polymer composition

Abstract

This specification discloses a polymer composition. The polymer composition includes a polysaccharide component, and the polysaccharide component includes a radically polymerizable functional group and a non-radically polymerizable functional group. Such a polysaccharide component can form a polymer including a polymer chain formed by polymerization of the radically polymerizable functional group and a covalent bond formed by reaction of the non-radically polymerizable functional group. The polymer can form a water-absorbent material with excellent water absorption, a biodegradable material with excellent biodegradability, or a material that is both a water-absorbent material and a biodegradable material. The present invention also provides uses of the polymer composition or polymer.

Description

[Technical Field]

[0001] This application claims the benefit of priority based on Korean Patent Application No. 10-2022-0104557, filed on August 22, 2022, and all contents disclosed in the documents of this Korean patent application are incorporated herein by reference.

[0002] The present invention relates to a polymer composition and its uses. [Background technology]

[0003] Hydrogel polymers, or hydrogels, are generally defined as crosslinked hydrophilic polymers. Such polymers can be used as materials known as SAPs (Super Absorbent Polymers). SAPs are materials that can absorb water tens to thousands of times their own weight. SAPs are used in a variety of applications, including hygiene products such as sanitary napkins and diapers, medical products, daily necessities, agricultural materials, gardening materials, transportation materials, civil engineering and construction materials, electrical and electronic equipment-related materials, and water treatment agents.

[0004] The hydrogels most commonly used as SAP materials are vinyl-based polymers such as cross-linked polyacrylic acid.

[0005] Although such materials are relatively inexpensive and have excellent water absorption capacity, they remain semi-permanently even after disposal, which causes various problems.

[0006] To solve this problem, there have been various attempts to produce SAP from so-called biodegradable materials.

[0007] However, currently known biodegradable materials are unable to form SAPs with balanced physical properties. For example, while the most typical physical property required for SAPs is water absorption, currently known SAPs made from biodegradable materials either fail to satisfactorily secure at least one of water absorption and biodegradability, or in some cases fail to secure both properties at an appropriate level. Summary of the Invention [Problem to be solved by the invention]

[0008] An object of the present invention is to provide a polymer composition that can ensure excellent water absorption capacity and biodegradability at the same time, and uses thereof. [Means for solving the problem]

[0009] In the present specification, when the measurement temperature affects the value of a physical property, the physical property refers to the property measured at room temperature unless otherwise specified.

[0010] As used herein, the term "room temperature" refers to a natural temperature that is not heated or sensed, and may refer to, for example, any temperature within the range of about 10°C to 30°C, or a temperature of about 23°C, or a temperature of about 25°C.

[0011] In the present specification, when the measurement pressure affects the value of a physical property, the physical property refers to the property measured at normal pressure, unless otherwise specified.

[0012] As used herein, the term "normal pressure" refers to pressure when not particularly reduced or increased, and can usually mean a pressure of about atmospheric pressure, for example, a pressure of about 740 mmHg to 780 mmHg or a pressure of about 1 atmosphere.

[0013] When the humidity at which a physical property is measured affects the value of the physical property referred to in this specification, the physical property is measured at standard humidity, which is typically about 40%, 45%, 50%, 55%, or 60% relative humidity, unless otherwise specified.

[0014] As used herein, unless otherwise specified, the term "alkyl" or "alkyl group" refers to an alkyl or alkyl group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms. Such alkyl or alkyl groups may be linear, branched, or cyclic. Such alkyl or alkyl groups may be optionally substituted with one or more substituents.

[0015] Unless otherwise specified, the term "alkylene" or "alkylene group" as used herein refers to a functional group in which two hydrogen atoms have been removed from an alkane and linked to another object, and the two hydrogen atoms have been removed from other carbon atoms of the alkane. Such alkylene or alkylene groups may be alkylene or alkylene groups having 2 to 20, 2 to 16, 2 to 12, 2 to 8, or 2 to 4 carbon atoms. Such alkylene or alkylene groups may be linear, branched, or cyclic. Such alkylene or alkylene groups may be optionally substituted with one or more substituents.

[0016] Unless otherwise specified, the term "alkylidene" or "alkylidene group" as used herein refers to a functional group in which two hydrogen atoms have been removed from an alkane and the group is linked to another object, and refers to a structure in which the two hydrogen atoms have been removed from one carbon atom of the alkane. Such an alkylidene or alkylidene group may be an alkylidene or alkylidene group having 1 to 20, 1 to 16, 1 to 12, 1 to 8, or 1 to 4 carbon atoms. Such an alkylidene or alkylidene group may be linear, branched, or cyclic. Such an alkylidene or alkylidene group may be optionally substituted with one or more substituents.

[0017] As used herein, the term "absorbent material" refers to a material that exhibits a centrifuge retention capacity (CRC) as defined herein.

[0018] As used herein, the term "biodegradable material" refers to a material that exhibits a degree of biodegradation as defined herein.

[0019] The present invention relates to a polymer composition. The polymer composition or the polymer (or polymer material) described below may be the water-absorbing material described above. The polymer composition or the polymer (or polymer material) described below may be the biodegradable material described above. The polymer composition or the polymer (or polymer material) described below may be the water-absorbing material described above and also the biodegradable material described above.

[0020] As used herein, the term "polymer composition" refers to a mixture that includes a polymer and also includes other components or a mixture that includes two or more polymers.

[0021] A polymer may refer to a substance formed by two or more units linked by a covalent bond. In one example, the polymer may be a substance having a structure in which two or more units are linked by a covalent bond and having a molecular weight above a certain level. There is no limitation on the range of the molecular weight, but the molecular weight of the polymer may be about 500 g / mol or more in weight average molecular weight (Mw). There is no particular upper limit on the weight average molecular weight, and for example, the weight average molecular weight of the polymer may be about 1,000,000 g / mol or less. The weight average molecular weight is a value measured by Gel Permeation Chromatography (GPC) using polystyrene as a calibration standard.

[0022] The lower limit of the polymer content in the polymer composition may be about 55 wt%, 60 wt%, 65 wt%, 70 wt%, 75 wt%, 80 wt%, 85 wt%, 90 wt%, or 95 wt%, and the upper limit may be 100 wt%, less than 100 wt%, 98 wt%, 96 wt%, 94 wt%, 92 wt%, or 90 wt%. The percentage may be greater than or equal to any one of the lower limits; or less than or equal to any one of the upper limits; or greater than or equal to any one of the lower limits and less than or equal to any one of the upper limits. Furthermore, when the polymer composition contains a solvent, the polymer content may be the polymer content in the polymer composition excluding the solvent.

[0023] The polymer may be a polysaccharide moiety.

[0024] As used herein, the term "polysaccharide component" refers to a component composed of one or more polysaccharides. That is, the polysaccharide component includes only polysaccharides. The polysaccharide component may include one or more polysaccharides. The two or more polysaccharides may refer to different types of polysaccharides or may include polysaccharides of the same type but with different physical properties such as molecular weight.

[0025] The term "polysaccharide" has its meaning as known in the art. Generally, a polysaccharide refers to a polymer molecule in which two or more units are linked by covalent bonds. The covalent bonds linking the units may be, for example, glycosidic bonds.

[0026] The units forming the polysaccharide may be composed of carbon, hydrogen, and oxygen, or may be biomolecules composed of carbon, hydrogen, oxygen, and nitrogen. The term "biomolecule" as used herein is to be interpreted as having the meaning commonly used in the art. Examples of biomolecules commonly known in the art include monosaccharides such as glucose, galactose, fructose, and xylose; disaccharides such as sucrose, lactose, maltose, and trehalose; polyols such as sorbitol and mannitol; oligosaccharides such as maltodextrin, dextrin, raffinose, stachyose, and fructooligosaccharides; and / or amino sugars such as glucosamine and N-acetylglucosamine. However, the types of biomolecules of the present invention are not limited to these.

[0027] If the polymer (e.g., polysaccharide component) contained in the polymer composition is in a crosslinked state and has water absorption ability, the polymer composition can form a material referred to herein as the hydrogel polymer material, polymer material, or hydrogel, or simply referred to as a polymer. Such hydrogel polymer material, hydrogel, polymer material, or polymer may be in a powder state formed through a pulverization process or the like.

[0028] The polymer composition may contain only the polysaccharide component as a polymer, or may contain other components in addition to the polysaccharide component. The polysaccharide component may exist in a polymerized and crosslinked state within the polymer composition. In such a case, the polymer composition may be referred to as a polymer material or simply as a polymer, as described below.

[0029] Examples of other components that may be contained in the polymer composition together with the polysaccharide component include, but are not limited to, a crosslinking agent that crosslinks the polysaccharide component, a polymer different from the polysaccharide component, or an initiator that induces polymerization of the polysaccharide component.

[0030] The lower limit of the polysaccharide content in the polymer composition may be about 55 wt%, 60 wt%, 65 wt%, 70 wt%, 75 wt%, 80 wt%, 85 wt%, 90 wt%, 92 wt%, 94 wt%, 96 wt%, or 98 wt%, and the upper limit may be about 100 wt%, less than 100 wt%, 98 wt%, 96 wt%, 94 wt%, 92 wt%, or 90 wt%. The percentage may be greater than or equal to any one of the lower limits; or less than or equal to any one of the upper limits; or greater than or equal to any one of the lower limits and less than or equal to any one of the upper limits. Furthermore, when the polymer composition contains a solvent, the content of the polymer may be the content of the polysaccharide component in the polymer composition excluding the solvent.

[0031] The higher the proportion of the polysaccharide component, the greater the biodegradability of the material. In the present invention, by using a specific type of polysaccharide as the polysaccharide component, appropriate polymerization and crosslinking can be carried out simultaneously, and the polymer composition after the polymerization and crosslinking can simultaneously exhibit the desired water absorption capacity and biodegradability.

[0032] When the polymer composition forms a water-absorbing material, the polymer composition, polymeric material or polymer formed therefrom may have a Centrifugal Retention Capacity (CRC) according to EDANA (European Disposables and Nonwovens Association) method WSP 241.3 of about 10 g / g, 12 g / g, 13 g / g, 14 g / g, 15 g / g, 16 g / g, 17 g / g, 18 g / g, 19 g / g, 20 g / g, 21 g / g, 22 g / g or 23 g / g at the lower limit, and about 60 g / g, 55 g / g, 50 g / g, 45 g / g, 40 g / g, 35 g / g, 30 g / g, 25 g / g, 20 g / g, 19 g / g, 18 g / g or 17 g / g at the upper limit. The centrifuge retention capacity (CRC) may be greater than or equal to any one of the lower limits described above; or greater than or equal to any one of the lower limits and less than or equal to any one of the upper limits described above. The polymer composition may exhibit this water retention capacity before or after the polysaccharide component is polymerized and crosslinked. The centrifuge retention capacity may be measured according to the European Disposables and Nonwovens Association (EDANA) WSP 241.3 standard, the details of which are described in "1. Evaluation of CRC (Centrifuge Retention Capacity)" in the Examples section of this specification.

[0033] When the polymer composition or polymer or polymeric material formed therefrom exhibits the centrifugal water retention capacity, the polymer composition, polymer or polymeric material may be defined as a water-absorbing material.

[0034] The polymer composition or a material formed therefrom can exhibit excellent biodegradability. For example, the polymer composition, polymer material, or polymer formed therefrom may be a biodegradable material. For example, the lower limit of the biodegradability of the polymer composition, polymer material, or polymer formed therefrom may be about 60%, 62%, 64%, 66%, 68%, 70%, 72%, 74%, 76%, 78%, 80%, 82%, 84%, 86%, or 88%, and the upper limit may be about 100%, 98%, 96%, 94%, 92%, 90%, 88%, 86%, 84%, 82%, 80%, 78%, 76%, 74%, or 72%. The biodegradability may be within a range that is equal to or exceeds any one of the lower limits; or may be equal to or exceeds any one of the lower limits and equal to or exceeds any one of the upper limits. The polymer composition can exhibit the biodegradability before or after the polysaccharide component is polymerized and crosslinked. The biodegradability can be measured according to ISO 14855-1 (2005), the details of which are described in "2. Measurement of Biodegradability" in the Examples section of this specification.

[0035] The polymer composition of the present invention can exhibit excellent water absorption as well as excellent biodegradability. In another example, the polymer composition can form a material that exhibits excellent water absorption as well as excellent biodegradability.

[0036] These properties can be achieved by simultaneously crosslinking and polymerizing a polysaccharide component, as described below. Typically, polysaccharide-based polymer materials have excellent biodegradability but poor water absorption capacity and crosslinking efficiency for use as a water-absorbing material. Therefore, to form a water-absorbing material using a polysaccharide-based material, a polysaccharide is typically blended with other components rather than using only the polysaccharide. However, in the present invention, a polysaccharide component having a specific type of functional group introduced therein is used. Such a polysaccharide component can undergo polymerization via the functional group, and crosslinking via the crosslinkable functional group contained in the polysaccharide component can also occur during polymerization. Therefore, such a polysaccharide component can be effectively crosslinked and polymerized while maintaining biodegradability, and can simultaneously exhibit excellent water absorption capacity and biodegradability after crosslinking and polymerization.

[0037] As described above, the polysaccharide contained in the polysaccharide component is a polymeric substance in which two or more units are linked by a covalent bond such as a glycosidic bond. Representative known polysaccharides include starch (green powder), dextrin, and chitosan. Therefore, the polysaccharide component may include, for example, one or more selected from starch (green powder), dextrin, and chitosan. The starch, dextrin, and chitosan contained in the polysaccharide component may be oxidized polysaccharides.

[0038] In one example, when the polysaccharide is starch, the weight ratio of amylose to amylopectin (amylose:amylopectin) in the starch may be in the range of about 1:99 to 50:50. In this case, the functional groups described below may be introduced into either the amylose or the amylopectin, or into both. The reaction to introduce the functional groups described below can occur in both the amylose and the amylopectin, but more efficient modification may be possible when the amylopectin content is higher than the amylose content.

[0039] For example, the starch may have a gelatinization temperature in the range of about 50°C to 90°C and a peak viscosity (BU) in the range of 50 to 1000.

[0040] The starch may be any known starch without any particular limitation, and may be, for example, one or more types selected from potato starch, corn starch, rice starch, wheat starch, tapioca starch, polymeric starch, etc.

[0041] Such polysaccharides may comprise at least two or more monosaccharide units linked by a covalent bond (e.g., glycosidic bond), where the monosaccharide units may be exemplified by the biomolecules described above, including, but not limited to, glucose, galactose, fructose, xylose, glucosamine, and N-acetylglucosamine.

[0042] In the present invention, a component having both a radically polymerizable functional group and a non-radically polymerizable functional group is used as the polysaccharide component. Since the polysaccharide component includes a polysaccharide, a polysaccharide having both a radically polymerizable functional group and a non-radically polymerizable functional group may be used as the polysaccharide, or the polysaccharide component may be composed by mixing a polysaccharide having a radically polymerizable functional group and a polysaccharide having a non-radically polymerizable functional group.

[0043] As used herein, the term "non-radically polymerizable functional group" refers to a functional group that does not participate in a radical reaction, such as a functional group that does not contain an unsaturated bond, as described below. While such a non-radically polymerizable functional group does not participate in the radical reaction, it can form a covalent bond through a chemical reaction with another functional group, as described below. Such a non-radically polymerizable functional group may be a functional group inherently possessed by a polysaccharide or polysaccharide component. For example, a hydroxy group possessed by starch or dextrin, an amino group possessed by chitosan, or a carboxyl group possessed by oxidized starch may be used as the non-radically polymerizable functional group. Therefore, for example, the non-radically polymerizable functional group may be one or more selected from the group consisting of a hydroxy group, an amino group, and a carboxyl group, but is not limited thereto.

[0044] As used herein, the term "radically polymerizable functional group" refers to a functional group that can form a polymer chain through a radical reaction. Such functional groups typically include functional groups containing unsaturated bonds (e.g., carbon-carbon double bonds). For example, the radically polymerizable functional group may be an alkenyl group or an alkynyl group, a functional group containing an alkenyl group, a functional group containing an alkynyl group, or a functional group containing an alkenylene group or an alkynylene group.

[0045] Unless otherwise specified, the term "alkenyl" or "alkenyl group" used herein refers to an alkenyl or alkenyl group having 2 to 20, 2 to 16, 2 to 12, 2 to 8, or 2 to 4 carbon atoms (e.g., a vinyl group or an allyl group). Such an alkenyl or alkenyl group may be linear, branched, or cyclic. Such an alkenyl or alkenyl group may be optionally substituted with one or more substituents.

[0046] Unless otherwise specified, the term "alkynyl" or "alkynyl group" used herein refers to an alkynyl or alkynyl group having 2 to 20, 2 to 16, 2 to 12, 2 to 8, or 2 to 4 carbon atoms. Such alkynyl or alkynyl groups may be linear, branched, or cyclic. Such alkynyl or alkynyl groups may be optionally substituted with one or more substituents.

[0047] Unless otherwise specified, the term "alkenylene" or "alkenylene group" used herein refers to an alkenylene or alkenylene group having 2 to 20, 2 to 16, 2 to 12, 2 to 8, or 2 to 4 carbon atoms (e.g., a vinylene group or an arylidene group). Such an alkenylene or alkenylene group may be linear, branched, or cyclic. Such an alkenylene or alkenylene group may be optionally substituted with one or more substituents.

[0048] Unless otherwise specified, the term "alkynylene" or "alkynylene group" used herein refers to an alkynylene or alkynylene group having 2 to 20, 2 to 16, 2 to 12, 2 to 8, or 2 to 4 carbon atoms. Such an alkynylene or alkynylene group may be linear, branched, or cyclic. Such an alkynylene or alkynylene group may be optionally substituted with one or more substituents.

[0049] Polysaccharides generally do not contain radically polymerizable functional groups. Therefore, the polysaccharides may be modified to introduce the radically polymerizable functional groups. The method for modifying the polysaccharides to introduce the radically polymerizable functional groups is not particularly limited, and for example, the method described below can be applied.

[0050] Such modified polysaccharides may contain modified monosaccharide units as units. The modified monosaccharide units refer to units into which functional groups not present in the original units, such as functional groups containing the radically polymerizable functional groups, have been introduced by chemical treatment.

[0051] In one example, the radical polymerizable functional group introduced into the modified monosaccharide unit can be represented by the following Chemical Formula 1.

[0052] [ka]

[0053] In Chemical Formula 1, M1 is hydrogen or a metal, and when M1 is a metal, the O-M1 bond is an ionic bond.

[0054] The functional group of Chemical Formula 1 may be introduced into the unit by bonding the oxygen atom on the left side of Chemical Formula 1 to the backbone of the unit.

[0055] The double bond contained in the radically polymerizable functional group of Chemical Formula 1 may be present in the polymer composition in a state where the double bond state is maintained, or may be present in a state where the double bond is polymerized. In such a case, a polymer chain may be present in the polysaccharide component through the polymerization reaction.

[0056] In Chemical Formula 1, M1 is hydrogen or a metal. The type of the metal is not particularly limited, and may generally be an alkali metal such as lithium, sodium, potassium, or cesium.

[0057] The polymer may contain both a functional group in which M1 is hydrogen and a functional group in which M1 is a metal in Chemical Formula 1.

[0058] The functional groups can be introduced by reacting a polysaccharide with an unsaturated dicarboxylic acid or an anhydride thereof to replace hydroxyl and / or amino groups present in the polysaccharide unit with the functional group. Examples of the dicarboxylic acid or anhydride include, but are not limited to, maleic acid or maleic anhydride, and salts of maleic acid may also be used.

[0059] The functional group of Chemical Formula 1 is one example of a radical polymerizable functional group that can be introduced into a polysaccharide component. If the radical polymerizable functional group can be introduced in an appropriate manner, other functional groups besides the functional group of Chemical Formula 1 can also be used.

[0060] The lower limit of the substitution rate of the radical polymerizable functional group of the polysaccharide component, such as that of Formula 1, may be about 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, or 90%, and the upper limit thereof may be about 300%, 295%, 290%, 285%, 280%, 275%, 270%, 265%, 260%, 255%, 250%, 245%, 240%, 235%, The substitution rate may be about 230%, 225%, 220%, 215%, 210%, 205%, 200%, 195%, 190%, 185%, 180%, 175%, 170%, 165%, 160%, 155%, 150%, 145%, 140%, 135%, 130%, 125%, 120%, 115%, 110%, 105%, 100%, 95%, 90%, or 85%. The substitution rate may be within a range that is equal to or exceeds any one of the lower limits described above; or within a range that is equal to or exceeds any one of the lower limits described above and equal to or exceeds any one of the upper limits described above.

[0061] As used herein, the substitution rate refers to the degree to which a hydroxyl group or amino group present in a unit contained in a polysaccharide or polysaccharide component has been substituted with a predetermined functional group (e.g., the radically polymerizable functional group), and is the average value of the degree of substitution for each unit present in the polysaccharide or polysaccharide component. For example, if the unit is a glucose unit, the unit before modification has three hydroxyl groups. Therefore, if all of the hydroxyl groups are substituted with the radically polymerizable functional group, the substitution rate of the radically polymerizable functional group for the unit is 300%. However, the substitution rate refers to the average value of the degree of substitution for each unit present in a polysaccharide or polysaccharide component. For example, if the substitution rates for each unit in a polysaccharide containing five glucose units are 100%, 0%, 200%, 300%, and 100%, the average substitution rate is 140%. This substitution rate is determined based on the average value of the degree of substitution for the polysaccharide or polysaccharide component. 1 This can be confirmed through H NMR analysis. 1 The functional groups substituted with the hydroxyl or amino groups present in the polysaccharide or polysaccharide component can be quantified through H NMR analysis, so the substitution rate can be confirmed. If necessary, the polysaccharide or polysaccharide component before modification can be analyzed. 1 The substitution rate can be calculated taking into account the results of H NMR analysis. 1 Methods for quantifying functional groups through 1 H NMR analysis are well known.

[0062] Since hydroxyl groups and amino groups present in the polysaccharide component must also function as the non-radical polymerizable functional groups, the substitution rate is important for smooth polymerization by the radical polymerizable functional groups and crosslinking by the non-radical polymerizable functional groups. In the present invention, effective crosslinking and polymerization are possible by controlling the substitution rate of the functional groups containing the radical polymerizable functional groups within the above range.

[0063] When the radical polymerizable functional group is the functional group of Formula 1, the polysaccharide component or polysaccharide may contain a unit of Formula 2 below.

[0064] [ka]

[0065] In Chemical Formula 2, R1 is a hydroxy group, an amino group, or an alkylcarbonylamino group, L1 is an alkylene group or an alkylidene group, and M1 is hydrogen or a metal. When M1 is a metal, the O-M1 bond in Chemical Formula 2 may be an ionic bond. Specific types of the metal for M1 in Chemical Formula 2 are as described in Chemical Formula 1. Specific types of the alkyl, alkylene, or alkylidene group in Chemical Formula 2 are the same as those described at the beginning of this specification.

[0066] As described in Chemical Formula 1, the radical polymerizable functional group of Chemical Formula 2 may exist in a state where the double bond is maintained, or in a state where the double bond is polymerized.

[0067] The polysaccharide component may simultaneously have a functional group in which M1 is hydrogen and a functional group in which M1 is a metal in Chemical Formula 2.

[0068] In chemical formula 2, when R1 is a hydroxy group, it generally represents a case where the unit is derived from a so-called glucose unit; when R1 is an amino group, it generally represents a case where the unit is derived from a so-called glucosamine unit; and when R1 is an alkylcarbonylamino group, it generally represents a case where the unit is derived from N-acetylglucosamine.

[0069] The polysaccharide component may also have other functional groups introduced therein in addition to the functional group containing the radically polymerizable functional group, such as the functional group of Chemical Formula 1. Such other functional groups include, for example, the functional group represented by Chemical Formula 3 below.

[0070] [ka]

[0071] In Chemical Formula 3, L2 is an alkylene group or an alkylidene group, M2 is hydrogen or a metal, and when M2 is a metal, the O-M2 bond is an ionic bond. The specific types of the alkylene group or alkylidene group in Chemical Formula 3 are the same as those defined at the beginning of this specification.

[0072] The functional group of the formula 3 may be introduced into the unit by bonding L2 on the left side of the formula 3 to the backbone of the unit.

[0073] In Chemical Formula 3, M2 is hydrogen or a metal. The type of the metal is not particularly limited, and may generally be an alkali metal such as lithium, sodium, potassium, or cesium.

[0074] The polysaccharide component may simultaneously have a functional group in which M2 is hydrogen in the above formula 3 and a functional group in which M2 is a metal.

[0075] The functional group can be introduced by reacting the polysaccharide with an acetic acid chloride such as chloroacetic acid to substitute the hydroxy group present in the polymer unit with the functional group.

[0076] The lower limit of the substitution rate of the functional group of Chemical Formula 3 in the polysaccharide component may be about 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, or 95%, and the upper limit thereof may be about 300%, 295%, 290%, 285%, 280%, 275%, 270%, 265%, 260%, 255%, 250%, 245%, 240%, or 255%. %, 235%, 230%, 225%, 220%, 215%, 210%, 205%, 200%, 195%, 190%, 185%, 180%, 175%, 170%, 165%, 160%, 155%, 150%, 145%, 140%, 135%, 130%, 125%, 120%, 115%, 110%, 105%, 100%, 95%, 90%, 85%, 80%, 75%, or 70%. The substitution rate may be greater than or equal to any one of the lower limits; or less than or equal to any one of the upper limits; or greater than or equal to any one of the lower limits and less than or equal to any one of the upper limits. The definition of the substitution rate and the method for measuring it are the same as those defined for the radical polymerizable functional group. 1 This can be confirmed through H NMR analysis.

[0077] In one example, the unit containing the functional group of Formula 3 may be a unit represented by Formula 4 below.

[0078] [ka]

[0079] In Chemical Formula 4, R2 is a hydroxy group, an amino group, or an alkylcarbonylamino group, L2 and L3 are each independently an alkylene group or an alkylidene group, and M2 is hydrogen or a metal.

[0080] When M2 is a metal, the O-M2 bond is an ionic bond.

[0081] The specific types of metals of M2 in Formula 4 are the same as those described in Formula 3.

[0082] In Chemical Formula 4, the specific types of alkyl, alkylene, or alkylidene groups are the same as those defined above.

[0083] In the polysaccharide, a functional group in which M2 is hydrogen in the above formula 4 and a functional group in which M2 is a metal may exist simultaneously.

[0084] The polysaccharide component may have an appropriate molecular weight. For example, the weight average molecular weight (Mw) of the polymer composition, polymer material, or polymer may be in the range of about 500 g / mol to 1,000,000 g / mol. Within this range, a desired degree of crosslinking can be imparted as needed, and the resulting polymer material can stably exhibit desired properties (biodegradability, water absorption, etc.).

[0085] The polymer composition may further comprise a cross-linking agent for cross-linking the polysaccharide component, which may be a compound having functional groups capable of reacting with the non-radically polymerizable functional groups of the polysaccharide component.

[0086] The lower limit of the number of functional groups of the crosslinker that can react with non-radically polymerizable functional groups of the polysaccharide component may be 2, 3, or 4, and the upper limit may be 10, 9, 8, 7, 6, 5, 4, 3, or 2. The number of functional groups may be within a range that is equal to or exceeds any one of the above lower limits; or within a range that is equal to or exceeds any one of the above lower limits and is equal to or exceeds any one of the above upper limits.

[0087] The type of crosslinking agent is not particularly limited as long as it contains a functional group that reacts with the non-radically polymerizable functional group of the polysaccharide component.

[0088] For example, the crosslinking agent may be at least one selected from the group consisting of a multifunctional epoxy compound, an epoxysilane compound, an aminosilane compound, epichlorohydrin, an aldehyde compound such as formaldehyde or glutaraldehyde, oxidized sucrose, acyl chloride, carbonate, diamine, diol, carbon disulfide, phosphoryl chloride, divinylbenzene, an organic acid, and an organic acid anhydride.

[0089] In order to ensure the desired physical properties by not inhibiting the polymerization efficiency due to the above-mentioned radical reactive functionality and by carrying out effective crosslinking, it may be advantageous to use a specific type of crosslinking agent.

[0090] As an example, the cross-linking agent may be an organic acid having two or more carboxyl groups, an anhydride of the organic acid, or an organic compound having two or more formyl groups.

[0091] The organic acid, anhydride or organic compound may be comprised of only carbon, oxygen and hydrogen.

[0092] When the crosslinking agent is used, a crosslinked structure including, for example, an ester bond formed by the reaction of a carboxyl group of the crosslinking agent with a hydroxyl group in the polysaccharide component, or a covalent bond as shown in Chemical Formula 5 below formed by the reaction of a formyl group of the crosslinking agent with an amino group in the polysaccharide component may be realized.

[0093] [ka]

[0094] The bond of Formula 5 has a polysaccharide or polysaccharide component on one side and a crosslinker on the other side.

[0095] The type of organic acid used in the crosslinking agent is not particularly limited, but an organic acid having a molecular weight of about 90 g / mol to 300 g / mol or about 100 g / mol to 250 g / mol can be used. The range of the number of carboxyl groups in the organic acid is the same as the number of functional groups in the crosslinking agent described above.

[0096] Examples of such organic acids include, but are not limited to, citric acid, succinic acid, pimelic acid, and adipic acid.

[0097] The organic acids or their anhydrides can be used as the crosslinking agents.

[0098] The organic compound having two or more formyl groups that can be used in the crosslinking agent is not particularly limited, but an organic compound having a molar mass of about 90 g / mol to 200 g / mol or about 90 g / mol to 150 g / mol can be used. The range of the number of formyl groups in the organic compound is the same as the number of functional groups in the crosslinking agent described above.

[0099] Such organic compounds may include, but are not limited to, glutaraldehyde.

[0100] When applicable, the weight ratio of the crosslinker in the polymer composition relative to 100 parts by weight of the polysaccharide component may be about 1 part by weight, 5 parts by weight, 10 parts by weight, 15 parts by weight, 20 parts by weight, or 25 parts by weight at the lower limit, and about 100 parts by weight, 70 parts by weight, 50 parts by weight, 45 parts by weight, 40 parts by weight, 35 parts by weight, 30 parts by weight, 25 parts by weight, 20 parts by weight, 15 parts by weight, or 10 parts by weight at the upper limit. The ratio may be greater than or equal to any one of the lower limits; or less than or equal to any one of the upper limits; or greater than or equal to any one of the lower limits and less than or equal to any one of the upper limits.

[0101] Within such a range, the efficiency of polymerization by the radically polymerizable functional groups of the polysaccharide component is not inhibited, and efficient crosslinking may be possible.

[0102] The polymer composition may include any necessary ingredients in addition to the polysaccharide component and crosslinker.

[0103] For example, an initiator component (eg, a polymerization initiator) capable of inducing polymerization through the double bonds can be included in the polymer composition.

[0104] The initiator component may be any known component that can induce polymerization of the radically polymerizable functional group without any particular limitation. For example, known radical polymerization initiators may be used as the initiator component. For example, oxidizing agents such as ammonium persulfate or ammonium cerium nitrate, or other radical polymerization initiators may be used as the initiator component.

[0105] The proportion of the initiator component is not particularly limited, and it is advisable to use it in a catalytic amount that can induce the polymerization reaction of the radically polymerizable functional group.

[0106] For example, in the presence of an oxidizing agent, which is the initiator component, polymerization by the radically polymerizable functional groups present in the polysaccharide component and crosslinking, polymerization, or grafting between the radicals generated by oxidation of the oxidizing agent and the radically polymerizable functional groups can occur to form polymer chains.

[0107] The present invention also relates to a polymeric material containing the polymeric composition or formed from the polymeric composition, which may also be simply called a polymer (or hydrogel).

[0108] The polymeric material can include polymer chains formed by polymerization of radically polymerizable functional groups of a polysaccharide component of the polymer composition and covalent bonds formed by reaction of non-radically polymerizable functional groups of the polysaccharide component with functional groups of the crosslinker.

[0109] The specific types of the radically polymerizable functional group and the non-radically polymerizable functional group, the substitution rate of the functional group in the polysaccharide or polysaccharide component, and the type of the crosslinking agent are as described above. The covalent bond may also be an ester bond as described above or a covalent bond of Formula 5.

[0110] Such polymeric materials may be biodegradable, water-absorbent, or both, as described above, and thus may exhibit the centrifugal water-retention capacity and / or biodegradability described above.

[0111] The polymer material can be used in a variety of applications because it exhibits excellent water absorption and biodegradability at the same time.

[0112] For example, the polymer material may be used as a water-absorbing material for hygiene products such as diapers and sanitary napkins, or other applications requiring absorption. If necessary, the polymer material may be subjected to additional crosslinking, surface treatment, or physical grinding processes to enhance its efficiency in the hygiene products or water-absorbing materials.

[0113] The present invention therefore relates to absorbent materials or sanitary articles (such as diapers and sanitary napkins) comprising said polymeric materials.

[0114] The specific method of applying the polymer material to form the water-absorbent material or sanitary product is not particularly limited, and for example, the method of applying an existing SAP to form the water-absorbent material or sanitary product may be used in the same manner. [Effects of the Invention]

[0115] The present invention provides a polymer composition and uses thereof. The polymer composition includes a polysaccharide component, and the polysaccharide component includes a radically polymerizable functional group and a non-radically polymerizable functional group. Such a polysaccharide component can form a polymer including a polymer chain formed by polymerization of the radically polymerizable functional group and a covalent bond formed by reaction of the non-radically polymerizable functional group. The polymer can form a water-absorbent material with excellent water absorption, a biodegradable material with excellent biodegradability, or a material that is both a water-absorbent material and a biodegradable material. The present invention also provides uses of the polymer composition or polymer. [Brief explanation of the drawings]

[0116] [Figure 1] FIG. 1 shows the results of 1H NMR analysis of the modified polysaccharide produced in Production Example 1. [Figure 2] FIG. 2 shows the results of 1H NMR analysis of the modified polysaccharide produced in Production Example 2. DETAILED DESCRIPTION OF THE INVENTION

[0117] The present invention will be described in detail below through examples and comparative examples, but the scope of the present invention is not limited to the following examples.

[0118] 1. Evaluation of Centrifuge Retention Capacity (CRC)

[0119] Centrifugal water retention capacity (CRC) was measured according to EDANA (European Disposables and Nonwovens Association) WSP 241.3. Approximately 0.2 g (W0) of the resulting polymer was placed in a nonwoven envelope, sealed, and then immersed in saline. The saline solution used was a 0.9 wt% NaCl aqueous solution. After maintaining this condition for approximately 30 minutes, the envelope was centrifuged at 250 G for 3 minutes to remove water, and the envelope's mass (g, W2) was measured. An identical nonwoven envelope without the polymer was immersed in the same saline solution. After maintaining this condition for approximately 30 minutes, the envelope was centrifuged at 25 G for 3 minutes to remove water, and the envelope's mass (g, W1) was measured. The measurement results were substituted into the following formula A to calculate CRC (g / g). The evaluation was performed under constant temperature and humidity conditions (23±1°C, relative humidity: 50±10%).

[0120] [Formula A] CRC(g / g)={[W2(g)-W1(g)] / W0(g)}-1

[0121] 2. Measurement of biodegradability

[0122] Biodegradation was measured according to the method specified in ISO 14855-1 (2005). This standard is a method for measuring the aerobic biodegradation of plastic materials under composting conditions, and calculates the biodegradation of a polymer by quantifying the amount of carbon dioxide released by microbial metabolism of the material. The polymer was subjected to composting conditions according to the standard and the biodegradation was measured for six months. The biodegradation was calculated as the ratio of the theoretical amount of carbon dioxide generated to the actual amount of carbon dioxide generated. The theoretical amount of carbon dioxide generated and the biodegradation rate can be calculated using the following formulas C and D, respectively.

[0123] [Formula C] Theoretical carbon dioxide generation (ThCO2, g / container) = M T O T ×C T O T ×(44 / 12)

[0124] In formula C, M T O T is the amount (g) of total dry solids of the test material (polymer) added to the compost at the start of the measurement, and CTOT means the percentage of organic carbon (g / g) contained in the total dry solids of the test material.

[0125] [Formula D] Biodegradation (%)=[{(CO2) T -(CO2) B} / ThCO2]×100

[0126] In Equation D, (CO2)T is the cumulative amount of carbon dioxide evolved from the composting vessels in the test material (g / vessel), (CO2)B is the average cumulative amount of carbon dioxide evolved from the inoculum vessels (g / vessel), and ThCO2 is the theoretical carbon dioxide evolution determined from Equation C above.

[0127] <Production Example 1>

[0128] A polysaccharide (modified starch) (compound A) containing a modified monosaccharide unit of the following chemical formula A was prepared in the following manner. The modified monosaccharide unit of the following chemical formula A is a monosaccharide unit into which a maleic acid group (a substituent in which M1 in chemical formula 1 is a hydrogen atom) has been introduced.

[0129] [ka]

[0130] 15 g of starch and 50 mL of DMSO (dimethyl sulfoxide) were placed in a 500 mL RBF (Round Bottom Flask) and gelatinized at 65°C for 2 hours. Potato starch was used as the starch. Approximately 30 g of maleic anhydride was added to the gelatinized starch and reacted at 65°C for approximately 3 hours. After the reaction was completed, the temperature was lowered to room temperature (approximately 25°C), and acetone was added to form a precipitate. The precipitate was collected and dried in a vacuum oven at 40°C for one day to obtain the target product (Compound A) in a solid phase.

[0131] The substitution rate of the obtained target product (compound A) is 1 It can be determined through H NMR analysis. 1 H NMR analysis included a Varian Unity Inova (500 MHz) spectrometer with a triple-resonance 5 mm probe. 1 The analysis is carried out at room temperature (approximately 25°C) using a H NMR spectrometer. 1 For the H NMR analysis, an Avance Neo instrument manufactured by Bruker was used. Specifically, 50 mg of the target solid (compound A) obtained above was mixed with 200 mg of a 30% DCl solution in DO, and the mixture was stirred at 50° C. for about 1 hour to induce a hydrolysis reaction. 1 1 H NMR analysis can be performed. 1 The substitution rate of the maleic acid group on the green powder was confirmed by H NMR analysis. 1 This is the result of 1 H NMR analysis, and the substitution rate calculated based on this was about 81%.

[0132] <Production Example 2>

[0133] A polysaccharide (modified chitosan) (compound B) containing a modified monosaccharide unit of the following chemical formula B was prepared in the following manner. The modified monosaccharide unit of the following chemical formula B is a monosaccharide unit into which a maleic acid group (a substituent in which M1 in chemical formula 1 is a hydrogen atom) has been introduced.

[0134] [ka]

[0135] 15g of chitosan and 300mL of DMSO (dimethyl sulfoxide) were placed in a 500mL RBF (Round Bottom Flask) and gelatinized by stirring at 65°C for 30 minutes. Approximately 30g of maleic anhydride was added to the gelatinized chitosan and reacted at 65°C for approximately 3 hours. After the reaction was complete, the temperature was lowered to room temperature (approximately 25°C) and acetone was added to form a precipitate.

[0136] The precipitate was collected and dried in a vacuum oven at 40°C for one day to obtain the target product (compound B) in a solid phase.

[0137] The substitution rate of the obtained target product (compound B) is 1 It can be determined through H NMR analysis. 1 H NMR analysis included a Varian Unity Inova (500 MHz) spectrometer with a triple-resonance 5 mm probe. 1 The analysis is carried out at room temperature (approximately 25°C) using a H NMR spectrometer. 1 For the H NMR analysis, an Avance Neo instrument manufactured by Bruker was used. Specifically, 50 mg of the target solid (compound A) obtained above was mixed with 200 mg of a 30% DCl solution in DO, and the mixture was stirred at 50° C. for about 1 hour to induce a hydrolysis reaction. 1 H NMR analysis can be performed.

[0138] The aforementioned 1 The substitution rate of the maleic acid group on the chitosan was confirmed by H NMR analysis. 1 This is the result of 1 H NMR analysis, and the substitution rate calculated based on this was about 94%.

[0139] Example 1

[0140] A polymer composition was prepared by mixing Compound (A) from Preparation Example 1 and a crosslinker (citric acid) in a weight ratio of 2.8:0.2 (Compound (A):crosslinker) with distilled water, and adding approximately 2 mol% of ammonium cerium nitrate as an initiator. The mixture was then stirred at 35°C for 2 hours to allow polymerization and crosslinking via double bonds to proceed, producing a biodegradable polymer with water absorption capabilities. Ethanol was added to precipitate the polymer, which was then dried in a vacuum oven at 40°C.

[0141] <Example 2>

[0142] A polymer material was produced in the same manner as in Example 1, except that the weight ratio of compound (A) and crosslinking agent (citric acid) in Production Example 1 was changed to 2.6:0.4 (compound (A):crosslinking agent).

[0143] Example 3

[0144] A polymer material was produced in the same manner as in Example 1, except that the weight ratio of compound (A) and crosslinking agent (citric acid) in Production Example 1 was changed to 2.4:0.6 (compound (A):crosslinking agent).

[0145] <Comparative Example 1>

[0146] A polymer material was prepared as in Example 1, but without applying a crosslinking agent, only applying compound (A).

[0147] <Comparative Example 2>

[0148] A polymer material was prepared as in Example 1, except that compound (A) was not applied and only citric acid was applied.

[0149] Example 4

[0150] Compound (B) of Preparation Example 2 and glutaraldehyde, a crosslinking agent, were mixed in distilled water at a weight ratio of 2.8:0.2 (compound (B):crosslinking agent), and ammonium cerium nitrate was added as an initiator at a ratio of about 2 mol % to prepare a polymer composition.

[0151] The polymer composition was stirred at 35°C for 2 hours to allow polymerization and crosslinking of the double bonds to occur, producing a biodegradable polymer with water absorption. The polymer was precipitated by adding ethanol and dried in a vacuum oven at 40°C.

[0152] <Example 5>

[0153] A polymer material was prepared in the same manner as in Example 4, except that the weight ratio of compound (B) and crosslinking agent (glutaraldehyde) in Preparation Example 2 was changed to 2.6:0.4 (compound (B):crosslinking agent).

[0154] Example 6

[0155] A polymer material was prepared in the same manner as in Example 4, except that the weight ratio of compound (B) and crosslinking agent (glutaraldehyde) in Preparation Example 2 was changed to 2.4:0.6 (compound (B):crosslinking agent).

[0156] <Comparative Example 3>

[0157] A polymer material was prepared as in Example 4, but without applying a crosslinker, only compound (B) was applied.

[0158] <Comparative Example 4>

[0159] A polymer material was prepared as in Example 4, except that compound (B) was not applied and only glutaraldehyde was applied.

[0160] The results of measuring the physical properties of the polymer materials of the examples and comparative examples are shown in Table 1 below.

[0161] [Table 1]

[0162] Comparing Examples 1 to 3 with Comparative Example 1, and Examples 4 to 6 with Comparative Example 3 in Table 1, it can be seen that the Examples exhibit superior water absorption capacity and / or biodegradability compared to Comparative Examples 1 and 3, which used only polysaccharide components.

Claims

1. a polysaccharide component having a radically polymerizable functional group and a non-radically polymerizable functional group; and A polymer composition comprising a compound having two or more functional groups capable of reacting with the non-radically polymerizable functional group.

2. The polymer composition according to claim 1, wherein the non-radically polymerizable functional group is a hydroxy group, an amino group, or a carboxyl group.

3. 2. The polymer composition according to claim 1, wherein the radically polymerizable functional group comprises at least one selected from the group consisting of an alkenyl group, an alkynyl group, an alkenylene group, and an alkynylene group.

4. 2. The polymer composition according to claim 1, wherein the substitution rate of the radically polymerizable functional group in the polysaccharide component is within the range of 10% to 300%.

5. The polymer composition according to claim 1, wherein the radical polymerizable functional group is a functional group represented by the following formula 1: 【Chemical 1】 In chemical formula 1, M １ is hydrogen or a metal, M １ When is a metal, O-M １ The bond is an ionic bond.

6. 2. The polymer composition of claim 1, wherein the polysaccharide component comprises units of Formula 2: 【Chemistry 2】 In chemical formula 2, R １ is a hydroxy group, an amino group, or an alkylcarbonylamino group, and L １ is an alkylene group or an alkylidene group, M １ is hydrogen or a metal, M １ When is a metal, O-M １ The bond is an ionic bond.

7. 2. The polymer composition according to claim 1, wherein the compound is an organic acid having two or more carboxyl groups, an anhydride of the organic acid, or an organic compound having two or more formyl groups.

8. 8. The polymer composition according to claim 7, wherein the organic acid has a molar mass in the range of 90 g / mol to 300 g / mol and the organic compound has a molar mass in the range of 90 g / mol to 200 g / mol.

9. 2. The polymer composition of claim 1, wherein the compound is citric acid, citric anhydride, succinic acid, succinic anhydride, pimelic acid, pimelic anhydride, adipic acid, adipic anhydride or glutaraldehyde.

10. 2. The polymer composition of claim 1, wherein the compound is present in an amount of 1 to 50 parts by weight per 100 parts by weight of the polysaccharide component.

11. The polymer composition of claim 1 , further comprising a polymerization initiator.

12. 2. The polymer composition according to claim 1, further comprising a radical polymerization initiator.

13. a polysaccharide component having a radically polymerizable functional group and a non-radically polymerizable functional group; and a compound having two or more functional groups capable of reacting with the non-radically polymerizable functional group; A polymer characterized in that the radically polymerizable functional groups of the polysaccharide component form a polymer chain, and the non-radical polymerizable functional groups of the polysaccharide component form a covalent bond with the functional groups of a compound.

14. The polymer according to claim 13, wherein the covalent bond is an ester bond or a bond represented by the following formula 5: 【Chemistry 3】

15. The polymer according to claim 13, wherein the compound is an organic acid having two or more carboxyl groups, an anhydride of the organic acid, or an organic compound having two or more formyl groups.

16. 16. The polymer according to claim 15, wherein the organic acid has a molar mass in the range of 90 g / mol to 300 g / mol and the organic compound has a molar mass in the range of 90 g / mol to 200 g / mol.

17. 14. The polymer according to claim 13, characterized in that the compound is citric acid, citric anhydride, succinic acid, succinic anhydride, pimelic acid, pimelic anhydride, adipic acid, adipic anhydride or glutaraldehyde.

18. 14. The polymer according to claim 13, characterized in that it has a centrifugal water retention capacity according to EDANA (European Disposables and Nonwovens Association) method WSP 241.3 of at least 10 g / g.

19. The polymer according to claim 13, characterized in that it has a biodegradability of 60% or more.

20. A water-absorbing material comprising the polymer of claim 13.

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