorbent polymer compositions, or PSA, and can be specified in terms of the vacuum fraction and extent of binding of the particulate superabsorbent polymer compositions. Gel permeability is a mass property of particulate superabsorbent polymeric compositions, as a whole, and is related to the particle size distribution, particle shape, open pore connection, shear modulus and surface modification of the swollen gel. In practical terms, the permeability of the particulate superabsorbent polymer composition is a measure of how quickly the liquid flows through the mass of swollen particles. Low permeability indicates that the liquid cannot flow easily through the particulate superabsorbent polymer compositions, which is generally referred to as gel blocking, and that any forced flow of liquid (such as a second application of urine when using the diaper) must have an alternative route (for example, diaper leak).
[0008] Surface treatment of particulate superabsorbent polymers is already well known. To improve the permeability of particulate superabsorbent polymers, ionic complexation of the carboxyl groups close to the surface, using polyvalent metal cations, has been disclosed in the prior art. US 6,620,889 discloses superabsorbents, which are cross-linked to the surface with a combination of a polyol and a cation salt in aqueous solution. The anion of the salt can be chloride, bromide, sulfate, carbonate, nitrate, phosphate, acetate or lactate. The use of aluminum sulphate
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6/80 as a surface treatment of particulate superabsorbent polymeric compositions is disclosed in WO 2005/108 472 A1, which describes a process which includes treating a base polymer with a water-soluble polyvalent metal salt and an organic acid or your salt. The multivalent metal salt is preferably aluminum sulfate. The organic acid or salt is selected from a range of acids that include citric acid, glyoxylic acid, glutaric acid, succinic acid, tartaric acid and lactic acid, or alkali or ammonium salts thereof.
[0009] However, aluminum sulfate is also known to be acidic, with a pH value of less than 4, and is well below the values of about 7 pH of human skin. The aluminum sulfate applied on the surface of the particulate superabsorbent polymer will generate an acidic surface. Since a sanitary article comprising superabsorbent polymers is in contact with, or close to, or is otherwise beside a user's skin, it is desirable to control the pH of the surface of the superabsorbent polymers in order to reduce the risk of irritation of the skin.
[0010] It is also known that the solubility of aluminum ions and their salts, such as aluminum sulfate, in water, is dependent on pH. At pH levels between 4 and 9.5, aluminum sulfate becomes insoluble in water and precipitation occurs, resulting in a suspension of aluminum hydroxide. A suspension is known to be more difficult to handle than a solution in a production process.
[0011] US 5,559,263 describes a method for preparing an aqueous solution of aluminum having a pH between about 5.0 and about 9.0 at a concentration of at least about 3.1 percent in
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7/80 weight of aluminum. The solution comprises citrates as chelating binders for aluminum ions. Chelating binders can compete with carboxyl groups near the surface of the superabsorbent polymer to form ionic complexes with aluminum ions, which can lessen the effects of increasing the permeability of aluminum ions.
[0012] It is therefore an object of the present invention to provide a particulate superabsorbent polymer composition having improved compatibility with human skin. It is also an object of the present invention to provide a particulate superabsorbent polymer composition that exhibits excellent properties, such as the ability to maintain high liquid permeability and liquid retention even when the amount of particulate superabsorbent polymer composition is increased by a percentage. in weight based on that of the absorbent structure.
SUMMARY OF THE INVENTION [0013] The present invention comprises a process for producing a particulate superabsorbent polymer composition that comprises the following steps: a) providing a particulate superabsorbent polymer, b) preparing a neutralized multivalent metal salt in the form of a solution water having a pH value of about 5 to about 9, and c) applying the neutralized multivalent metal salt solution from step b) over the surface of the particulate superabsorbent polymer, where the particulate superabsorbent polymer composition has a degree of neutralization of more than about 25 mol%, and has a
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8/80 numeric Gel Bed Permeability of at least about [8000 and ^-0 ' ^18x ] Darcy where x is the numerical value of Centrifuge Holding Capacity; a Centrifuge Retention Capacity greater than about 25 g / g, and an absorption capacity under load of 6205.3 Pa from about 16 g / g to 24 g / g. It has been found that the surface treatment of the particulate superabsorbent polymer with a neutralized multivalent metal salt solution increases certain properties of the particulate superabsorbent polymer composition, in particular, the permeability in a gel bed.
[0014] An embodiment of the present invention further includes a particulate superabsorbent polymer composition made by the above process. In an embodiment of the present invention, the particulate superabsorbent polymer composition comprising a polymer comprises: a) about 55 to about 99.9% by weight of the polymerizable unsaturated acid group containing monomers, b) from 0 to about 40% by weight of polymerised, ethylenically unsaturated monomers, copolymerizable with a); c) from about 0.001 to about 5.0% by weight based on the weight of a) an internal cross-linking agent; d) about 0.001 to about 5.0% by weight based on the dry particulate superabsorbent polymer composition of the surface crosslinking agent applied on the surface of the superabsorbent polymer particle; ee) from 0.01 to about 5% by weight, based on the dry particulate superabsorbent polymer composition of a neutralized multivalent metal salt applied to the particle surface, in the form of an aqueous solution having a pH value of about 5 to about 9, where the composition
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9/80 has a degree of neutralization of the polymerizable unsaturated acid group containing monomers is more than about 25%, and the particulate superabsorbent polymer composition has the numerical value characteristics of a GBP gel bed permeability of at least about [8000 and ^-0 , ^18x ] Darcy where x is the numerical value of the centrifuge holding capacity, a centrifugal holding capacity greater than about 25g / g and an absorption under load at 6205.3 Pa from about 18g / g and about 22g / g.
[0015] An embodiment of the present invention further includes a particulate superabsorbent polymer composition comprising: a) about 55 to about 99.9% by weight of the polymerizable unsaturated acid group containing monomers, b) from 0 to about 40% by weight of polymerised, ethylenically unsaturated monomers, copolymerizable with a); c) from about 0.001 to about 5.0% by weight based on the weight of a) an internal cross-linking agent, in which components a), b) and c) are polymerized in a hydrogel which is granulated in polymer particulate superabsorbent having a surface; d) from about 0.001 to about 5.0% by weight based on the dry particulate superabsorbent polymer composition of the surface crosslinking agent composition applied to the surface of the particulate superabsorbent polymer; ee) from 0.01% to about 5% by weight, based on the dry particulate superabsorbent polymer composition of the aluminum salt composition applied to the surface of the particulate superabsorbent polymer, in the form of an aqueous solution having a pH value of about 5 to about 9.0, where said
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10/80 aluminum salt solution comprises aluminum cations and anions of a deprotonated hydroxyl mono-carboxylic acid with a molar ratio of carboxylic anions to aluminum cations between about 0.75: 1 and about 1.5: 1.
[0016] In addition, the present invention is directed to absorbent compositions or sanitary articles, such as diapers, which may contain the superabsorbent polymer compositions of the present invention.
[0017] Numerous other aspects and advantages of the present invention will emerge from the following description.
BRIEF DESCRIPTION OF THE DRAWINGS [0018] The background and other characteristics, aspects and advantages of the present invention will be better understood in relation to the following description, attached claims and accompanying drawings, in which:
[0019] FIG 1 is a side view of the test apparatus used for the Free Swelling Gel Bed Permeability Test;
[0020] FIG 2 is a cross-sectional side view of a cylinder / bowl arrangement set employed in the Free Swelling Gel Bed Permeability Test shown in FIG 1;
[0021] FIG 3 is a top view of a plunger employed in the Free Swelling Gel Bed Permeability Test shown in FIG 1; and [0022] FIG 4 is a side view of the test apparatus used for the Load Absorbance Test.
DEFINITIONS
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11/80 [0023] It should be noted that, when used in the present description, the terms comprise, comprising, and other derivatives of the term root comprise are intended to be open terms that specify the presence of any indicated characteristics, elements, integers , steps or components, and are not intended to prevent the presence or addition of one or more additional features, elements, integers, steps, components or groups thereof.
[0024] As used herein, the term about modifying the amount of an ingredient in the compositions of the invention or used in the methods of the invention refers to the variation in the numerical quantity that can occur, for example, through typical measurement and measurement procedures. handling liquids used to make concentrates or use solutions in the real world; through inadvertent error in these processes; through differences in the manufacture, origin, or purity of the ingredients used to make the compositions or perform the methods; and the like. The term also covers amounts that differ due to different equilibrium conditions for the resulting composition from a particular initial blend. Whether or not modified by the term on the claims includes equivalent amounts.
[0025] The term absorbent article, as used herein, refers to devices that absorb and retain body exudates and, more specifically, refers to devices that are placed against or in close proximity to the user's body to absorb and contain the various exudates released by the body. Absorbent items may include diapers, training pants, adult clothing
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12/80 incontinents, feminine hygiene products, pillows, breast pads, bibs, dressing products, and so on. Absorbent articles may also include floor cleaning articles, food industry articles and the like. As used herein, the term body fluids or body excreta includes, but is not limited to, blood, urine, vaginal secretions, breast milk, sweat and fecal matter.
[0026] The term Centrifuge Holding Capacity (CRC) as used herein refers to the ability of the particulate superabsorbent polymer to retain liquid contained therein and after being saturated subjected to centrifugation under controlled conditions and is indicated as grams of retained liquid per gram of sample weight (g / g), as measured by the
Centrifuge established here.
[0027] The terms crosslinking, crosslinking, crosslinking agent, or crosslinking, as used herein refer to any means to effectively make materials normally soluble in water, substantially insoluble in water, but intumescible. Such a crosslinking means can include, for example, physical entanglement, crystalline domains, covalent bonds, complexes and ionic associations, hydrophilic associations, such as hydrogen bonding, hydrophobic associations or Van der Waals forces.
[0028] The term internal crosslinking agent or crosslinking monomer as used herein refers to the use of a crosslinking agent in the monomer solution to form the polymer.
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13/80 [0029] The term Darcy is a CGS unit of permeability. A Darcy is the permeability of a solid through which a cubic centimeter of fluid, with a viscosity of one centipoise, will flow in one second through a section one centimeter thick and one square centimeter, in cross section, if the difference in pressure between the two sides of the solid is an atmosphere. It turns out that the permeability has the same area units, since there is no SI permeability unit, square meters are used. A Darcy is equal to about 0.98692 x 10 ^-12 m ² or about 0. 98692 x 10 ^-8 cm ² .
[0030] The term diaper, as used here, refers to an absorbent article generally used by babies and incontinent people, on the lower part of the trunk, in order to surround the wearer's waist and legs and which is specifically adapted for receive and contain urinary and fecal waste.
[0031] The term disposable, as used herein, refers to absorbent articles that are not intended to be washed or otherwise recovered or reused as an absorbent article after a single use. Examples of such disposable absorbent articles include, but are not limited to, personal care absorbent articles, medical / health absorbent articles, and household / industrial absorbent articles.
[0032] The term dry particulate superabsorbent polymer composition, as used herein generally refers to the superabsorbent polymer composition with less than about 10% moisture.
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14/80 [0033] The term gel permeability is a property of particle mass, as a whole, and is related to the distribution of particle size, particle shape, and connection of the empty pores between the particles, shear modulus , and modification of the swollen gel surface. In practical terms, the gel permeability of the superabsorbent polymer composition is a measure of how quickly the liquid flows through the mass of swollen particles. Low gel permeability indicates that liquid cannot flow easily through the superabsorbent polymer composition, which is generally referred to as gel blocking, and that any forced flow of liquid (such as a second application of urine during diaper use) ) must have an alternate path (for example, diaper leak).
[0034] The term median particle size of a given sample of particles of superabsorbent polymer composition is defined as the particle size, which splits the sample in half on a mass basis, that is, half of the sample by weight it has a particle size larger than the mass average particle size and half of the mass sample has a particle size smaller than the mass average particle size. Thus, for example, the average particle size mass of a sample of particles of the superabsorbent polymer composition is 2 microns, if half of the sample by weight is measured as more than 2 microns.
[0035] The terms particle, particles, and the like, when used with the term superabsorbent polymer, refer to the form of discrete units. Units can comprise flakes,
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15/80 fibers, agglomerates, granules, powders, spheres, powder materials, or the like, as well as combinations thereof. The particles can have any desired shape: for example, cubic, polyhedral, spherical or semi-spherical, rounded or semi-rounded, angular, irregular, etc. Shapes that have a high aspect ratio, such as needles, flakes and fibers, are also contemplated for inclusion here. The terms particles or particulates can also include an agglomeration that comprises more than one individual particle, in particles, or the like. In addition, a particle, particulate, or any desired agglomeration of the same, can be composed of more than one type of material.
[0036] The terms particulate superabsorbent polymer and particulate superabsorbent polymer composition [0037] refer to the form of superabsorbent polymer and superabsorbent polymer compositions in discrete form, wherein the particulate superabsorbent polymer and particulate superabsorbent polymer compositions can have a size of particle less than 1000pm, or from about [0038] 150 pm to about 850pm.
[0039] The term permeability, when used here, means a measure of the effective bonding of a porous structure, in this case, cross-linked polymers, and can be specified in terms of the vacuum fraction, and the extent of bonding of the particulate superabsorbent polymer composition. .
[0040] The term polymer includes, but is not limited to, homopolymers, copolymers, for example, block, graft,
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16/80 random, and alternating copolymers, terpolymers, etc., and mixtures and modifications thereof. In addition, unless otherwise specifically limited, the term polymer includes all possible configurational isomers of the material. Such configurations include, but are not limited to, isotactic, syndiotactic, and atactic symmetries.
[0041] The term polyolefin as used herein, generally includes, but is not limited to, materials such as polyethylene, polypropylene, polyisobutylene, polystyrene, ethylene vinyl acetate copolymer, and the like, homopolymers, copolymers, terpolymers, etc., of them, and their mixtures and modifications. The term polyolefin should include all possible structures of the same, which include, but are not limited to, isotactic, synodiotactic, and random symmetries. Copolymers include block and atactic copolymers.
[0042] The term superabsorbent polymer, as used herein, refers to water-insoluble, water-insoluble, organic or inorganic materials, including superabsorbent polymers and superabsorbent polymer compositions capable, under the most favorable conditions, of absorbing at least about 10 times its weight, or at least about 15 times its weight, or at least about 25 times its weight of an aqueous solution containing 0.9 weight percent sodium chloride.
[0043] The term superabsorbent polymer composition, as used herein, refers to a superabsorbent polymer comprising a surface additive according to the present invention.
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17/80 [0044] The term superabsorbent polymer pre-product as used herein refers to a material that is produced by carrying out all the steps of producing a superabsorbent polymer, as described herein, up to and including drying of the material, and coarse grinding in a crusher.
[0045] The term cross-linked surface as used herein refers to the level of functional cross-links at the periphery of the surface of the superabsorbent polymer particle, which is generally higher than the level of functional cross-links within the polymer particle superabsorbent. As used herein, surface describes the outer boundaries facing the particle.
[0046] The term thermoplastic, as used herein, describes a material that softens when exposed to heat and which returns to a substantially non-softened condition when cooled to room temperature.
[0047] The term% by weight or% by weight as used herein and referring to the components of the dry particulate superabsorbent polymer composition, is to be interpreted based on the weight of the dry superabsorbent polymer composition, unless otherwise specified. way.
[0048] These terms can be defined with additional language in the remaining parts of the specification.
DETAILED DESCRIPTION OF THE INVENTION [0049] While typical aspects of the embodiment and / or embodiments have been indicated for the purpose of illustration, this detailed description and the attached drawings should not be
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18/80 considered as a limitation within the scope of the invention. Thus, various modifications, adaptations and alternatives can occur to those skilled in the art without departing from the spirit and scope of the present invention. As a hypothetical illustrative example, a disclosure in the present application of a range from 1 to 5 will be considered to support claims at any of the following ranges: 1-5, 1-4, 1-3, 1-2; 2-5, 2-4, 2-3, 3-5, 3-4 and 4-5.
[0050] In an embodiment of the present invention, the superabsorbent polymer composition is a crosslinked polymer comprising: a) from about 55% by weight to about 99.9% by weight of the polymerizable unsaturated acid group containing monomers , b) from 0 to about 40% by weight of ethylenically unsaturated polymerized copolymerizable monomers, with a); c) between about 0.001% by weight to about 5.0% by weight of a) internal cross-linking agent; d) from about 0.001% by weight to 5.0% by weight based on the dry particulate superabsorbent polymer composition of a surface crosslinking agent applied to the particle surface; and e) from about 0.01% by weight to about 5% by weight, based on the weight of dry particulate superabsorbent polymer composition of a neutralized multivalent metal salt solution applied to the particle surface, where the composition has a degree of neutralization of more than about 25 mol%.
[0051] The aqueous solution of the neutralized multivalent salt may comprise a multivalent cation and an anion of deprotonated organic acid. Multivalent salt having a pH value equal to or close to that of human skin will reduce the risk of irritation
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19/80 of the skin. In addition, a superabsorbent polymer composition with significantly improved permeability and high absorption capacity under load is unexpectedly obtained by coating the superabsorbent polymer with the multivalent salt solution having adjusted pH and suitable molar ratio of organic acid to multivalent cation.
[0052] A suitable superabsorbent polymer can be selected from natural, biodegradable, synthetic and modified natural polymers and materials. The term cross-linked used in reference to the superabsorbent polymer refers to any means for effectively making materials normally soluble in water, substantially insoluble in water, but intumescible. Such a crosslinking means can include, for example, physical entanglement, crystalline domains, covalent bonds, complexes and ionic associations, hydrophilic associations, such as hydrogen bonds, hydrophobic associations or Van der Waals forces. Superabsorbent polymers include internal crosslinking and may also include surface crosslinking.
[0053] A superabsorbent polymer, as established in the embodiments of the present invention is obtained through the initial polymerization, from about 55% to about 99.9% by weight of the superabsorbent polymer of the polymerizable unsaturated acid group containing monomers. A suitable monomer includes any of these containing carboxyl groups, such as acrylic acid, methacrylic acid, or 2-acrylamido-2-methylpropanesulfonic acid, or mixtures thereof. It is desirable that at least about 50% by weight,
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20/80 and more desirable that at least about 75% by weight of the acid groups are carboxyl groups.
[0054] The process for making a superabsorbent polymer, as established in the embodiments of the present invention, is obtained through the initial polymerization, from about 55% to about 99.9% by weight of the superabsorbent polymer of the polymerizable unsaturated acid group containing monomers. A suitable polymerizable monomer includes any of these containing carboxyl groups, such as acrylic acid, methacrylic acid, or 2-acrylamido-2-methylpropanesulfonic acid, or mixtures thereof. It is desirable that at least about 50% by weight and more desirable that at least about 75% by weight of the acid groups are carboxyl groups.
[0055] The acid groups are neutralized, the extent of at least about 25 mol%, that is, the acid groups are desirably present as sodium, potassium, or ammonium salts. In some respects, the degree of neutralization can be at least about 50 mol%. In some aspects, it is desirable to use polymers obtained by polymerization of acrylic acid or methacrylic acid, the carboxyl groups of which are neutralized to the extent of about 50 mol% to about 80 mol%, in the presence of internal cross-linking agents.
[0056] As for acrylic acid, it is important to use acrylic acid, which is known for its content for being pure, that is, acrylic acid having at least 99.5% by weight of concentration, or at least the concentration of 99.7% by weight, or at least 99.8% by weight. The main component of this
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21/80 monomer can be acrylic acid or acrylic acid and an acrylate salt. Acrylic acid impurities can include water, propionic acid, acetic acid and diacrylic acid, commonly called an acrylic acid dimer. Diacrylic acid content should be 1000 ppm or less, or [0057] 500 ppm or less, or 300 ppm or less, when acrylic acid is used in the process. In addition, it is important to minimize the production of β-hydroxyproprionic acid during the neutralization process of less than about 1000 ppm, or less than about 500 ppm, of β-hydroxypropionic acid.
[0058] Furthermore, in acrylic acid, the content of protoanemonine and / or furfural is 0 to 20 ppm, by weight, in terms of value converted to acrylic acid. In light of the physical properties and improved characteristics of the water-absorbing resin, the content of protoanemonine and / or furfural in the monomer is not more than 10 ppm, by weight, or 0.01 to 5 ppm, by weight, or 0.05 at 2 ppm by weight, or from 0.1 to 1 ppm by weight, in terms of value converted to acrylic acid.
[0059] Furthermore, in the monomer, it is preferred that the amount of aldehyde component with the exception of furfural and / or maleic acid is as small as possible, for the same reason. Specifically, the content of the aldehyde component other than furfural and / or maleic acid can be from 0 to 5 ppm, by weight, or from 0 to 3 ppm, by weight, or from 0 to 1 ppm, by weight, or 0 ppm by weight (no higher than limit detection) in terms of value converted to acrylic acid. Examples of the non-furfural aldehyde component include benzaldehyde, acrolein, acetaldehyde and the like.
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In addition, in the particulate water-absorbing monomer or agent of the present invention, the saturated carboxylic acid content consisting of acetic acid and / or propionic acid is not more than 1000 ppm by weight, or from 10 to 800 ppm, by weight, or from 100 to 500 ppm, by weight, in terms of value converted to acrylic acid.
[0061] In some respects, the suitable monomer that can be copolymerized with the ethylenically unsaturated monomer may include, but is not limited to, acrylamide, methacrylamide, hydroxyethyl acrylate, dimethylaminoalkyl (meth) acrylate, ethoxylates (meth) acrylates, dimethylaminopropyl or acrylamidopropyltrimethylammonium chloride. Such a monomer can be present in a range from 0% by weight to about 40% by weight of the copolymerized monomer.
[0062] When partially neutralized or totally neutralized, the acrylate salt is transformed into a polymer in the particulate water-absorbing agent after polymerization, the converted value based on acrylic acid can be determined by converting the partially neutralized polyacrylate salt or fully salt neutralized is assumed to be completely non-neutralized equimolar polyacrylic acid.
[0063] The superabsorbent polymer of the invention also includes internal cross-linking agents. The internal cross-linking agent has at least two ethylenically unsaturated double bonds or an ethylenically unsaturated double bond and a functional group that is reactive with respect to the acid groups of the polymerizable unsaturated acid group containing monomers or various functional groups that
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23/80 are reactive with the acid groups that can be used as the internal cross-linking component and that is present during the polymerization of the polymerizable unsaturated acid group containing monomers.
[0064] Examples of internal cross-linking agents include unsaturated aliphatic amides, such as methylenebisacryl- or methacrylamide or ethylenebisacrylamide, and, in addition, aliphatic esters of polyols or alkoxylated polyols with ethylenically unsaturated acids, such as di (meth) acrylates or tri ( met) butanediol or ethylene glycol acrylate, polyglycols or trimethylolpropane, trimethylolpropane di- and triacrylate esters, which is preferably oxyalkylated, preferably ethoxylated, with 1 to 30 mol of alkylene oxide, acrylate and glycerol esters methacrylate pentaerythritol and glycerin and oxyethylated pentaerythritol with preferably 1 to 30 mol of ethylene oxide and, in addition, allyl compounds, such as allyl (meth) acrylate, allyl alkoxylated (meth) acrylate, preferably reacted with 1 to 30 mol of ethylene oxide, trialyl cyanurate, trialyl isocyanurate, maleic acid diallyl ester, poly-allyl esters, trimethoxy vinyl silane, vinyl triethoxysilane, polysiloxane comprising at least two groups vinyl, tetraallyloxyethane, tetraallyloxyethane, trialylamine, tetraalylethylenediamine, diols, polyols, hydroxy or allyl acrylate compounds and allyl esters of phosphoric acid or phosphoric acid, and in addition, they are monomers capable of cross-linking, such as the N-methylol compounds of unsaturated amides, such as acrylamide or methacrylamide, and the derived ethers.
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24/80
Ionic cross-linking agents, such as multivalent metal salts, can also be employed. Mixtures of the mentioned crosslinking agents can also be used.
[0065] Internal cross-linking agents or mixtures thereof for use in accordance with the present invention are used in amounts from about 0.001% by weight to about 5% by weight, or from about 0.2% by weight to about of 3% based on the total amount of the polymerizable unsaturated acid group containing monomer.
[0066] In another embodiment, the superabsorbent polymer can include from about 0.001% by weight to about 0.1% by weight based on the total amount of the polymerizable unsaturated acid group containing a second internal crosslinking agent monomer which may contain compositions comprising at least two ethylenically unsaturated double bonds, for example, methylenebisacrylamide or -methacrylamide or ethylenebisacrylamide, in addition, the mono- or polycarboxylic esters of unsaturated polyols, such as, for example, diacrylates or triacrylates, for example, butanodiol diacrylate or ethylene glycol or -methacrylate; trimethylolpropane triacrylate, as well as its alkoxylated derivatives, in addition, allyl compounds, such as allyl (meth) acrylate, trialyl cyanurate, maleic acid diallyl ester, polyalyl ester, tetraalyloxyethane, [0067] di- and trialylamine, tetralylethylenediamine , allyl esters of phosphoric acid or phosphorous acid. In addition, compounds with at least one functional group reactive to acid groups can also be used. Examples of these include
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25/80 N-methylol compounds of amides, such as methacrylamide or acrylamide and the ethers derived therefrom, as well as the di- and polyglycidyl compounds.
[0068] The usual initiators, such as, for example, azo or peroxo compounds, redox systems or UV initiators, (sensitizers), and / or radiation are used for the initiation of polymerization by free radicals. In some respects, primers can be used to initiate polymerization by free radicals. Suitable initiators include, but are not limited to, azo or peroxo compounds, redox systems or ultraviolet initiators, sensitizers and / or radiation.
[0069] Polymerization forms a superabsorbent polymer gel, which is granulated into particles of superabsorbent polymer, or particulate superabsorbent polymer. The particulate superabsorbent polymer generally includes particle sizes ranging from about 50pm to about 1000pm, or from about 150pm to about 850pm. The present invention can include at least about 40% by weight of the particles having a particle size of about
300 pm to about 600pm, at least about 50% by weight of the particles having a particle size of about 300 pm to about 600pm, or at least about 60% by weight the particles with a particle size of about from 300 pm to about 600pm as measured by sieving through a standard American screen of 30 and is retained on a standard American screen of
50. In addition, the superabsorbent polymer particle size distribution of the present invention can include less than about 30% by weight of particles having a larger size
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26/80 at about 600pm, and less than about 30% by weight of particles having a size less than about 300 pm, measured using, for example, a RO-TAP ® Model B Mechanical Sifter available from WS Tyler, Inc., Mentor Ohio. While the particles are used as an example of the physical form of the superabsorbent polymers, the invention is not limited to this form, and is applicable to other forms, such as fibers, films, foams, spheres, rods and the like.
[0070] In one embodiment, the particulate superabsorbent polymer can then be treated on the surface with chemicals and treatments as defined herein. In particular, the surface of the particulate superabsorbent polymer can be cross-linked, generally referred to as the cross-linked surface, by the addition of a surface cross-linking agent and heat treatment. In general, surface crosslinking is a process that is believed to increase the crosslinking density of the polymer matrix in the vicinity of the particulate superabsorbent polymer surface with respect to the crosslinking density within the particles.
[0071] Desirable surface crosslinking agents can include chemicals with one or more functional groups that are reactive to the pendant groups on the polymer chains, typically acid groups. Surface crosslinking agents can include compounds that comprise at least two functional groups that can react with functional groups of a polymer structure in a condensation reaction (condensation crosslinker), an addition reaction or a ring opening reaction. These compounds
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27/80 can include condensation crosslinking agents, such as, for example, diethylene glycol, triethylene glycol, polyethylene glycol, glycerin, polyglycerin, propylene glycol, diethanolamine, triethanolamine, polyoxypropylene, oxyethylene-oxypropylene block copolymers, sorbitan acid esters, graffiti acid esters esters of polyoxyethylene sorbitan fatty acids, trimethylolpropane, pentaerythritol, polyvinyl alcohol, sorbitol,
1.3-dioxolan-2-one (ethylene carbonate), 4-methyl-1,3-dioxolan2-one (propylene carbonate), 4,5-dimethyl-1,3-dioxolan-2-one,
4.4- dimethyl-1,3-dioxolan-2-one, 4-ethyl-1,3-dioxolan-2-one, 4-hydroxymethyl-1,3-dioxolan-2-one, 1,3-dioxane-2-one, 4-methyl-1,3-dioxane-2-one, 4,6-dimethyl-1,3-dioxane-2-one, as well as 1,3dioxane-2-one. The amount of surface crosslinking agent can be present in an amount of about 0.01% by weight to about 5% by weight of the dry particulate superabsorbent polymer composition, and as about 0.1% by weight at about 3% by weight and, as from about 0.1% by weight to about 1% by weight, based on the weight of the dry particulate superabsorbent polymer composition.
[0072] After the superabsorbent polymer particles have been brought into contact with the surface crosslinking agent or with the fluid comprising the surface crosslinking agent, the heat treated particulate superabsorbent polymer may include heating the superabsorbent polymer into coated particles at a about 50 to about 300 ° C, or about 75 to about 275 ° C, or between about 150 to about
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28/80 [0073] 250 ° C, and for a time of about 5 to about 90 minutes depending on the temperature, so that the outer region of the polymer structure is more strongly cross-linked compared to the inner region (i.e. , superficial crosslinking). The duration of the heat treatment is limited by the risk that the desired property profile of the polymeric structures is destroyed as a result of the heat effect [0074] In a particular aspect of the cross-linking surface, the particulate superabsorbent polymer is coated with, or treated on the surface , with an alkylene carbonate, such as ethylene carbonate, followed by heating to affect surface crosslinking, which can improve the surface crosslink density and the gel strength characteristics of the superabsorbent particulate polymer. More specifically, the crosslinking agent is coated on the surface of the particulate superabsorbent polymer by mixing the particulate superabsorbent polymer with an aqueous alcoholic solution of the alkylene surface crosslinking carbonate. The amount of alcohol in the aqueous alcoholic solution can be determined by the solubility of the alkylene carbonate and is kept as low as possible, for various reasons, for example, for protection against explosions. Suitable alcohols are methanol, isopropanol, ethanol, butanol, or butyl glycol, as well as mixtures of these alcohols. In some respects, the solvent is desirably water, which is typically used in an amount of about 0.3 wt% to about 5.0 wt%, based on the weight of the dry particulate superabsorbent polymer composition. In still others
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29/80 aspects, the alkylene carbonate surface crosslinking agent can be applied from a powder mixture, for example, with an inorganic carrier material, such as silicon dioxide (SiO2), or in a state of sublimation vapor alkylene carbonate.
[0075] To achieve the desired surface crosslinking properties, alkylene carbonate must be evenly distributed in the particulate superabsorbent polymer. For this purpose, mixing is carried out in suitable mixers known in the art, such as fluidized bed mixers, paddle mixers, rotary drum mixers, or double screw mixers. It is also possible to coat the particulate superabsorbent polymer during one of the process steps for the production of the particulate superabsorbent polymer. In a particular aspect, a suitable process for this purpose is the reverse suspension polymerization process.
[0076] The heat treatment, which follows the coating treatment of the particulate superabsorbent polymer, can be carried out as follows. In general, the heat treatment is at a temperature of about 100 ° C to about 300 ° C. Low temperatures are possible if highly reactive epoxy crosslinking agents are used. However, if an alkylene carbonate is used, then the heat treatment is suitably at a temperature of about 150 ° C to about 250 ° C. In this particular aspect, the treatment temperature depends on the residence time and the type of alkylene carbonate. For example, at a temperature of around 150 ° C, heat treatment
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30/80 is done for an hour or more. In contrast, at a temperature of about 250 ° C, a few minutes (for example, from about 0.5 minutes to about 5 minutes) are sufficient to achieve the desired surface cross-linking properties. Heat treatment can be carried out in conventional dryers or ovens known in the art.
[0077] In addition to the crosslinking surface, the particulate superabsorbent polymeric compositions can still be surface treated with other chemical compositions.
[0078] The absorbent polymers according to the invention may comprise between 0.01% by weight to about 5% by weight of a neutralized multivalent metal salt, based on the weight of the mixture, on the polymer surface. The neutralized polyvalent metal salt is preferably soluble in water. Examples of preferred metal cations include the cations of Al, Fe, Zr, Mg and Zn. Preferably, the metal cation has a valence of at least 3, with Al being most preferred. Mixtures of multivalent metal salts can also be used.
[0079] The neutralized multivalent metal salt may include a chelating anion. Chelating anions suitable in the present invention should be able to form a water-soluble complex with polyvalent metal cations, without compromising the performance-enhancing effects of multivalent metal cations. Examples of preferred chelating anions are the anions of hydroxyl monocarboxylic acids such as lactic acid, glycolic acid, gluconic acid or 3-hydroxypropionic acid. The molar ratio of organic acid to multivalent metal cation is preferably between
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31/80 about 0.5: 1 to about 2: 1, preferably between about 0.75: 1 and about 1.5: 1.
[0080] The polyvalent metal salt can be a neutralized aluminum salt in the form of an aqueous solution, which can be prepared by mixing an aluminum compound with an organic acid (salt), and adjusting the pH with a base or acid, using means well known to those skilled in the art. Examples of aluminum compounds that can be used in the present invention include: aluminum chloride, aluminum sulfate, aluminum nitrate, polyaluminium chloride, sodium aluminate, potassium aluminate, ammonium aluminate, aluminum hydroxide and aluminum oxide.
[0081] The mixture of the aluminum compound with the organic acid (salt) can be acidic or basic. And the pH can be adjusted to the desired range, with a base material or acid. Examples of base materials for pH adjustment include, but are not limited to, sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate or sodium bicarbonate. Examples of acidic materials for pH adjustment include, but are not limited to, hydrochloride, sulfuric acid, methylsulfonic acid, or carbon dioxide in water. Acid aluminum salts such as aluminum chloride, aluminum sulfate, aluminum nitrate and polyaluminium chloride, or basic aluminum salts, such as sodium aluminate, potassium aluminate and ammonium aluminate, can be used for the pH adjustment.
[0082] The neutralized multivalent metal salt suitable in the present invention has a pH of about 5 to about 9, or about 5.5 to about 8, or about 6 to about 7, in a solution
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32/80 aqueous to a concentration of at least about 5 weight percent.
[0083] The neutralized multivalent metal salt can be added at various stages of the surface treatment of the particulate superabsorbent polymer. For example, the neutralized multivalent metal salt can be added to the crosslinking solution and applied to the surface of the particulate superabsorbent polymer, together with the surface crosslinking solution, or the neutralized multivalent metal salt can be added separately from the crosslinking solution. surface, but as part of the surface crosslinking step, or the neutralized multivalent metal salt can be added after the surface crosslinking step.
[0084] The particulate superabsorbent polymer and the appropriately neutralized multivalent metal salt are mixed by dry mixing or in solution, or in an aqueous solution by means well known to those skilled in the art. With the dry mixture, a binder can be used in an amount that is sufficient to ensure that a substantially uniform mixture of salt and the superabsorbent polymer is maintained. The binder can be water or a volatile organic compound having a boiling point of at least 150 ° C. Examples of binders include water, polyols such as propylene glycol, glycerin and poly (ethylene glycol). The neutralized multivalent metal salt can be applied to the surface of the superabsorbent polymer, before or after the surface crosslinking step.
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[0085] In addition to the surface crosslinking agent, and the neutralized multivalent metal salt, the particulate superabsorbent polymer composition of the present invention can be surface treated with 0% to about 5% by weight, or from about 0.001 % to about 5% by weight, or from 0.01% to about 0.5% based on the dry particulate superabsorbent polymer composition of a polymeric coating, such as a thermoplastic coating, or a cationic coating, or a combination of a thermoplastic coating and a cationic coating. In certain particular aspects, desirably, the polymeric coating is a polymer that can be in the form of a solid, emulsion, suspension, colloidal, or solubilized state, or combinations thereof. Polymeric coatings suitable for the present invention may include, but are not limited to, a thermoplastic coating having a thermoplastic melting temperature in which the polymeric coating is applied on the particle surface coinciding with or followed by a temperature of the superabsorbent polymer particle treated at about the thermoplastic melting temperature.
[0086] Examples of thermoplastic polymers include polyolefins, polyethylene, polyester, polyamide, polyurethane, polybutadiene-styrene, linear low density polyethylene (LDPE), ethylene-acrylic acid (EAA) copolymer, ethylene-alkyl methacrylate copolymer (EMA ), polypropylene (PP), maleate polypropylene, ethylene vinyl acetate copolymer (EVA), polyester, polyamide, and mixtures of all polyolefin families, such as mixtures of PP, EVA, EMA, EEA, EBA, HDPE,
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34/80
PEMD, LDPE, LLDPE, and / or VLDPE can also be used advantageously. The term polyolefin, as used herein, is defined above. In particular aspects, maleate polypropylene is a preferred thermoplastic polymer for use in the present invention. A thermoplastic polymer can be functionalized to have additional benefits, such as water solubility or dispersibility.
[0087] Polymeric coatings of the present invention can also include a cationic polymer. A cationic polymer, as used herein refers to a polymer or mixture of polymers comprising a functional group, or groups that have the potential to become positively charged ions on the ionization of an aqueous solution. Functional groups suitable for a cationic polymer include, but are not limited to, primary, secondary or tertiary amino groups, imino groups, amide groups, imide groups, and quaternary ammonium groups. Examples of synthetic cationic polymers include salts or partial salts of poly (vinyl amines), poly (allylamines), poly (ethyleneimine), poly (vinyl propanol amino ethers), poly (acrylamidopropyltrimethylammonium chloride), (poly diallydimethylammonium chloride) ). Examples of naturally-based cationic polymers include partially deacetylated chitin, chitosan, and chitosan salts. Synthetic polypeptides such as polyasparagines, polylysines, polyglutamines and polyarginines are also suitable cationic polymers.
[0088] The absorbent polymers according to the invention can include from about 0% to about 5% by weight, or about 0.001%
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35/80 to about 3% by weight, or from about 0.01% to about 2% by weight based on the weight of the dry particle composition of superabsorbent polymer, water-insoluble inorganic powder. Examples of insoluble inorganic powders include silicon dioxide, silica, titanium dioxide, aluminum oxide, magnesium oxide, zinc oxide, talc, calcium phosphate, clays, diatomatous earth, zeolites, bentonite, kaolin, hydrotalcite, activated clays, etc. The insoluble inorganic powder additive can be a single compound or a mixture of compounds selected from the list above. Examples of silica include colloidal silica, precipitated silica, silicon dioxide, silicic acid and silicates. In certain particular aspects, microscopic non-crystalline silicon dioxide is desirable. Products include Sipernat® 22S and Aerosil® 200 available from Evonik Corporation, Parsippany, New Jersey. In some respects, the particle diameter of the inorganic powder can be 1,000, 000 or less, such as 100, or less.
[0089] The superabsorbent polymer according to the invention can also include the addition of from 0% to about 5% by weight, or from about 0.001% to about 3% by weight, or from about 0.01% to about of 2% by weight based on the weight of powder and dry composition of superabsorbent polymer particles, of a surfactant for the surface of the polymer particle. It is preferred that these be added immediately before, during or immediately after the surface crosslinking step.
[0090] Examples of such surfactants include anionic, nonionic, cationic and amphoteric surface active agents, such as salts of coconut fatty acids, amines and amides, and their salts,
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36/80 alkylsulfuric ester salts, alkylbenzene sulfonic acid salts, dialkyl sulfo-succinate alkyl phosphate salt, and polyoxyethylene alkyl sulfate salt, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenol ether, polyoxyethylene alkyl ether polyoxyethylene sorbitan fatty, fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene-alkylamine, fatty acid esters, and the oxyethylene-oxypropylene block polymer; alkyl amine salts, quaternary ammonium salts, and lauryl dimethylamine oxide. However, it is not necessary to restrict the surfactant to those mentioned above. Such surfactants can be used individually or in combination.
[0091] Superabsorbent polymers can also include from 0% to about 30% by weight, or from about 0.001% to about 25%, or from about 0.01% to about 20% by weight based on weight of the superabsorbent polymer composition of dry particles, water soluble polymers, such as partially or completely polyvinyl acetate hydrolyzate, polyvinylpyrrolidone, starch or starch derivatives, polyglycols or polyacrylic acids, preferably in polymerized form. The molecular weight of these polymers is not critical, as long as they are soluble in water. Preferred water-soluble polymers are starch and polyvinyl alcohol. The preferred content of such water-soluble polymers in which the absorbent polymer according to the invention is 0.30% by weight, or 0 to 5% by weight, based on the total amount of the dry particulate superabsorbent polymer composition. Water-soluble polymers, synthetic polymers, preferably
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37/80 such as polyvinyl alcohol, can also serve as a graft base for the monomers to be polymerized.
[0092] Superabsorbent polymers can also include from 0% to about 5% by weight, or from about 0.001% to about 3% by weight, or from about 0.01% to about 2% by weight based on the weight of the dry particulate superabsorbent polymer composition, dusting agents, such as hydrophilic and hydrophobic dusting agents such as those described in U.S. Patents 6,090,875 and 5,994,440.
[0093] In some respects, additional surface additives can optionally be employed with superabsorbent polymer particles, such as odor-binding substances, such as cyclodextrins, zeolites, inorganic or organic salts, and similar materials, defoamer additives, flow modifying agents, viscosity modifying surfactants, and the like.
[0094] In some respects, the particulate superabsorbent polymer compositions of the present invention can, after a heat treatment phase, be treated with water so that the particulate superabsorbent polymer composition has a water content of up to about 10% by weight of the superabsorbent polymer composition. This water can be added with one or more of the surface additives from those above added to the superabsorbent polymer.
[0095] The particulate superabsorbent polymer composition according to the invention can desirably be prepared by various methods described in the art, including the following two methods.
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38/80
The particulate superabsorbent polymer composition can be prepared continuously or batchwise in an industrial form, on a large scale, including the surface crosslinking surface treatment to be carried out according to the invention. [0096] According to a method, the monomer is partially neutralized by adding any caustic such as sodium hydroxide, to add the monomer or monomers to the caustic. Then the partially neutralized monomer, such as acrylic acid, is converted to a gel by polymerization by free radicals, in aqueous solution, in the presence of crosslinking agents, and any other components, and the gel is crushed, dried, ground and sieved. out to the desired particle size, thus forming a particulate superabsorbent polymer. This polymerization can be carried out continuously or discontinuously. [0097] For the present invention, the particle size of the high capacity superabsorbent polymer composition is dependent on manufacturing processes including milling and sieving. It is well known to those skilled in the art that the particle size distribution of the particulate superabsorbent polymer resembles a normal distribution, or a bell-shaped curve. It is also known that, for various reasons, the normal distribution of the particle size distribution can be tilted in any direction.
[0098] According to another method for making particulate superabsorbent polymer, reverse suspension and emulsion polymerization can also be used for the preparation of the products according to the invention. According to these processes, a solution
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39/80 aqueous, partially neutralized monomer, such as acrylic acid, is dispersed in a hydrophobic organic solvent, with the aid of protective colloids and / or emulsifiers, and polymerization is initiated by free radical initiators. The internal cross-linking agents can be dissolved in the monomer solution and are measured together with it, or are added separately and, optionally, during polymerization. The addition of a water-soluble polymer, as a graft base, optionally takes place through the solution of monomers or by direct introduction into the oil phase. The water is then removed azeotropically from the mixture, and the polymer is filtered off and, optionally, dried. Internal crosslinking can be carried out by polymerization in a polyfunctional crosslinking agent, dissolved in the monomer solution and / or by reaction of suitable crosslinking agents with functional groups of the polymer during the polymerization steps.
[0099] The result of these methods is a particulate superabsorbent polymer, here referred to as a superabsorbent polymer pre-product. A superabsorbent polymer pre-product, as used herein, is produced by repeating all steps of placing the superabsorbent polymer, up to and including drying the material, and coarse grinding in a crusher, and removing particles larger than about 850pm and less than about 150 pm. The superabsorbent polymer pre-product is then treated on the surface including surface crosslinking to form the particulate superabsorbent polymer composition.
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40/80 [0100] The particulate superabsorbent polymer composition of the present invention has certain characteristics, or properties, measured by Free Swell Gel Bed Permeability (GBP), Gel Bed Permeability with a load of about 2068.4 Pa ( 2068.4 Pa GBP), Centrifuge Holding Capacity (CRC), and Absorption under Load of about 6204.3 Pa (6204.3 Pa AUL). The Gel Bed Permeability Free Assay (BRL) is a measure of the permeability of a bed of superabsorbent material swollen in Darcy (for example, separated from the absorbent structure) under a confining pressure, after which it is commonly referred to as swelling. In this context, the term swelling-free means that the superabsorbent material is allowed to swell without a swelling restriction charge after absorbing the test solution, as will be described. Gel bed permeability under load of about 2068.4 Pa (2068.4 Pa BRL) is a measure of the permeability of a bed of Darcy-swollen superabsorbent material (for example, separated from the absorbent structure) under a restraining pressure after what is commonly referred to as 2068.4 Pa Conditions ”. In this context, the term 2068.4 Pa means that the superabsorbent material is allowed to swell under a confining pressure of 2068.4 Pa by absorbing the test solution, as will be described.
[0101] The Test Centrifuge Retention Capacity (CRC) measures the ability of composing particulate superabsorbent polymer to retain liquid contained therein and after being saturated subjected to centrifugation under controlled conditions. THE
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The resulting holding capacity is indicated as grams of liquid retained per gram of sample weight (g / g).
[0102] Test Absorption Under Load (AUL) measures the ability of the particles of the superabsorbent polymer particle composition to absorb a 0.9 weight percent solution of sodium chloride in distilled water at room temperature (test solution ), while the material is under a load of 6205.3 Pa.
[0103] All Centrifuge Retention Capacity, Absorbency under Load and Gel Bed Permeability values set forth herein should be understood to be determined by the Centrifuge Retention Capacity Test, Load Test Absorbance, and Permeability Test at Gel bed as provided.
[0104] A particulate superabsorbent polymer composition produced by a process of the present invention can have a centrifuge holding capacity of about 25 g / g to about 50 g / g, or from about 27 to about 35 g / g, and an absorption capacity under load from 6205.3 Pa about 16g / g and about 24g / g, or from about 18 to about 22g / g, a swelling-free gel bed permeability of about 20 at about 200 Darcy, and gel bed permeability under the load of 2068.4 Pa, at least about 0.8 Darcy.
[0105] Surprisingly, the particulate superabsorbent polymer compositions according to the invention show a significant improvement in permeability, that is, an improvement in the transport of liquid in the bloated state, while maintaining a high absorption and retention capacity.
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42/80 [0106] In an embodiment of the present invention, the particulate superabsorbent polymer composition is a crosslinked polymer in which the particulate superabsorbent polymer composition has a GBP of at least about [5000 and ^-0 ' ^18x ] Darcy , or at least about [8000 and ^-0.18x ] Darcy where x is the numerical value of CRC. Such superabsorbent polymers have a CRC of about 25 to 35 g / g and a GBP value of at least about 20 Darcy, and AUL [0107] 6205, 3 Pa to about 18 g / g to 22 g / g. In another embodiment, the particulate superabsorbent polymer composition has a CRC of about 30 to about 35 g / g, and a GBP value of at least about 30 Darcy. In another embodiment, the particulate superabsorbent polymer composition has a GBP of at least about [12,000 and ^-0.18x ], or the GBP is at least about [10500 and ^-0.18x ], or particulate superabsorbent polymer composition has a CRC of about 27 and about 30g / g, a GBP value of at least about 40Darcy, and a load absorbing capacity of 6205.3 Pa (AUL) of about 18g / g ga 22 g / g.
[0108] The superabsorbent polymer particle compositions according to the present invention can be used in many absorbent articles, including diapers, sanitary napkins, or wound linings, and have the property that they quickly absorb large amounts of menstrual blood, urine or other body fluids. Since the agents according to the invention retain the absorbed liquids, even under pressure and are also able to distribute more liquid inside the building in the bloated state, they are more desirably employed in
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43/80 higher concentrations, in relation to the hydrophilic fiber material, such as lanugo, when compared to the current conventional superabsorbent compositions. They are also suitable for use as a homogeneous superabsorbent layer without cotton content within the fabric construction, as a result of which fine articles are particularly possible. Polymers are also suitable for use in hygiene articles (incontinence products) for adults.
[0109] Absorbent articles generally include a core, which may include from about 60 to 100% by weight of the particulate superabsorbent polymer composition, or may be a fiber web, including 0 to about 40% by weight of the fibrous web. such as cellulose, or the core can include at least about 90% by weight of the superabsorbent polymer particle composition and up to 10% by weight of cellulose fiber, or it can include at least about 95% by weight of the composition of particulate superabsorbent polymer and up to about 5% by weight of nanofiber fibers wherein the nanofiber fibers include fibers having a diameter of less than about 10pm, or less than about 1 pm.
[0110] Absorbent articles, such as diapers, may include: (a) a liquid-permeable top sheet, (b) a liquid-impermeable bottom sheet, (c) a core positioned between (a) and (b), and comprising about 10% to 100%, and preferably about 50% to about 100% by weight, of the superabsorbent polymer particle composition, and from 0% to 90% by weight of hydrophilic fiber material,
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44/80 [0111] (d) optionally, a layer of fabric positioned directly above and below said core (c) and (e) optionally an acquisition.
[0112] The preparation of laminates in the widest sense, and extrusion and co-extruded structures, wet and dry bonded, as well as subsequently bonded, is also possible as well as other preparation processes. A combination of these possible processes with another is also possible.
[0113] The polymers according to the invention are also used in absorbent articles that are suitable for other uses. In particular, the polymers of this invention can be used in absorbent compositions for absorbents of water or aqueous liquids, preferably in constructions for the absorption of body fluids, in foam and foam-like structures, in packaging materials, in constructions of plant growth, as soil improving agents or as vehicles of active compounds. For this, they are processed into a network by mixing with paper or down or synthetic fibers or by distributing the superabsorbent polymers between substrates of paper, cotton or non-woven fabrics or by transforming them into support materials.
[0114] They are best suited for use in absorbent compositions, such as wound pads, sanitary pads, packaging, agricultural pads, food trays and lozenges, and the like.
[0115] Surprisingly, the superabsorbent polymers according to the invention show a significant improvement in
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45/80 permeability, that is, an improvement in the transport of liquid in the swollen state, while maintaining a high absorption and retention capacity.
TEST PROCEDURES
Centrifuge Hold Capacity Test (CRC).
[0116] The CRC test measures the ability of the particulate superabsorbent polymer composition to retain liquid contained therein and after it has been saturated and subjected to centrifugation under controlled conditions. The resulting holding capacity is indicated as grams of liquid retained per gram of sample weight (g / g). The sample to be tested is prepared from particles that are pre-screened using a North American 30 mesh pattern and retained on a North American 50 mesh screen.
As a result, the superabsorbent polymer particle composition sample comprises particles in the range of about 300 to about 600 microns. The particles can be pre-tested by hand or automatically.
[0117] Retention capacity is measured by placing about 0.16 grams of sample particles from the pre-screened superabsorbent polymer composition into a water-permeable bag containing the sample, allowing a test solution (0, 9 weight percent sodium chloride in distilled water) is absorbed freely by the sample. A heat-sealed tea bag material, such as that available from Dexter Corporation (having a business location in Windsor Locks, Connecticut, USA), as per designation of the heat-sealed filter paper model 1234T works well for most applications. The bag is formed
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46/80 folding 5 inches by 3 inches of sample bag material in half and heat sealing at two open ends to form a 2.5 inch per 3 inch rectangular pouch. The heat seals are about 0.25 inches inside the edge of the material. After the sample is placed inside the bag, the open end of the rest of the bag is also heat sealed. Empty bags are also made to serve as controls. Three samples are prepared for each particulate superabsorbent polymer composition to be tested.
[0118] The sealed bags are submerged in a pan containing the test solution at about 23 ° C, causing the bags to be kept until completely wet. After wetting, the samples of the superabsorbent polymer particle composition remain in the solution for about 30 minutes, at which point they are removed from the solution and temporarily placed on a flat, non-absorbent surface.
[0119] The wet bags are then placed in the baskets where the wet bags are separated from each other and are placed on the outer circumferential edge of the basket, where the cart is an appropriate centrifuge capable of subjecting the samples to a g force of about 350 A suitable centrifuge is a Clay Adams Dynac II, model # 0103, with a water collection basket, a digital rpm meter, and a machined drain basket adapted to hold and drain samples from the flat bag. When multiple samples are centrifuged, the samples are placed in opposite positions inside the centrifuge to balance the cart during rotation. The bags (including wet ones, empty bags) are centrifuged at
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47/80 about 1,600 rpm (for example, to achieve a target g force of around 350g of force with a variation of about 240 to about 360g of force), for 3 minutes. G-force is defined as a unit of inertial force on a body that is subjected to rapid acceleration or gravity, equal to 32 m / s ² at sea level. The bags are removed and weighed, with the empty bags (controls) being weighed first, followed by the bags containing the samples of particles of superabsorbent polymer composition. The amount of solution retained by the superabsorbent polymer particle composition sample, taking into account the solution retained by the bag itself, is the centrifugal retention capacity (CRC) of the superabsorbent polymer, expressed as grams of liquid per gram of superabsorbent polymer. . More particularly, the holding capacity is determined by the following equation:
[0120] CRC = [sample bag after centrifugation - empty bag after centrifuge - dry sample weight] / dry sample weight [0121] The three samples are tested, and the results are weighted to determine the CRC of the superabsorbent polymer composition in particles.
Swelling Free Bed Permeability Test (FSGBP) [0122] As used herein, the Permeability Test on
Swelling Free Gel Bed, also referred to as Gel Bed Permeability Swelling Pressure Test under [0123] 0 Pa (FSGBP), determines the permeability of a bed of swollen gel particles (for example, such as particles of the superabsorbent polymer composition, or the superabsorbent polymer particles, before being treated
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48/80 superficially), where it is commonly referred to as swelling-free conditions. The term free of swelling means that the gel particles are allowed to swell without a repressive charge over the absorption test solution, as will be described. An apparatus suitable for carrying out the Permeability test on a Gel bed is shown in Figures 1, 2 and 3, and generally indicated as 500. The test apparatus set 528 comprises a sample container, generally indicated at 530, and a plunger, generally indicated by 536. The plunger comprises a rod 538 which has a cylinder drilled with a hole from the longitudinal axis and a head 550 positioned at the bottom of the axis. The orifice of shaft 562 has a diameter of about 16 mm. The plunger head is attached to the shaft, just like by grip. Twelve holes 544 are drilled in the radial axis of the shaft, positioned three times every 90 degrees having diameters of about 6.4 mm. The 538 shaft is made 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.
[0124] The plunger head 550 has a concentric inner ring with seven holes 560 and an outer ring 14 with holes 545, all holes with a diameter of about 8.8mm, as well as a hole of about 16mm aligned with the shaft. The plunger head 505 is manufactured from a Lexan rod or equivalent material, and is approximately 16 mm high and has a diameter sized in such a way that it fits inside the cylinder 534 at a minimum distance from the wall, but still slides freely. The total length of the plunger head 505 and shaft 538 is about
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49/80 of 8.25 cm, but can be machined at the top of the well to obtain the desired mass of the plunger 536. The plunger 536 includes a 100 mesh fabric made of 564 stainless steel fabric that is biaxially stretched and attached to the lower end of the plunger 536. The web is attached to the plunger head 550 using a suitable solvent that causes the web to be firmly adhered to the plunger head 550. Care must be taken to prevent excess solvent from migrating to exposed portions of the screen and reduce the open area for liquid flow. Acrylic adhesive, Weld-On # 4, from IPS Corporation (having a business location in Gardena, California, USA) is a suitable adhesive.
[0125] The sampling vessel 530 comprises a cylinder 534 and a 4006 stainless steel mesh screen of cloth 566, which is biaxially stretched and attached to the lower end of the cylinder 534. The screen is connected to the cylinder with a suitable solvent which causes the screen to be firmly adhered to the cylinder. Care must be taken to prevent excess solvent from migrating to the exposed portions of the screen and reducing the open area for the flow of the liquid. Acrylic adhesive, Weld-On # 4, from IPS Corporation is a suitable adhesive. A sample of gel particles, as indicated as 568 in figure 2, is supported on the screen 566 inside the cylinder 534 during the test.
[0126] Cylinder 534 can be drilled from a transparent Lexan rod or equivalent material, or can be cut from LEXAN tubing or equivalent material, and has an inside diameter of about 6 cm (for example, a cross-sectional area of about 28.27 cm 2), with a wall thickness
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50/80 of about 0.5 cm and a height of approximately 7.95 cm. A pitch is machined for the outer diameter of cylinder 534 such that a region 534a with an outer diameter of 66 mm for the bottom exists for 31 mm of cylinder 534. An O ring 540 that fits the diameter of region 534a can be placed at the top of the step.
[0127] The annular weight 548 has a drilled counter-hole about 2.2 cm in diameter and 1.3 cm deep, so that it slides freely on the 538 axis. The annular weight also has a through hole 548a about 16 mm. The ring weight 548 can be made of stainless steel or other suitable materials resistant to corrosion in the presence of the test solution, which is a 0.9 weight percent sodium chloride solution in distilled water. The total weight of the plunger 536 and annular weight 548 is equal to about 596 grams (g), which corresponds to a pressure applied to the sample 568 of about 2068.4 Pascals or about 20.7 dynes / cm ² , across a sample area of about 28.27 cm ² .
[0128] When the test solution flows through the test apparatus during the test, as described below, the 530 sampling vessel is usually seated in a 600 spillway. The purpose of the weir is to divert liquid that overflows the top of the 530 vessel from the sample and divert the excess liquid to a separate collection device 601. The dam can be positioned above a scale 602 with a cup 603 resting on it to collect saline passing through the swollen sample 568.
[0129] For the Gel Bed Permeability Test in swelling-free conditions, the plunger 536, with the weight
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548 seated therein, it is placed in an empty sample container 530 and the height from the top of the weight 548 to the bottom of the sample container 530 is measured using an appropriate meter to an accuracy of 0.01 mm. The thickness gauge force applied during the measurement should be as low as possible, preferably less than about 0.74 Newton. It is important to measure the height of each empty sample container 530 of plunger 536, and combination of weight 548 and to maintain control of plunger 536 and weight 548 is used when using multiple tester. The same plunger 536 and weight 548 should be used for the measurement when the sample 568 is then swelled to saturation. It is also desirable that the base of which the sample cup 530 rests on the level, and the upper surface of the weight 548 is parallel to the bottom surface of the sample cup 530.
[0130] The sample to be tested is prepared from the particle superabsorbent polymer composition, which is pre-screened through a North American standard 30 mesh and is retained in a North American standard 50 mesh. As a result, the test sample is composed of particles in the range of about 300 to about 600 microns. Superabsorbent polymer particles can be pre-filtered with, for example, a Model B RO-TAP Mechanical Sieve Shaker available from WS Tyler, Inc., Mentor Ohio. Crusher is conducted for 10 minutes. Approximately 2.0 g of the sample is placed in the sampling vessel 530 and spread evenly over the bottom of the sample vessel. The container, with 2.0 g of sample, without the plunger 536 and weight 548 of it, is then immersed in the solution
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52/80 of 0.9% saline for a period of about 60 minutes to saturate the sample and allow the sample to be free of swelling from any load containment. During saturation, the sample 530 is located on a mesh located in the liquid reservoir, so that the sample cup 530 is raised slightly above the bottom of the liquid reservoir. The mesh does not inhibit the flow of saline into the 530 sample cup. The proper mesh can be obtained as part number 7308 from Eagle Supply and Plastic, having a place of business in Appleton, Wisconsin, USA Saline does not fully cover the particles of composition of superabsorbent polymers, as would be evidenced by a perfectly flat saline surface in the test cell. In addition, saline depth is not allowed to fall so low that the cell's inner surface is defined exclusively by the swollen superabsorbent, rather than saline.
[0131] At the end of this period, the plunger system 536 and weight 548 is placed on the saturated sample 568 in the sample container 530 and then the sampling container 530, the plunger 536, weight 548, and the sample 568 are removed from the solution. After removal and before being measured, the sampling vessel 530, the plunger 536, the weight 548, and the sample 568 are left to stand for approximately 30 seconds on a large, flat, suitable, non-deformable plate grid, uniform thickness. The thickness of the saturated sample 568 is determined by measuring the height of the upper part of the weight 548 lower part of the sampling vessel 530, using the same thickness gauge previously used, provided that the zero point is identical to the
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53/80 of the first height measurement. The sampling vessel 530, the plunger 536, weight 548, and the sample 568 can be placed on a large grid of flat, non-deformable plate, of uniform thickness, which will provide drainage. The plate has an overall dimension of 7.6 inches by 7.6 inches, and each has a cell size grid of 1.59 inches long by 1.59 inches wide by 1.12 inches deep . A large grid of suitable flat, non-deformable plate material is a parabolic diffuser panel, catalog number 1624K27, available from McMaster Carr Supply Company, having an office in Chicago, Illinois, USA, which can be cut to the appropriate dimensions . This large, flat, non-deformable mesh must also be present when measuring the height of the initial empty set. Height measurement should be done as soon as possible after the thickness gauge is involved. The height measurement obtained from measuring the sample of the empty container 530, the plunger 536, weight 548 is subtracted from that obtained after measuring the height by saturating the sample 568. The resulting value is the thickness or height H of the swollen sample.
[0132] The permeability measurement starts, providing a 0.9% saline flow to the sampling vessel 530 with the sample 568 saturated, the plunger 536, weight 548 inside. The flow rate of the test solution into the container is adapted to cause the saline solution to overflow the upper part of the cylinder 534 resulting in a consistent main pressure equal to the height of the sample container 530. The test solution can be added via any appropriate means,
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54/80 sufficient to guarantee a small but consistent amount of overflow from the top of the cylinder, such as with a 604 metering pump. Excess liquid is diverted to a 601. selective collection device. passes through sample 568 versus time is measured gravimetrically using the 602 scale and 603 beaker. Data points from the 602 scale are collected every second for at least 60 seconds after the burst started. Data collection can be done manually or with data collection software. The flow rate, Q, across the swollen sample 568 is determined in units of grams / second (g / s) by an adjustment of linear least squares of the fluid that passes through the sample 568 (in grams) as a function of time (in seconds) ).
[0133] Permeability of cm ² is obtained through the following equation:
K = [Q * H * p] / [A * p * P] where K = Permeability (cm ² ), Q = flow rate (g / s), h = height of the swollen sample (cm), μ = viscosity of the liquid (poise) (about one centipoise for the test solution used with this test), A = cross-sectional area for the liquid flow (28.27 cm ² for the sample container used with this test), ρ = density of the liquid (g / cm ³ ) (approximately one g / cm ³ , for the test solution used with this test) and
P = hydrostatic pressure (dynes / cm ² ) (usually about 7797 dynes / cm ² ). The hydrostatic pressure is calculated from P = ρ * g * H, where ρ = density of the liquid (g / cm3), g = acceleration
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55/80 gravitational, nominally 981 cm / sec ² eh = fluid height, for example, 7.95 cm for the Gel Bed Permeability Test described here.
[0134] A minimum of two samples have been tested and the results are weighted to determine the gel bed permeability of the sample of the particulate superabsorbent polymer composition.
Permeability Test on Gel Bed under load of 2068.4 Pa (2068.4 Pa GBP) [0135] Permeability on Gel Bed under load at 2068.4 Pa is tested in the way of Permeability Test on Gel Bed free of charge swelling, except that plunger 536 and weight 548 are placed on dry sample 568 of sampling container 530 before assembly is submerged in 0.9% saline.
Absorption under load test ((6205.3 Pa) AUL) [0136] The Absorption under load test (AUL) measures the ability of the particulate superabsorbent polymer to absorb a 0.9 weight percent chloride solution sodium in distilled water at room temperature (test solution), while the material is under a load of 6205.3 Pa. The apparatus for the AUL test consists of:
• An AUL assembly including a cylinder, a 4.4 g piston, and a standard weight of 317 gm. The components of this set are described in further detail below.
• A square plastic tray with a flat bottom wide enough to allow the glass frits to be placed on the bottom, without contact with the walls of the
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56/80 tray. A plastic tray that is 9 by 9 (22.9 cm x 22.9 cm), with a depth of 0.5 to 1 (1.3 cm to 2.5 cm) is commonly used for this test method.
• A 9 cm diameter of sintered glass frit with a C porosity (25-50 microns). This frit is prepared in advance by equilibrating in saline solution (0.9% sodium chloride in distilled water, by weight). In addition to being washed with at least two portions of fresh saline, the frit must be immersed in saline solution for at least 12 hours before the AUL measurements.
• Whatman grid, with 1.9 cm in diameter of filter paper circles.
• A supply of saline solution (0.9% sodium chloride in distilled water, by weight).
[0137] Referring to figure 4, cylinders 412 of the AUL 400 set used to contain particles of superabsorbent polymer composition 410 are made from one inch (2.54 cm) in diameter of slightly machined thermoplastic tubing, to be sure of concentricity. After machining, a 400 mesh of stainless steel woven from steel wire 414 is connected to the bottom of the cylinders 412 by heating the steel wire fabric 414 with a flame until it incarnates, after which the cylinders 412 are made on the cooled steel wire fabric. A soldering iron can be used to touch up the seal if it is unsuccessful or breaks. Care must be taken to keep the base flat and smooth and not to deform the inside of the 412 cylinders.
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57/80 [0138] The 4.4 g (416) piston is made from solid material one inch in diameter (for example, Plexiglas ®) and is machined to fit closely without connection to the 412 cylinders.
[0139] A standard weight 317gm 418 is used to provide an immobilized load 62.053 dyne / cm ² (about 6205.3 Pa). The weight is cylindrical, 1 inch (2.5 cm) in diameter, the weight of stainless steel, which is machined to fit closely without connecting to the cylinder.
[0140] Unless otherwise specified, a sample 410 corresponds to a layer of at least about 300 gsm. (0.16g) of particles of superabsorbent polymer composition is used to test the AUL. Sample 410 is made from particles of the superabsorbent polymer composition, which are pre-screened by the North American # 30 mesh pattern and retained in the American # 50 mesh. Particles of the superabsorbent polymer composition can be pre-screened with, for example, a
RO-TAP ® Model B mechanical sieve shaker available from WS Tyler, Inc., Mentor Ohio. Crusher is conducted for about 10 minutes.
[0141] The inside of the cylinder 412 is cleaned with an antistatic cloth, before placing the particles of the superabsorbent polymer composition 410 onto the cylinders 412.
[0142] The desired amount of the sample of sieved superabsorbent polymer composition particles 410 (about 0.16 g) is weighed out on paper and evenly distributed over wire fabric 414 at the bottom of cylinder 412. The weight gives
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58/80 composition of superabsorbent polymer in particles at the bottom of the cylinder is registered as 'SA', for use in the AUL calculation described below. Care is taken to ensure that there is no superabsorbent polymer composition in particles that stick to the cylinder wall. After carefully placing 4.4g on piston 412 and 317g of weight 418 on the particles of the superabsorbent polymer composition 410 on cylinders 412, the AUL 400 assembly including the cylinder, plunger, weight, and particles of the superabsorbent polymer particle composition is heavy, and the weight is recorded as weight A.
[0143] A 424 sintered fried glass (described above) is placed on plastic tray 420, with saline solution 422 added at a level equal to that of the upper surface of glass mass 424. A single circle of filter paper 426 is placed gently over the glass mass 424, and the AUL 400 assembly with the superabsorbent polymer particle composition 410 is then placed on top of filter paper 426. The AUL 400 assembly is then left to remain on top of filter paper 426 for a one-hour test period, paying particular attention to keeping the level of saline in the tray constant. At the end of the one hour test period, the AUL device is then weighed, with this value recorded as 'B' weight.
[0144] The AUL (6205.3 Pa) is calculated as follows:
AUL (2068.4 Pa) = (B-A) / SA where
A = Weight of AUL Unit with dry SAP
B = Weight of AUL Unit with SAP after 60 minutes of absorption
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SA = Real SAP weight [0145] A minimum of two tests are performed and the results are weighted to determine the AUL value under load of 6205.3 Pa. Samples of particles of superabsorbent polymer composition are tested at about 23 ° C and about 50% relative humidity.
EXAMPLES [0146] The following are Comparative Examples 1-7 of the SAP Pre-Product, and Examples 1-14 are presented to illustrate product inventions that include the composition of superabsorbent polymer particles, an absorbent article, and processes for making the particulate superabsorbent polymer composition as defined in the claims, and does not limit the scope of the claims. Unless otherwise indicated, all parts and percentages are based on the composition of superabsorbent polymer in dry particles.
SAP A pre-product [0147] A superabsorbent polymer can be made as follows. In a polyethylene container equipped with a stirrer and cooling coils, [0148] 2.0 kg of 50% NaOH and 3.32 kg of distilled water and cooled to 20 ° C were added. 0.8 kg of glacial acrylic acid was then added to the caustic solution and the solution again cooled to 20 ° C. 4.8 g of polyethylene glycol acrylate monoalyleter, 4.8 g of ethoxylated trimethylol triacrylate Sartomer® 454, and 1.6 kg of glacial acrylic acid, were added to the first solution, followed by cooling to 4-6 ° C. Nitrogen was bubbled through the monomer solution for about 5 minutes. The solution
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60/80 monomer was then discharged into a rectangular tray. 80g of 1% by weight of aqueous H2O2 solution, 120 g of 2% by weight aqueous sodium persulfate solution and 72g of 0.5% by weight aqueous sodium erythorbate solution was added to the monomer solution to initiate the reaction of polymerization. The stirrer was stopped and the monomer was started and allowed to polymerize for 20 minutes.
[0149] A particulate superabsorbent polymer can be prepared as follows. The resulting hydrogel was chopped and extruded with a commercial Hobart 4M6 extruder, followed by drying in a forced air oven Procter & Schwartz model 062 at 175 ° C for 12 minutes with the flow up and 6 minutes with the air flow down over a perforated 20-inch x 40-inch metal tray for a final product moisture level of less than 5% by weight. The dry material was ground in a PRODEVA shredder model 315-S, ground in a three-stage MPI 666-F roller mill and sieved with a Minox MTS 600DS3V to remove particles larger than 8 50μη and smaller than 150 μη. The SAP A pre-product obtained was then subjected to surface modification, as described in the following examples and comparative examples.
[0150] Comparative examples of polymer composition in 1-7 superabsorbent particles can be prepared as follows.
Comparative Example 1 [0151] 1.84 g of aluminum sulfate hydrate (technical grade, commercially available from Fisher Scientific) was dissolved in 8 g of deionized water. The pH of the solution was tested as 2.8. Ethylene carbonate (2g) was dissolved in the solution of
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61/80 aluminum sulfate and the resulting mixture was applied to the surface of 200 g of SAP A pre-product using a finely atomized spray from a Paasche VL spray while the SAP particles were fluidized in air and mixed continuously . The coated material was then heated in a convection oven at 185 ° C for 25 minutes for surface crosslinking. The composition of the comparative superabsorbent polymer particles was then sieved with US standard 20/100 mesh sieves to remove particles greater than 850pm and less than 150 pm.
Comparative Example 2 [0152] 1.82 g of aluminum lactate (marketed by SigmaAldrich) was dissolved in 8 g of deionized water. The pH of the solution was tested as 3.7. Ethylene carbonate (2 g) was dissolved in the aluminum lactate solution and the resulting mixture was applied to the surface of 200 g of SAP A pre-product using a finely atomized spray from a Paasche VL spray while the particles SAP were fluidized in air and mixed continuously. The coated material was then heated in a convection oven at 185 ° C for 35 minutes for surface crosslinking. The composition of the comparative superabsorbent polymer particles was then sieved with 20/100 American standard mesh sieves to remove particles greater than 850pm and less than 150 pm.
Comparative Example 3 [0153] 1.84 g of aluminum sulfate hydrate (technical grade, commercially available from Fisher Scientific) and 0.59 g
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62/80 lactic acid (88%, commercially available from Archer Daniels Midland Company (ADM) of Decatur, Illinois 62526, USA) was dissolved in 8 g of deionized water. The pH of the solution was tested as 1.0. Ethylene carbonate [0154] (2 g) was dissolved in the previous solution and the resulting mixture was applied to the 200 g SAP A pre-product surface using a finely atomized spray from a Paasche VL spray while the particles SAP were fluidized in air and mixed continuously. The coated material was then heated in a convection oven at 185 ° C for 35 minutes for surface crosslinking. The composition of the comparative superabsorbent polymer particles was then
sifted with sieves 20/100 in mesh pattern From USA to remove the larger particles than what 8 50pm and smaller than that 150 pm.Comparative Example 4[0155] 1.84 g of hydrate sulfate aluminum (degree technician, available commercially to leave in Fisher Scientific) and 0.76 g
sodium lactate (commercially available from SigmaAldrich) were dissolved in 8 g of deionized water. The pH of the solution was tested as 2.8. Ethylene carbonate (2 g) was dissolved in the previous solution and the resulting mixture was applied to the surface of 200 g of SAP A pre-product using a finely atomized spray from a Paasche VL spray while the SAP particles were fluidized in air and mixed continuously. The coated material was then heated in a convection oven at 185 ° C for 35 minutes to
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63/80 superficial crosslinking. The composition of the comparative superabsorbent polymer particles was then sieved with standard 20/100 US mesh sieves to remove particles greater than 850pm and less than 150 pm.
Comparative Example 5 [0156] 0.48 g of sodium aluminate (commercially available from Sigma-Aldrich) was dissolved in 8 g of deionized water. The pH of the solution was tested as 14. Ethylene carbonate (2 g) was dissolved in the previous solution and the resulting mixture was applied to the surface of 200 g of SAP A Pre-product using a finely atomized spray from a water spray. Paasche VL while the SAP particles were fluidized in air and mixed continuously. The coated material was then heated in a convection oven at 185 ° C for 50 minutes for surface crosslinking. The composition of the comparative superabsorbent polymer particles was then sieved with standard 20/100 North American mesh sieves to remove particles greater than 850pm and less than 150 pm.
Comparative Example 6 [0157] 3.44 g of aluminum lactate (marketed by SigmaAldrich) was dissolved in 15.28 g of deionized water. 1.45 grams of a sodium hydroxide solution (50% in water) was added to the solution to increase the pH to 6.4. The molar ratio of aluminum lactate in the solution was 3: 1. Ethylene carbonate (2 g) was dissolved in 10.08 g of the previous solution and the resulting mixture was applied to the surface of 200 g of SAP A Pre-product using a finely atomized spray from a
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64/80 Paasche VL spray while the SAP particles were fluidized in air and continuously mixed. The coated material was then heated in a convection oven at 185 ° C for 45 minutes for surface crosslinking. The composition of the comparative superabsorbent polymer particles was then sieved with standard 20/100 North American mesh sieves to remove particles greater than 850pm and less than 150 pm.
Comparative Example 7 [0158] To a 600 ml beaker were added 160 g of water, 40 g of sodium hydroxide solution (50% weight / weight in water), and 41 g of sodium aluminate (commercially available from Sigma-Aldrich). The mixture was stirred to give a clear solution. A solution of citric acid monohydrate (105 g, commercially available from Sigma-Aldrich) in 150 g of water was added to the beaker, while the container was cooled in an ice bath. The resulting mixture was a clear solution with a pH value of 7. The molar ratio of aluminum citrate in the solution was about 1: 1.
[0159] 4.0 g of aluminum citrate solution, 2.0 g of ethylene carbonate, and 4.0 g of deionized water were mixed to give a clear solution. The resulting mixture was applied to the surface of 200 g of SAP A Pre-product using a finely atomized spray from a Paasche VL spray while the SAP particles were fluidized in air and mixed continuously. The coated material was then heated in a convection oven at 185 ° C for 40 minutes for surface crosslinking. The composition of the polymer particles
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Comparative 65/80 superabsorbent was then sieved with 20/100 North American mesh sieves to remove particles greater than 850pm and less than 150 pm.
[0160] The superabsorbent polymeric particle compositions of the present invention can be made as follows, as set forth in Examples 1-14.
Example 1 [0161] To a 100 ml beaker were added 4.09 g of lactic acid (88%, commercially available from ADM) and 16.57 g of water. The beaker was cooled in an ice bath and 10.15 g of sodium hydroxide pad solution (50% w / w in water) added slowly. The mixture was stirred to give a clear solution. A solution of aluminum sulfate hydrate (24.78 g, 48% by weight / weight in water) was added to the beaker, while the container was cooled in an ice bath. The resulting mixture was a clear solution with a pH of 6.5. The molar ratio of aluminum lactate in the solution was about 1: 1.
[0162] 11.12 g of the aluminum salt solution is obtained here, 2.0 g of ethylene carbonate, and 1 g of deionized water were mixed to give a clear solution. The resulting mixture was applied to the surface of 200 g of SAP A Pre-product using a finely atomized spray from a Paasche VL spray while the SAP particles were fluidized in air and mixed continuously. The coated material was then heated in a convection oven at 185 ° C for 35 minutes for surface crosslinking. The composition of the comparative superabsorbent polymer particles was then sieved with sieves
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66/80 20/100 American standard mesh to remove particles greater than 850pm and less than 150 pm.
Example 2 [0163] To a 1000 ml beaker was added 49 g of lactic acid (88%, commercially available from ADM) and 161.5 g of water. The beaker was cooled in an ice bath and the solution was stirred with a magnetic stir bar. A solution of sodium aluminate (73.2 g, 43% by weight / weight in water) was added to the beaker. Then, a solution of aluminum sulfate hydrate (59.3 g, 48% by weight / weight in water) was added to the beaker. The resulting mixture was a clear solution with a pH value of 6.3. The molar ratio of aluminum lactate in the solution was about 1.1: 1. The neutralized aluminum salt solution obtained was used to modify the SAP surface.
[0164] 5.7 g of the neutralized aluminum salt solution, 2.0 g of ethylene carbonate, and 4.0 g of deionized water were mixed to give a clear solution. The resulting mixture was applied to the surface of 200 g of SAP A Pre-product using a finely atomized spray from a Paasche VL spray while the SAP particles were fluidized in air and mixed continuously. The coated material was then heated in a convection oven at 185 ° C for 40 minutes for surface crosslinking. The composition of the comparative superabsorbent polymer particles was then sieved with 20/100 American standard mesh sieves to remove particles greater than 850pm and less than 150 pm.
Example 3
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67/80 [0165] Same as Example 2, except the coated material is heated to 185 ° C for 70 minutes.
Example 4 [0166] In a polyethylene container equipped with a stirrer and cooling coils, 2.0 kg of 50% NaOH and 3.32 kg of distilled water cooled to 20 ° C were added.
[0167] 0.8 kg of glacial acrylic acid was then added to the caustic solution and the solution again cooled to 20 ° C. 7.2 g of polyethylene glycol acrylate monoallyleter, 7.2 g of ethoxylated trimethylol triacrylate 454 and 1.6 kg of glacial acrylic acid, was added to the first solution, followed by cooling to 4-6 ° C. Nitrogen was bubbled through the monomer solution for about 5 minutes. The monomer solution was then discharged into a rectangular tray. 80g of 1% by weight of aqueous H2O2 solution, 120 g of 2% by weight aqueous sodium persulfate solution and 72g of 0.5% by weight aqueous sodium erythorbate solution was added to the monomer solution for start the polymerization reaction. The stirrer was stopped and the monomer was started and allowed to polymerize for 20 minutes. The resulting hydrogel was chopped and extruded with a commercial Hobart 4M6 extruder, followed by drying in a forced air oven Procter & Schwartz model 062 at 175 ° C for 12 minutes with the flow up and 6 minutes with the air flow down over a perforated 20-inch x 40-inch metal tray for a final product moisture level of less than 5% by weight. The dry material was coarsely ground in a PRODEVA model 315-S, ground in a three-stage MPI 666-F roller mill and
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68/80 sieved with a Minox MTS 600DS3V to remove particles greater than 850pm and less than 150 pm. A SAP A Pre-product obtained was then submitted to the surface modification.
[0168] The same neutralized aluminum salt solution as described in Example 2 was used for the modification of the SAP surface. 5.7 g of the neutralized aluminum salt solution, 2.0 g of ethylene carbonate, and 4.0 g of deionized water were mixed to give a clear solution. The resulting mixture was applied to the surface of 200 g of SAP A Pre-Product obtained here using a finely atomized spray from a Paasche VL sprayer while the SAP particles were fluidized in air and mixed continuously. The coated material was then heated in a convection oven at 185 ° C for 55 minutes for surface crosslinking. The composition of the comparative superabsorbent polymer particles was then sieved with 20/100 American standard mesh sieves to remove particles greater than 850pm and less than 150 pm.
Example 5 [0169] 1.60 g of glycolic acid (commercially available from SigmaAldrich) and 12.95 g of water were added to a 100 ml beaker. The beaker was cooled in an ice bath and the solution was stirred with a magnetic stir bar. A solution of sodium aluminate (10.18 g, 20% by weight / weight in water) was added to the beaker. Then, a solution of aluminum sulfate hydrate (4.84 g, 40% by weight / weight in water) was added to the beaker. The resulting mixture was a clear solution with a pH value of 6.6. The molar ratio of aluminum glycolate
Petition 870190138489, of 12/23/2019, p. 74/110
69/80 of the solution was about 0.7: 1. The neutralized aluminum salt solution obtained was used to modify the SAP surface.
[0170] 9.86 g of the neutralized aluminum salt solution obtained here and 2.0 g of ethylene carbonate were mixed to give a clear solution. The resulting mixture was applied to the surface of 200 g of SAP A Pre-product using a finely atomized spray from a Paasche VL spray while the SAP particles were fluidized in air and mixed continuously. The coated material was then heated in a convection oven at 185 ° C for 55 minutes for surface crosslinking. The composition of the comparative superabsorbent polymer particles was then sieved with 20/100 American standard mesh sieves to remove particles greater than 850pm and less than 150 pm.
Example 6 [0171] 1.92 g of glycolic acid (commercially available from SigmaAldrich) and 13.01 g of water were added to a 100 ml beaker. The beaker was cooled in an ice bath and the solution was stirred with a magnetic stir bar. A solution of sodium aluminate (10.37 g, 20% by weight / weight in water) was added to the beaker. Then, a solution of aluminum sulfate hydrate (4.49 g, 40% by weight / weight in water) was added to the beaker. The resulting mixture was a clear solution with a pH value of 6.0. The molar ratio of aluminum glycolate in the solution was about 0.81: 1. The aluminum salt solution
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Neutralized 70/80 obtained was used to modify the SAP surface.
[0172] 9.93 g of the neutralized aluminum salt solution obtained here and 2.0 g of ethylene carbonate, were mixed to give a clear solution. The resulting mixture was applied to the surface of 200 g of SAP A Pre-product using a finely atomized spray from a Paasche VL spray while the SAP particles were fluidized in air and mixed continuously. The coated material was then heated in a convection oven at 185 ° C for 55 minutes for surface crosslinking. The composition of the comparative superabsorbent polymer particles was then sieved with 20/100 American standard mesh sieves to remove particles greater than 850pm and less than 150 pm.
Example 7 [0173] 2.26 g of glycolic acid (commercially available from SigmaAldrich) and 13.07 g of water were added to a 100 ml beaker. The beaker was cooled in an ice bath and the solution was stirred with a magnetic stir bar. A solution of sodium aluminate (10.58 g, 20% by weight / weight in water) was added to the beaker. Then, a solution of aluminum sulfate hydrate (4.11 g, 40% by weight / weight in water) was added to the beaker. The resulting mixture was a clear solution with a pH of 6.2. The molar ratio of aluminum glycolate in the solution was about 0.95: 1. The neutralized aluminum salt solution obtained was used to modify the SAP surface.
Petition 870190138489, of 12/23/2019, p. 76/110
71/80 [0174] 10.01 g of the neutralized aluminum salt solution obtained here and 2.0 g of ethylene carbonate were mixed to give a clear solution. The resulting mixture was applied to the surface of 200 g of SAP A Pre-product using a finely atomized spray from a Paasche VL spray while the SAP particles were fluidized in air and mixed continuously. The coated material was then heated in a convection oven at 185 ° C for 55 minutes for surface crosslinking. The composition of the comparative superabsorbent polymer particles was then sieved with 20/100 American standard mesh sieves to remove particles greater than 850pm and less than 150 pm.
Example 8 [0175] The same neutralized aluminum salt solution as described in Example 2 was used for the modification of the SAP surface. 5.7 g of the neutralized aluminum salt solution, 0.4 g of ethylene glycol, and 4.0 g of deionized water were mixed to give a clear solution. The resulting mixture was applied to the surface of 200 g of SAP A Pre-product using a finely atomized spray from a Paasche VL spray while the SAP particles were fluidized in air and mixed continuously. The coated material was then heated in a convection oven at 185 ° C for 55 minutes for surface crosslinking. The composition of the comparative superabsorbent polymer particles was then sieved with 20/100 American standard mesh sieves to remove particles greater than 850pm and less than 150 pm.
Petition 870190138489, of 12/23/2019, p. 77/110
72/80
Example 9 [0176] The same neutralized aluminum salt solution as described in Example 2 was used for the modification of the SAP surface. 5.7 g of the neutralized aluminum salt solution, 0.4 g of glycerol and 4.0 g of deionized water were mixed to give a clear solution. The resulting mixture was applied to the surface of 200 g of SAP A Pre-Product using a finely atomized spray from a Paasche VL spray while the particulate superabsorbent polymer was fluidized in air and mixed continuously. The coated material was then heated in a convection oven at 185 ° C for 55 minutes for surface crosslinking. The composition of the comparative superabsorbent polymer particles was then sieved with 20/100 American standard mesh sieves to remove particles greater than 850pm and less than 150 pm.
Example 10 [0177] The same neutralized aluminum salt solution as described in Example 2 was used for the modification of the SAP surface. 5.7 g of the neutralized solution of aluminum salt, 2.0 g of ethylene carbonate, and 2.0 g of deionized water were mixed to give a clear solution. The resulting mixture was applied to the surface of 200 g of SAP A Pre-product using a finely atomized spray from a Paasche VL spray while the SAP particles were fluidized in air and mixed continuously. Then, a suspension containing 1.0 g of kaolin (commercially available from Thiele Kaolin Company, Sanderville, GA 31082 USA) and 2.75 g of water was
Petition 870190138489, of 12/23/2019, p. 78/110
73/80 sprayed on SAP particles. The coated material was heated in a convection oven at 185 ° C for 55 minutes for surface crosslinking. The composition of the comparative superabsorbent polymer particles was then sieved with 20/100 American standard mesh sieves to remove particles greater than 850pm and less than 150 pm.
Example 11 [0178] A solution containing 2.0 g of ethylene carbonate, and
6.0 g of deionized water was applied to the surface of 200 g of SAP A Pre-product using a finely atomized spray from a Paasche VL spray while the SAP particles were fluidized in air and mixed continuously. The coated material was then heated in a convection oven at 185 ° C for 55 minutes for surface crosslinking. The particulate superabsorbent polymer composition was subjected to additional surface treatment with the same neutralized aluminum salt solution as described in Example 2. 5.7 g of the neutralized aluminum salt solution, 0.2 g of polyethylene glycol (molecular weight 8000), and 4.0 g of deionized water were mixed to give a clear solution. The resulting mixture was applied to the surface of the crosslinked particulate material obtained here using a finely atomized spray from a Paasche VL sprayer while the SAP particles were fluidized in air and mixed continuously. The coated material was relaxed at room temperature for at least 1 hour before testing.
Example 12
Petition 870190138489, of 12/23/2019, p. 79/110
74/80 [0179] The same neutralized aluminum salt solution as described in Example 2 was used for the modification of the SAP surface. 5.7 g of the neutralized aluminum salt solution, 0.2 g of polyethylene glycol (molecular weight 8000), and 4.0 g of deionized water were mixed to give a clear solution. The resulting mixture was applied to the superabsorbent polymer particle composition, obtained in Example 2, using a finely atomized spray from a Paasche VL spray while the SAP particles were fluidized in air and mixed continuously. The coated material was relaxed at room temperature for at least 1 hour before testing. Example 13 [0180] The same neutralized aluminum salt solution as described in Example 2 was used for the modification of the SAP surface. 5.7 g of the neutralized aluminum salt solution, 0.2 g of polyethylene glycol (molecular weight 8000), and 4.0 g of deionized water were mixed to give a clear solution. The resulting mixture was applied to the particulate superabsorbent polymer composition obtained in Example 4, using a finely atomized spray from a Paasche VL spray while the SAP particles were fluidized in air and mixed continuously. The coated material was relaxed at room temperature for at least 1 hour before testing. Example 14 [0181] In a polyethylene container equipped with a stirrer and cooling coils, 2.0 kg of 50% NaOH and 3.32 kg of distilled water cooled to 20 ° C were added.
Petition 870190138489, of 12/23/2019, p. 80/110
75/80 [0182] 0.8 kg of glacial acrylic acid was then added to the caustic solution and the solution again cooled to 20 ° C. 8.2 g of monoallyl polyethylene glycol acrylate, 8.2 g of polyethylene glycol diacrylate 300 and 1.6 kg of glacial acrylic acid were added to the first solution, followed by cooling to 4-6 ° C. Nitrogen was bubbled through the monomer solution for about 5 minutes. The monomer solution was then discharged into a rectangular tray. 80g of 1% by weight of aqueous H2O2 solution, 120 g of 2% by weight aqueous sodium persulfate solution and 72g of 0.5% by weight aqueous sodium erythorbate solution were added to the monomer solution to initiate the polymerization reaction. The stirrer was stopped and the monomer was started and allowed to polymerize for 20 minutes. The resulting hydrogel was chopped and extruded with a commercial Hobart 4M6 extruder, followed by drying in a forced air oven Procter & Schwartz model 062 at 175 ° C for 12 minutes with the flow up and 6 minutes with air flow down over a perforated 20-inch x 40-inch metal tray for a final product moisture level of less than 5% by weight. The dry material was coarsely ground in a PRODEVA model 315-S crusher, ground in a three-stage IPM 666-F laminator, and sieved with a Minox MTS 600DS3V to remove particles greater than 850pm and less than 150pm. The pre-product A obtained was then subjected to surface modification.
[0183] The same neutralized aluminum salt solution as described in Example 2 was used for the modification of the SAP surface. 55.7 g of the neutralized salt solution
Petition 870190138489, of 12/23/2019, p. 81/110
76/80 aluminum, 2.0 g of ethylene carbonate, and 4.0 g of deionized water were mixed to give a clear solution. The resulting mixture was applied to the surface of 200 g of SAP pre-product obtained here using a finely atomized spray from a Paasche VL sprayer while the SAP particles were fluidized in air and mixed continuously. The coated material was then heated in a convection oven at 185 ° C for 70 minutes for surface crosslinking. The composition of the comparative superabsorbent polymer particles was then sieved with 20/100 US standard mesh sieves to remove particles greater than 850pm and less than 150 pm.
[0184] The results of the above examples and comparative examples are summarized in the following table.
Table 1
CompositionParticular ofpolymersuperabsorbent pH ofaluminum salt solution CRC(g / g) 6205.3PaAUL(g / g) GBP(Darcy) 2068.4GBP(Darcy) ExampleComparative 1 2.8 34 17.4 23 0, 6 ExampleComparative 2 3.7 32, 6 22, 9 7 1, 9 ExampleComparative 3 1 32 19, 9 13 2 ExampleComparative 4 2.8 32, 6 20, 9 12 1, 6
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77/80
Composition pH ofaluminum salt solution CRC(g / g) 6205.3PaAUL(g / g) GBP(Darcy) 2068.4GBP(Darcy) Privatepolymersuperabsorb inrnte ExampleComparative 5 14 32 19, 7 4 0, 5 ExampleComparative 6 6, 4 32.7 23.2 7 1, 8 ExampleComparative 7 7 32, 1 22, 6 4 at Example 16, 5 32 18, 8 37 1, 9 Example 26, 3 33, 1 19, 4 33 at Example 36, 3 31, 1 18.2 56 at Example 46, 3 28 19, 4 69 at Example 56, 6 31, 9 20, 1 38 1, 6 Example 66, 0 32, 8 19, 3 39 1.7 Example 76.2 33, 1 19, 8 31 1, 6 Example 86, 3 32.3 18.5 38 1.3 Example 96, 3 32, 6 18, 1 36 1, 6 Example 106, 3 32, 1 19, 5 46 2.5 Example 1163 31 18, 1 48 1, 1 Example 126, 3 32.4 20 42 2 Example 136, 3 27.3 19, 1 81 6, 6 Example 146, 3 33, 9 18, 6 41 at
Petition 870190138489, of 12/23/2019, p. 83/110
78/80 [0185] Table 2 summarizes the GBP values calculated according to the equations of GBP = 8,000 e-0.18x and GBP = 10,500 e-0.18x, where x = CRC.
Table 2
CompositionParticular ofpolymersuperabsorbent pH of the aluminum salt solution CRC (g / g) GBP = 8000e-0.18x(Darcy) GBP = 10500e-0.18x(Darcy) ExampleComparative 1 2.8 34 17, 6 23, 1 ExampleComparative 2 3.7 32, 6 22, 6 29, 7 ExampleComparative 3 1 32 25.2 33, 1 ExampleComparative 4 2.8 32, 6 22, 6 29, 7 ExampleComparative 5 14 32 25.2 33, 1 ExampleComparative 6 6.4 32.7 22.2 29.2 ExampleComparative 7 7 32, 1 24, 8 32.5 Example 1 6, 5 32 25.2 33, 1 Example 2 6, 3 33, 1 20, 7 27, 1 Example 3 6, 3 31, 1 29, 6 38, 9 Example 4 6, 3 28 51, 8 68, 0
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79/80
Composition pH of Particular of solution ofGBP = 8000 GBP = 10500 polymer salt ofe-0.18x e-0.18x superabsorbent aluminum CRC (g / g) (Darcy) (Darcy) Example 5 6, 6 31, 9 25, 7 33, 7 Example 6 6, 0 32, 8 21, 8 28, 6 Example 7 6.2 33, 1 20, 7 27, 1 Example 8 6, 3 32.3 23, 9 31.3 Example 9 6, 3 32, 6 22, 6 29, 7 Example 10 6, 3 32, 1 24, 8 32.5 Example 11 63 31 30.2 39, 6 Example 12 6, 3 32.4 23, 5 30, 8 Example 13 6, 3 27.3 58.7 77, 1 Example 14 6, 3 33, 9 17, 9 23, 5
[0186] The examples described for the process according to the invention, all showed a good overall performance, characterized by a high GBP and high AUL. Since the polyvalent metal salts in the present invention have a pH value similar to that of human skin, the superabsorbent polymer compositions according to the invention are expected to minimize the risk of skin irritation. The aluminum salts used in prior art are either acidic (Comparative Examples 1-4) or base (Comparative Example 5). In addition, GBP values in comparative examples 2-5 are quite low. Neutralized aluminum tri-lactate or aluminum citrate does not improve GBP
Petition 870190138489, of 12/23/2019, p. 85/110
80/80 desired. However, surface treatment with an aluminum salt according to the present invention leads to the desired combination of properties.
[0187] Notwithstanding the numerical intervals and the parameters that establish the broad scope of the invention are approximations, the numerical values established in the specific examples are presented as accurately as possible. Any numerical value, however, inherently contain certain errors necessarily resulting from the standard deviation found in their respective testing measurements. Except in operational examples or where otherwise indicated, all numbers expressing quantities of ingredients, reaction conditions, and so forth, used in the specification and claims are to be understood as being modified in all cases by the term about. Any numerical value, however, inherently contains some errors necessarily resulting from the standard deviation found in their respective test measurements.

权利要求:
Claims (20)
[1]
1. Composition of particulate superabsorbent polymer characterized by comprising a polymer comprising:
a) between 55% by weight to 99.9% by weight of the polymerizable unsaturated acid group containing monomers;
b) between 0% by weight to 40% by weight of ethylenically unsaturated, polymerized, copolymerizable monomers with a);
c) from 0.001% by weight to 5.0% by weight based on the weight of a) of an internal crosslinker, wherein components a),
b) and c) are polymerized in a hydrogel which is granulated into particles of superabsorbent polymer with a surface;
d) from 0.001% by weight to 5.0% by weight based on the dry weight of the particulate superabsorbent composition of the surface crosslinking agent applied to the surface of the particulate superabsorbent polymer; and
e) from 0.01% by weight to 5% by weight based on the dry weight of the particulate superabsorbent composition of a neutralized multivalent metal salt applied to the surface of the particulate superabsorbent polymer, in the form of an aqueous solution having a pH value from 5 to 9;
where the superabsorbent polymer composition has a degree of neutralization greater than 25 mol% and the particulate superabsorbent polymer composition has a numerical Gel Permeability value of at least [8000 and ^-0 ' ^18x ] Darcy where x is the value number of Centrifuge Holding Capacity, a
Petition 870190138489, of 12/23/2019, p. 88/110
[2]
2/6
Centrifuge Holding Capacity greater than 25 g / g and an absorption under load of 6.2 kPa (0.9 psi) from 16 g / g to 24 g / g.
2. Particulate superabsorbent polymeric composition according to claim 1, characterized in that the Gel Permeability is at least 20 Darcy.
[3]
3. Particulate superabsorbent polymeric composition, according to claim 1, characterized in that the Retention Capacity of the Centrifuge is greater than 27 g / g.
[4]
4. Particulate superabsorbent polymeric composition according to claim 1, characterized in that said neutralized multivalent metal salt has a pH value of 5.5 to
8.
[5]
5. Particulate superabsorbent polymeric composition according to claim 1, characterized in that said neutralized multivalent metal salt is a water-soluble aluminum salt, wherein said aluminum salt further comprises an organic acid or its salt.
[6]
6. Particulate superabsorbent polymeric composition according to claim 5, characterized in that said organic acid is selected from lactic acid, glycolic acid, gluconic acid, or 3-hydroxypropionic acid.
Petition 870190138489, of 12/23/2019, p. 89/110
3/6
[7]
7. Particulate superabsorbent polymer composition according to claim 5, characterized in that the molar ratio of said organic acid to aluminum is between 0.75: 1 to 1.5: 1.
[8]
8. Particulate superabsorbent polymeric composition characterized by comprising a polymer comprising:
a) between 55% by weight to 99.9% by weight of the polymerizable unsaturated acid group containing monomers;
b) from 0% by weight to 40% by weight of ethylenically unsaturated monomers, polymerized, copolymerizable with a);
c) from 0.001% by weight to 5.0% by weight based on the weight of a) an internal crosslinker, in which components a), b) and c) are polymerized in a hydrogel which is granulated in particles of superabsorbent polymers with a surface;
d) from 0.001% by weight to 5.0% by weight based on the dry weight of the particulate superabsorbent composition of the surface crosslinking agent applied to the surface of the particulate superabsorbent polymer; and
e) between 0.01% by weight to 5% by weight based on the dry weight of the particulate superabsorbent composition of aluminum salt applied to the surface of the particulate superabsorbent polymer, in the form of an aqueous solution having a pH value of 5 to 9 wherein said aluminum salt solution comprises aluminum cations and anions of a hydroxyl monocarboxylic acid
Petition 870190138489, of 12/23/2019, p. 90/110
4/6 deprotonated with a molar ratio of carboxylic anions to aluminum cations between 0.75: 1 and 1.5: 1.
[9]
9. Particulate superabsorbent polymeric composition according to claim 8, characterized in that the Gel Permeability is at least 30 Darcy.
[10]
10. Particulate superabsorbent polymer composition according to claim 8, characterized in that the Centrifuge Retention Capacity is greater than 27 g / g.
[11]
11. Process for the production of a particulate superabsorbent polymeric composition characterized by comprising the following steps:
a) providing a particulate superabsorbent polymer;
b) preparing a neutralized multivalent metal salt in the form of an aqueous solution having a pH value of 5.5 to 8;
c) applying the neutralized multivalent metal salt solution to the surface of the particulate superabsorbent polymer in which the particulate superabsorbent polymer composition has a degree of neutralization greater than 25 mol%, and the particulate superabsorbent polymer composition has the characteristics of a value numeric Gel Permeability of at least [8000 and ^-0.18x ] Darcy, where x is the numerical value of Centrifuge ^Holding Capacity; a Centrifuge Holding Capacity greater than 25 g / g and an Absorption Under Load at 6.2 kPa (0.9 psi) of 16 g / g and 24 g / g.
Petition 870190138489, of 12/23/2019, p. 91/110
5/6
[12]
Process according to claim 11, characterized in that said neutralized multivalent metal salt is the aluminum salt.
[13]
Process according to claim 11, characterized in that said aqueous solution further comprises a deprotonated organic acid.
[14]
Process according to claim 13, characterized in that said deprotonated organic acid is selected from lactic acid, glycolic acid, gluconic acid, or 3-hydroxypropionic acid.
[15]
Process according to claim 13, characterized in that the amount of the neutralized multivalent metal salt is 0.01 to 5% by weight based on the dry particulate superabsorbent composition.
[16]
16. Process for the production of a particulate superabsorbent polymeric composition characterized by comprising the following steps:
a) providing a particulate superabsorbent polymer;
b) placing the superabsorbent polymer in contact with an aqueous solution comprising a multivalent cation and an anion of a
Petition 870190138489, of 12/23/2019, p. 92/110
6/6 deprotonated organic acid with a molar ratio of organic acid to multivalent cation between 0.75: 1 to 1.5: 1;
wherein said aqueous solution has a pH value of 5.5 to 8, and said organic acid is a hydroxyl monocarboxylic acid.
[17]
17. Process according to claim 16, characterized in that said multivalent cation is the aluminum cation Al ³⁺ .
[18]
18. Process according to claim 16, characterized in that said organic acid is selected from lactic acid, glycolic acid, gluconic acid, or 3-hydroxypropionic acid.
[19]
19. Process according to claim 16, characterized in that said particulate superabsorbent polymeric composition has the characteristics of a GBP permeability in Gel number of at least [8000 and ^-0 ' ^18x ] Darcy where x is the numerical value of Centrifuge Holding Capacity, a centrifuge holding capacity greater than 25 g / g and an Absorbance Under Load at 6.2 kPa (0.9 psi) of 16 g / g to 24 g / g.
[20]
20. Absorbent article characterized by comprising the particulate superabsorbent polymeric composition as defined in claim 1.

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公开号 | 公开日

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WO2012143215A1|2012-10-26|

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TW201304825A|2013-02-01|

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KR101827038B1|2018-02-07|

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CN103547603A|2014-01-29|

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BR112013024336A2|2016-12-20|

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US9102806B2|2015-08-11|

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US20140316040A1|2014-10-23|

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TWI535464B|2016-06-01|

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EP2699608B1|2014-12-03|

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CN103547603B|2015-11-25|

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JP5717917B2|2015-05-13|

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JP2014512440A|2014-05-22|

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US20120267570A1|2012-10-25|

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KR20140026511A|2014-03-05|

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EP2699608A1|2014-02-26|

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法律状态:
2018-04-03| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|

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2020-01-14| B09A| Decision: intention to grant|

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2020-02-11| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 28/03/2012, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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US13/091,844|US8802786B2|2011-04-21|2011-04-21|Particulate superabsorbent polymer composition having improved performance properties|

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US13/091,844|2011-04-21|

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PCT/EP2012/055472|WO2012143215A1|2011-04-21|2012-03-28|Particulate superabsorbent polymer composition having improved performance properties|

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