Polymer composition

Abstract

The present specification discloses a polymer composition. The polymer composition comprises a polysaccharide component, wherein the polysaccharide component comprises a radical polymerizable functional group and a non-radical polymerizable functional group. Such a polysaccharide component may form a polymer comprising a polymer chain formed by polymerization of radically polymerizable functional groups and a covalent bond formed by reaction of non-radically polymerizable functional groups. The polymer may form an absorbent material having excellent absorbency, form a biodegradable material having excellent biodegradability, or form a material that is an absorbent material and at the same time a biodegradable material. The invention also provides a use of the polymer composition or the 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, the disclosure of which is incorporated herein by reference in its entirety.

[0002] The present application relates to polymer compositions and uses thereof. Background Art

[0003] Hydrogel polymers or hydrogels are generally defined as cross-linked hydrophilic polymers. Such polymers can be used as materials referred to as SAP (Super Absorbent Polymer). SAP is a material that can absorb moisture several tens to several thousand times of its own weight. SAP is used in various applications, such as sanitary products such as sanitary products or diapers, medical products, household materials, agricultural materials, gardening materials, transportation materials, civil engineering and construction materials, materials related to electrical and electronic equipment, or water treatment agents.

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

[0005] Such materials are relatively inexpensive and have excellent water absorption capacity, but cause various problems because they remain semi-permanently even after treatment.

[0006] In order to solve such problems, there are various attempts to manufacture SAP from so-called biodegradable materials.

[0007] However, the biodegradable materials known so far cannot form SAPs with balanced physical properties. For example, the most representative physical property required for SAP is absorption capacity, but in SAPs of biodegradable materials known so far, at least one of absorption capacity and biodegradability cannot be satisfactorily ensured, or in some cases, both physical properties cannot be ensured at appropriate levels. Summary of the invention

[0008] Technical issues

[0009] The present application aims to provide a polymer composition capable of simultaneously ensuring excellent absorption capacity and biodegradability and use thereof.

[0010] Technical Solution

[0011] Among the physical properties mentioned in this specification, when the measurement temperature affects the value of the physical property, unless specifically mentioned otherwise, the relevant physical property means the physical property measured at room temperature.

[0012] In the present specification, the term room temperature is a natural temperature without heating or cooling, which may mean, for example, any temperature within the range of about 10°C to 30°C, or a temperature around about 23°C, or a temperature around about 25°C.

[0013] Among the physical properties mentioned in this specification, when the measurement pressure affects the value of the physical property, unless specifically mentioned otherwise, the relevant physical property means the physical property measured under normal pressure.

[0014] In this specification, the term normal pressure refers to pressure when there is no particular decrease or increase, which may mean a pressure around normal atmospheric pressure, for example, a pressure around 740 mmHg to 780 mmHg, or a pressure around 1 atmosphere.

[0015] Among the physical properties mentioned in this specification, when measuring the physical property value affected by humidity, unless otherwise specifically stated, the relevant physical properties refer to the physical properties measured at a humidity in a standard state. The humidity in a standard state is generally a humidity of about 40%, 45%, 50%, 55% or 60% as a relative humidity.

[0016] In this specification, unless otherwise stated, the term alkyl or alkyl group means 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 an alkyl or alkyl group can be linear, branched or cyclic. Such an alkyl or alkyl group can also be optionally substituted with one or more substituents.

[0017] In this specification, unless otherwise indicated, term alkylene or alkylene group means the functional group that is connected to another object by isolating two hydrogen atoms from alkane, and it has the structure that two hydrogen atoms separate from other carbon atoms of alkane.Such alkylene or alkylene group can be alkylene or alkylene group with 2 to 20 carbon atoms, 2 to 16 carbon atoms, 2 to 12 carbon atoms, 2 to 8 carbon atoms or 2 to 4 carbon atoms.Such alkylene or alkylene group can be linear, branched or cyclic.Such alkylene or alkylene group can also optionally replace through one or more substituents.

[0018] In this specification, unless otherwise indicated, the term alkylidene or alkylidene group means a functional group that is connected to another object by isolating two hydrogen atoms from an alkane, and it has a structure in which two hydrogen atoms are separated from a carbon atom of an alkane. Such an alkylidene or alkylidene group can be an alkylidene or alkylidene group with 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 an alkylidene or alkylidene group can be linear, branched or cyclic. Such an alkylidene or alkylidene group can also optionally be substituted with one or more substituents.

[0019] In the present specification, the term absorbent material is intended to mean a material that exhibits a centrifuge retention capacity (CRC) as defined herein.

[0020] In this specification, the term biodegradable material means a material that exhibits a certain degree of biodegradability as defined herein.

[0021] The present application relates to polymer compositions. The polymer compositions or polymers (or polymer materials) to be described below may be the absorbent materials described above. The polymer compositions or polymers (or polymer materials) to be described below may be the biodegradable materials described above. The polymer compositions or polymers (or polymer materials) to be described below may be the biodegradable materials described above and the absorbent materials described above.

[0022] In the present specification, the term polymer composition means a mixture comprising a polymer and further comprising other components, or a mixture comprising two or more polymers.

[0023] Polymer can mean the material formed by connecting two or more unit bodies by covalent bonds. In an example, polymer can be a structure comprising two or more unit bodies connected by covalent bonds, and has a certain level or a larger molecular weight. The scope of molecular weight is not limited, but with respect to weight average molecular weight (Mw), the molecular weight of polymer can be about 500g / mol or more. The upper limit of weight average molecular weight is not particularly limited, and for example, the weight average molecular weight of polymer can be about 1,000,000g / mol or less. Weight average molecular weight is the value measured by GPC (gel permeation chromatography) using polystyrene as calibration standard sample.

[0024] The lower limit of the polymer content in the polymer composition can be about 55 weight %, 60 weight %, 65 weight %, 70 weight %, 75 weight %, 80 weight %, 85 weight %, 90 weight %, or 95 weight %, and its upper limit can be about 100 weight %, less than 100 weight %, 98 weight %, 96 weight %, 94 weight %, 92 weight %, or 90 weight %. The ratio can be in a range greater than or equal to, or greater than any one of the above lower limits; or in a range less than or equal to, or less than any one of the above upper limits; or in a range less than or equal to, or less than any one of the above upper limits while being greater than or equal to, or greater than any one of the above lower limits. In addition, when the polymer composition includes a solvent, the polymer content can be the polymer content of the polymer composition excluding the solvent.

[0025] The polymer may be a polysaccharide component.

[0026] In this specification, the term polysaccharide component means a component consisting of one or more polysaccharides. That is, the polysaccharide component contains only polysaccharides. The polysaccharides contained in the polysaccharide component can be one or two or more types. Here, two or more polysaccharides can also mean different types of polysaccharides, and can also include polysaccharides of the same type but different physical properties such as molecular weight.

[0027] The term polysaccharide has the meaning known in industry. Polysaccharides generally refer to polymer molecules in which two or more unit bodies are connected by covalent bonds. Here, in one example, the covalent bond connecting the unit bodies can be a glycosidic bond.

[0028] The unitary body forming polysaccharide can be a biomolecule consisting of carbon, hydrogen and oxygen, or a biomolecule consisting of carbon, hydrogen, oxygen and nitrogen. In this specification, the term biomolecule is interpreted as having the meaning commonly used in industry. Typically, as an example of biomolecule in industry, monosaccharides such as glucose, galactose, fructose or xylose, disaccharides such as sucrose, lactose, maltose or trehalose, polyols such as sorbitol or mannitol, oligosaccharides such as maltodextrin, dextrin, raffinose, stachyose or oligofructose, and / or amino sugars such as glucosamine or N-acetylglucosamine etc. are known, but the type of biomolecule in the present application is not limited to the aforementioned.

[0029] If the polymer (e.g., polysaccharide component) contained in the polymer composition is in a cross-linked state and has an absorption capacity, the relevant polymer composition may be referred to herein as a hydrogel polymer material, polymer material, or hydrogel, or may simply form a material referred to as a polymer. Such a hydrogel polymer material or hydrogel, polymer material, or polymer may also be in a powder state formed by a grinding process, etc.

[0030] The polymer composition may only include the polysaccharide component, or may also include other components except the polysaccharide component as polymer. In the polymer composition, the polysaccharide component may exist in a polymerized and cross-linked state. In this case, the polymer composition may also be referred to as the polymer material described below, or may be referred to as polymer for short.

[0031] Examples of other components that may be included in the polymer composition together with the polysaccharide component are not particularly limited, but may be exemplified by a crosslinking agent that crosslinks the polysaccharide component, a polymer different from the polysaccharide component, or an initiator that initiates polymerization of the polysaccharide component.

[0032] The lower limit of the content of the polysaccharide component in the polymer composition can be about 55 weight %, 60 weight %, 65 weight %, 70 weight %, 75 weight %, 80 weight %, 85 weight %, 90 weight %, 92 weight %, 94 weight %, 96 weight %, or 98 weight %, and the upper limit thereof can be about 100 weight %, less than 100 weight %, 98 weight %, 96 weight %, 94 weight %, 92 weight %, or 90 weight %. The ratio can be in a range of greater than or equal to or greater than any of the above lower limits; or in a range of less than or equal to or less than any of the above upper limits; or in a range of less than or equal to or less than any of the above upper limits while being greater than or equal to or greater than any of the above lower limits. In addition, when the polymer composition includes a solvent, the polymer content can be the content of the polysaccharide component in the polymer composition excluding the solvent.

[0033] The higher the ratio of the polysaccharide component, the greater the biodegradability of the material. In the present application, by applying a specific type of polysaccharide as the polysaccharide component, appropriate polymerization and crosslinking can be performed simultaneously, and the polymer composition after polymerization and crosslinking can simultaneously exhibit excellent absorption capacity and biodegradability.

[0034] When the polymer composition forms an absorbent material, the polymer composition, or the polymer material or polymer formed therefrom, may have a lower limit of the Centrifuge 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, and an upper limit of 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. The centrifuge retention capacity (CRC) can be in a range of greater than or equal to or greater than any one of the above lower limits; or in a range of less than or equal to or less than any one of the above upper limits while being greater than or equal to or greater than any one of the above lower limits. The polymer composition can exhibit retention capacity before or after the polymerization and crosslinking of the polysaccharide component. The centrifuge retention capacity can be measured according to the procedure of EDANA (European Disposables and Nonwovens Association) WSP 241.3, and its details are described in "1. Centrifuge Retention Capacity (CRC) Evaluation" in the Examples section of this specification.

[0035] When a polymer composition, or a polymer or polymer material formed therefrom, exhibits a centrifuge retention capacity, the polymer composition, polymer or polymer material may be defined as an absorbent material.

[0036] The polymer composition or the material formed therefrom can exhibit excellent biodegradability. For example, the polymer composition or the polymer material or polymer formed therefrom can be a biodegradable material. For example, the lower limit of the biodegradability of the polymer composition or the polymer material or polymer formed therefrom can be about 60%, 62%, 64%, 66%, 68%, 70%, 72%, 74%, 76%, 78%, 80%, 82%, 84%, 86%, or 88%, and the upper limit thereof can be about 100%, 98%, 96%, 94%, 92%, 90%, 88%, 86%, 84%, 82%, 80%, 78%, 76%, 74%, or 72%. The biodegradability can be in a range greater than or equal to or greater than any one of the above lower limits; or in a range less than or equal to or less than any one of the above upper limits while being greater than or equal to or greater than any one of the above lower limits. The polymer composition may exhibit biodegradability before or after polymerization and crosslinking of the polysaccharide component. Biodegradability may be measured according to the provisions of ISO 14855-1 (2005), and the details thereof are described in "2. Measurement of biodegradability" in the Examples section of this specification.

[0037] The polymer composition of the present application can exhibit excellent biodegradability and excellent absorbability. In another example, the polymer composition can form a material that exhibits excellent biodegradability and excellent absorbability.

[0038] Such characteristics can be ensured by applying a polysaccharide component to be described below as a polysaccharide component and simultaneously crosslinking and polymerizing. Generally, polysaccharide-based polymer materials have excellent biodegradability, but have low water absorption capacity and low crosslinking efficiency for application as absorbent materials. Therefore, generally, in order to form an absorbent material using a polysaccharide-based material, it is obtained by blending other components with the polysaccharide (rather than applying only the polysaccharide). However, in the present application, a polysaccharide component in which a specific type of functional group is introduced is applied as a polysaccharide component. A polysaccharide component of this type can be polymerized by the functional group, and at the same time as the polymerization, it is also crosslinked by the crosslinkable functional group contained in the polysaccharide component. Therefore, such a polysaccharide component can be effectively crosslinked and polymerized while maintaining biodegradability, and can simultaneously exhibit excellent absorption capacity and biodegradability after crosslinking and polymerization.

[0039] As described above, the polysaccharide contained in the polysaccharide component is a polymeric substance in which two or more units are linked by covalent bonds such as glycosidic bonds, and representative known polysaccharides include starch, dextrin or chitosan, etc. Therefore, in one example, the polysaccharide component may contain one or two or more selected from starch, dextrin and chitosan, etc. The starch, dextrin and chitosan contained in the polysaccharide component may also be polysaccharides in an oxidized state.

[0040] In one example, when the polysaccharide is starch, the weight ratio of amylose to amylopectin in the relevant starch (amylose: amylopectin) can be in the range of about 1:99 to about 50:50. In this case, the functional groups to be described below can be introduced into amylose or amylopectin, or can be introduced into both. The reaction of introducing the functional groups described below can occur in both amylose and amylopectin, but when the content of amylopectin is greater than that of amylose, more effective modification may be possible.

[0041] 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 1,000.

[0042] As the starch, any known starch may be applied without particular limitation, and for example, one or two or more types selected from potato starch, corn starch, rice starch, wheat starch, tapioca starch, and polymer starch may be applied.

[0043] Such a polysaccharide may include at least two or more monosaccharide units connected by covalent bonds (e.g., glycosidic bonds). At this time, the monosaccharide unit may be exemplified by the above-mentioned biomolecules, and may be specifically exemplified by glucose, galactose, fructose, xylose, glucosamine or N-acetylglucosamine, etc., but is not limited thereto.

[0044] In the present application, as the polysaccharide component, a component having both a radically polymerizable functional group and a non-radical polymerizable functional group is used. Since the polysaccharide component contains polysaccharides, a polysaccharide having both a radically polymerizable functional group and a non-radical polymerizable functional group may be applied as the relevant polysaccharide, or the polysaccharide component may be formed by mixing a polysaccharide having a radically polymerizable functional group and a polysaccharide having a non-radical polymerizable functional group.

[0045] In this specification, the term non-radical polymerizable functional group is a functional group that does not participate in free radical reaction, such as a functional group that does not contain unsaturated bonds as described below. Such non-radical polymerizable functional groups do not participate in free radical reaction, but can form covalent bonds by chemical reactions with other functional groups, as described below. Such non-radical polymerizable functional groups can be functional groups originally possessed by polysaccharides or polysaccharide components. For example, the hydroxyl group of starch or dextrin, the amino group of chitosan, or the carboxyl group of oxidized starch can be used as the non-radical polymerizable functional group. Therefore, for example, the non-radical polymerizable functional group can be one or more selected from hydroxyl, amino and carboxyl groups, but is not limited thereto.

[0046] In this specification, the term free radical polymerizable functional group means a functional group that can form a polymer chain by free radical reaction. Such functional groups include functional groups comprising unsaturated bonds (e.g., carbon-carbon double bonds). In an example, the free radical polymerizable functional group can be an alkenyl or alkynyl group, or a functional group comprising an alkenyl group, or a functional group comprising an alkynyl group, or a functional group comprising an alkenylene group, or a functional group comprising an alkynylene group.

[0047] In this specification, unless otherwise indicated, the term alkenyl or alkenyl group means an alkenyl or alkenyl group (e.g., vinyl group or allyl group, etc.) having 2 to 20 carbon atoms, 2 to 16 carbon atoms, 2 to 12 carbon atoms, 2 to 8 carbon atoms, or 2 to 4 carbon atoms. Such alkenyl or alkenyl groups can be linear, branched or cyclic. Such alkenyl or alkenyl groups can optionally be substituted with one or more substituents.

[0048] In this specification, unless otherwise indicated, the term alkynyl or alkynyl group means an alkynyl or alkynyl group (e.g., vinyl or allyl, etc.) having 2 to 20 carbon atoms, 2 to 16 carbon atoms, 2 to 12 carbon atoms, 2 to 8 carbon atoms, or 2 to 4 carbon atoms. Such alkynyl or alkynyl groups can be linear, branched or cyclic. Such alkynyl or alkynyl groups can optionally be substituted with one or more substituents.

[0049] In this specification, unless otherwise indicated, the term alkenylene or alkenylene group means an alkenylene or alkenylene group (e.g., vinylene group or allylene group, etc.) having 2 to 20 carbon atoms, 2 to 16 carbon atoms, 2 to 12 carbon atoms, 2 to 8 carbon atoms, or 2 to 4 carbon atoms. Such alkenylene or alkenylene groups can be linear, branched or cyclic. Such alkenylene or alkenylene groups can optionally be substituted with one or more substituents.

[0050] In this specification, unless otherwise indicated, the term alkynylene or alkynylene group means an alkynylene or alkynylene group (e.g., vinyl or allyl, etc.) having 2 to 20 carbon atoms, 2 to 16 carbon atoms, 2 to 12 carbon atoms, 2 to 8 carbon atoms, or 2 to 4 carbon atoms. Such alkynylene or alkynylene groups can be linear, branched or cyclic. Such alkynylene or alkynylene groups can optionally be substituted with one or more substituents.

[0051] Polysaccharides generally do not contain any free radical polymerizable functional groups. Therefore, polysaccharides can be modified to introduce free radical polymerizable functional groups. The method for modifying polysaccharides to introduce free radical polymerizable functional groups is not particularly limited, and for example, the following method to be described can be applied.

[0052] The polysaccharide thus modified may contain a modified monosaccharide unit as a unit. The modified monosaccharide unit means a unit into which a functional group not existing in the original unit, for example, a radical polymerizable functional group, is introduced by chemical treatment.

[0053] In one example, the radical polymerizable functional group introduced into the modified monosaccharide unit body may be represented by Formula 1 below.

[0054] [Formula 1]

[0055]

[0056] In Formula 1, M1 is hydrogen or a metal, and when M1 is a metal, the O—M1 bond is an ionic bond.

[0057] The functional group of Formula 1 may be introduced into the unit body by bonding the oxygen atom on the left side of the above Formula 1 to the skeleton of the unit body.

[0058] The double bond included in the radical polymerizable functional group of Formula 1 may exist in the polymer composition in a state of maintaining the double bond state, or the double bond may exist in a polymerized state. In this case, a polymer chain may also exist in the polysaccharide component due to the polymerization reaction.

[0059] In Formula 1, M1 is hydrogen or a metal. The type of the metal is not particularly limited, and it may generally be an alkali metal such as lithium, sodium, potassium or cesium.

[0060] In the polymer, a functional group in which M1 in the above formula 1 is hydrogen and a functional group in which M1 is a metal may exist at the same time.

[0061] The functional group can be introduced by reacting the polysaccharide with an unsaturated dicarboxylic acid or an anhydride thereof and replacing the hydroxyl and / or amino groups present in the unit body of the polysaccharide with the functional group. Examples of dicarboxylic acids or their anhydrides can be exemplified by maleic acid or maleic anhydride, but are not limited thereto, and salts of maleic acid can also be used.

[0062] The functional group of Formula 1 is one example of a radically polymerizable functional group that can be introduced into the polysaccharide component, and other functional groups than the functional group of Formula 1 may also be used if the radically polymerizable functional group can be introduced in a suitable manner.

[0063] The lower limit of the substitution rate of the free radical polymerizable functional groups in the polysaccharide component, such as Formula 1, can be about 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, or 90%, and the upper limit thereof can also be 300%, 295%, 290%, 285%, 280%, 275%, 270%, 265%, 260%, 255%, 250%, 245%, 240%, 235%, 250%, 265%, 270%, 280%, 290%, 285 ... %, 30%, 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 can be in the range of greater than, equal to, or greater than any of the above lower limits; or in the range of less than, equal to, or less than any of the above upper limits; or in the range of greater than, equal to, or greater than any of the above lower limits and less than, equal to, or less than any of the above upper limits.

[0064] In the present specification, the substitution rate is a value indicating the degree to which hydroxyl groups or amino groups, etc. present in a unit body contained in a polysaccharide or a polysaccharide component are replaced by a predetermined functional group (e.g., a free radical polymerizable functional group), and is an average value of the degree of substitution of each unit body present in the polysaccharide or the polysaccharide component. For example, if the unit body is a glucose (glucose) unit, there are three hydroxyl groups in the relevant unit before modification, and therefore, if all hydroxyl groups are replaced by free radical polymerizable functional groups, the substitution rate of the free radical polymerizable functional groups of the relevant unit is 300%. However, the substitution rate is an average value of the degree of substitution of each unit present in the polysaccharide or the polysaccharide component, so for example, when the substitution rates of each unit in a polysaccharide containing 5 glucose (glucose) units are 100%, 0%, 200%, 300% and 100%, the substitution rate is 140%, which is an average value. Such a substitution rate can be obtained by measuring the degree of substitution of the polysaccharide or the polysaccharide component. 1 H NMR analysis. That is, since1 H NMR analysis is used to quantify the presence of hydroxyl or amino groups and substituted functional groups in the polysaccharide or polysaccharide component, thereby determining the substitution rate and, if necessary, the molecular weight of the polysaccharide or polysaccharide component before modification. 1 The substitution rate was calculated from the results of H NMR analysis. 1 The method of quantitatively analyzing functional groups by H NMR analysis is known.

[0065] The hydroxyl or amino group present in the polysaccharide component must also function as a non-radical polymerizable functional group, so in order to smoothly carry out polymerization by the free radical polymerizable functional group and crosslinking by the non-radical polymerizable functional group, the substitution rate is of great significance. In the present application, by controlling the substitution rate of the functional group including the free radical polymerizable functional group within the above range, effective crosslinking and polymerization are possible.

[0066] When the radical polymerizable functional group is the functional group of Formula 1, the polysaccharide component or polysaccharide may include a unit body of Formula 2 below.

[0067] [Formula 2]

[0068]

[0069] In Formula 2, R1 is a hydroxyl group, an amino group, or an alkylcarbonylamino group, L1 is an alkylene group or an alkylidene group, and M1 is hydrogen or a metal. If M1 is a metal, the O-M1 bond of Formula 2 may be an ionic bond. The specific type of the metal of M1 in Formula 2 is the same as that described in Formula 1. In Formula 2, the specific types of the alkyl, alkylene, or alkylidene groups are the same as those described at the beginning of this specification.

[0070] As described in Formula 1, the radical polymerizable functional group of Formula 2 may exist in a state of maintaining a double bond, or the double bond may exist in a polymerized state.

[0071] In the polysaccharide component, in the above formula 2, a functional group in which M1 is hydrogen and a functional group in which M1 is a metal may exist at the same time.

[0072] In Formula 2, when R1 is a hydroxyl group, the unit body may generally be a case where the unit body is derived from a so-called glucose unit body; when R1 is an amino group, the unit body may generally be a case where the unit body is derived from a so-called glucosamine unit body; and when R1 is an alkylcarbonylamino group, the unit body may represent a case where the unit body is derived from N-acetylglucosamine.

[0073] In addition to the functional groups including free radical polymerizable functional groups such as the functional groups of the above Formula 1, other functional groups may be introduced into the polysaccharide component. Such other functional groups include, for example, the functional groups represented by the following Formula 3.

[0074] [Formula 3]

[0075]

[0076] In Formula 3, L2 is an alkylene or alkylidene group, M2 is hydrogen or a metal, and when M2 is a metal, the O-M2 bond is an ionic bond. In Formula 3, the specific type of the alkylene or alkylidene group is the same as defined at the beginning of this specification.

[0077] The functional group of the above Formula 3 may be introduced into the unit body, just as L2 on the left side in the above Formula 3 is bonded to the skeleton of the unit body.

[0078] In Formula 3, M2 is hydrogen or a metal. The type of the metal is not particularly limited, and it may generally be an alkali metal such as lithium, sodium, potassium or cesium.

[0079] In the polysaccharide component, in the above formula 3, a functional group in which M2 is hydrogen and a functional group in which M2 is a metal may exist at the same time.

[0080] The functional group can be introduced by reacting the polysaccharide with an acetic acid chloride such as chloroacetate and replacing the hydroxyl group present in the unit body of the polymer with the functional group.

[0081] The lower limit of the substitution rate of the functional group of the above 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 300%, 295%, 290%, 285%, 280%, 275%, 270%, 265%, 260%, 255%, 250%, 245%, 240%, or 250%. %, 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 in the range of greater than, equal to, or greater than any of the above lower limits; or in the range of less than, equal to, or less than any of the above upper limits; or in the range of greater than, equal to, or greater than any of the above lower limits and less than, equal to, or less than any of the above upper limits. The definition and measurement method of the substitution rate are the same as those defined for the free radical polymerizable functional group, which can also be determined by 1 Determined by H NMR analysis.

[0082] In one example, the unit body including the functional group of the above Formula 3 may be a unit body represented by the following Formula 4.

[0083] [Formula 4]

[0084]

[0085] In Formula 4, R2 is a hydroxyl 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.

[0086] When M2 is a metal, the O-M2 bond is an ionic bond.

[0087] The specific type of the metal of M2 in Formula 4 above is the same as described in Formula 3.

[0088] In Formula 4, specific types of the alkyl group, alkylene group or alkylidene group are the same as defined at the outset.

[0089] In the polysaccharide, in the above formula 4, a functional group in which M2 is hydrogen and a functional group in which M2 is a metal may exist at the same time.

[0090] The polysaccharide component can have an appropriate molecular weight level. For example, in one example, the weight average molecular weight (Mw) of the polymer composition, polymer material or polymer can be in the range of about 500 g / mol to 1,000,000 g / mol. Within such a range, when necessary, a desired sufficient degree of crosslinking can be imparted thereto, and the obtained polymer material can stably exhibit desired properties (biodegradability and absorption capacity, etc.).

[0091] The polymer composition may contain as an additional component a crosslinking agent for crosslinking the polysaccharide component. Such a crosslinking agent may be a compound having a functional group capable of reacting with a non-free radical polymerizable functional group of the polysaccharide component.

[0092] The lower limit of the number of functional groups that the crosslinking agent has that can react with the non-radical polymerizable functional groups of the polysaccharide component may be 2, 3 or 4, and the upper limit thereof may be 10, 9, 8, 7, 6, 5, 4, 3 or 2. The number of functional groups may be in the range of greater than, equal to or greater than any of the above lower limits; or in the range of less than, equal to or less than any of the above upper limits while being greater than, equal to or greater than any of the above lower limits.

[0093] The type of the crosslinking agent is not particularly limited as long as it contains a functional group reactive with the non-radical polymerizable functional group of the polysaccharide component.

[0094] For example, as the crosslinking agent, one or more selected from the group consisting of a polyfunctional epoxy compound, an epoxysilane compound, an aminosilane compound, epichlorohydrin, an aldehyde compound such as formaldehyde or glutaraldehyde, oxidized sucrose, an acid chloride, a carbonate, a diamine, a diol, carbon disulfide, phosphorus oxychloride, divinylbenzene, an organic acid, and an organic acid anhydride can be used.

[0095] In order to perform effective cross-linking without impairing the polymerization efficiency by the above-mentioned radical-reactive functional groups and to ensure desired physical properties, the use of a specific type of cross-linking agent may be advantageous.

[0096] In one example, as the cross-linking agent, an organic acid having two or more carboxyl groups, an anhydride of an organic acid, or an organic compound having two or more formyl groups may be used.

[0097] The organic acid, the anhydride of the organic acid or the organic compound may consist only of carbon, oxygen and hydrogen.

[0098] When a crosslinking agent is used, for example, a crosslinking structure including an ester bond formed by a reaction between a carboxyl group of the crosslinking agent and a hydroxyl group in the polysaccharide component, or a covalent bond formed by a reaction between a formyl group of the crosslinking agent and an amino group in the polysaccharide component such as the following formula 5 can be achieved.

[0099] [Formula 5]

[0100] -N=-

[0101] The polysaccharide or polysaccharide component is present on one of the two sides of the bond of the above formula 5, and the cross-linking agent is present on the other side.

[0102] The type of organic acid available as a crosslinking agent is not particularly limited, but an organic acid having a molecular weight of about 90 to 300 g / mol or about 100 to 250 g / mol can be used. The number of carboxyl groups in the organic acid ranges from the same as the number of functional groups in the above crosslinking agent.

[0103] Such an organic acid may be exemplified by citric acid, succinic acid, pimelic acid, or adipic acid, but is not limited thereto.

[0104] An organic acid or anhydride thereof can be used as the crosslinking agent.

[0105] The type of the organic compound having two or more formyl groups as a 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 number of formyl groups in the organic compound ranges the same as the number of functional groups in the above crosslinking agent.

[0106] Examples of such organic compounds include glutaraldehyde, but are not limited thereto.

[0107] If applicable, the weight ratio of the crosslinking agent 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 relative to 100 parts by weight of the polysaccharide component in the polymer composition, and the upper limit thereof may be 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. The ratio may be in the range of greater than or equal to or greater than any of the above lower limits; or in the range of less than or equal to or less than any of the above upper limits; or in the range of less than or equal to or less than any of the above upper limits while being greater than or equal to or greater than any of the above lower limits.

[0108] Within such a range, effective cross-linking may be possible without impairing the polymerization efficiency by the radical polymerizable functional group of the polysaccharide component.

[0109] The polymer composition may contain any necessary components in addition to the polysaccharide component and the cross-linking agent.

[0110] For example, an initiator component (eg, a polymerization initiator) capable of initiating polymerization through double bonds may be included in the polymer composition.

[0111] As such initiator component, any known component can be used without particular limitation, as long as it can initiate polymerization of a free radical polymerizable functional group. For example, a known free radical polymerization initiator can be used as the initiator component. For example, an oxidant such as ammonium persulfate or ammonium cerium nitrate or other free radical polymerization initiators can be used as the initiator component.

[0112] The ratio of the initiator component is not particularly limited, wherein it may be used in a catalytic amount capable of initiating a polymerization reaction of a radical polymerizable functional group.

[0113] For example, in the presence of an oxidizing agent as an initiator component, polymerization through free radical polymerizable functional groups present in the polysaccharide component, and crosslinking, polymerization or grafting through free radicals generated by the oxidation action of the oxidizing agent and free radical polymerizable functional groups to form polymer chains can be performed.

[0114] The present application also relates to a polymer material comprising or formed from the polymer composition.The polymer material may also be simply referred to as a polymer (or hydrogel).

[0115] The polymer material may comprise polymer chains formed by polymerization of free radical polymerizable functional groups of the polysaccharide component of the polymer composition and covalent bonds formed by reaction of non-free radical polymerizable functional groups of the polysaccharide component with functional groups of the crosslinking agent.

[0116] The specific types of free radical polymerizable functional groups and non-free radical polymerizable functional groups, the substitution ratio of functional groups in the polysaccharide or polysaccharide component, and the type of crosslinking agent are as described above. In addition, as described above, the covalent bond may be an ester bond, or may be a covalent bond of Formula 5 above.

[0117] Such a polymer material may be the above-mentioned biodegradable material, may be an absorbent material, or may be an absorbent material at the same time as a biodegradable material. Thus, the material may exhibit centrifugal retention capacity and / or biodegradability as described above.

[0118] The polymer material can be used in various applications by simultaneously exhibiting excellent absorbency and biodegradability.

[0119] For example, the polymer material can be used as a sanitary product such as a diaper or sanitary napkin, or as an absorbent material for other applications requiring absorption. If necessary, the polymer material can also be further cross-linked, surface treated or physically ground to improve the efficiency of being used as a sanitary product or absorbent material.

[0120] Therefore, the present application relates to absorbent materials or sanitary products (eg, diapers, sanitary napkins, etc.) comprising the polymer material.

[0121] A specific method of forming an absorbent material or sanitary article by applying a polymer material is not particularly limited, and, for example, a method of forming an absorbent material or sanitary article by applying an existing SAP may be used in the same manner.

[0122] Beneficial Effects

[0123] The application can provide polymer compositions and uses thereof. The polymer composition comprises a polysaccharide component, wherein the polysaccharide component comprises a functional group that can be free radical polymerized and a functional group that cannot be free radical polymerized. Such a polysaccharide component can form a polymer comprising a polymer chain formed by polymerization of the functional group that can be free radical polymerized and a polymer of a covalent bond formed by the reaction of the functional group that cannot be free radical polymerized. The polymer can form an absorbent material with excellent absorbency, a biodegradable material with excellent biodegradability, or a material that is formed as an absorbent material and is simultaneously a biodegradable material. The application can also provide the use of the polymer composition or the polymer. BRIEF DESCRIPTION OF THE DRAWINGS

[0124] Figure 1To show the modified polysaccharide prepared in Preparation Example 1 1 Graph of the H NMR analysis results.

[0125] Figure 2 To show the modified polysaccharide prepared in Preparation Example 2 1 Graph of the H NMR analysis results. DETAILED DESCRIPTION

[0126] Hereinafter, the present application will be described in detail through Examples and Comparative Examples, but the scope of the present application is not limited to the following Examples.

[0127] 1. Centrifuge retention capacity (CRC) assessment

[0128] Centrifuge retention capacity (CRC) is measured according to EDANA (European Disposables and Nonwovens Association) WSP 241.3. About 0.2g (W0) of the polymer obtained is placed in a nonwoven bag, sealed, and then immersed in a physiological saline solution. As a physiological saline solution, a NaCl aqueous solution with a concentration of 0.9 weight % is used. This state is maintained for about 30 minutes, and water is removed from the bag under the condition of 250G using a centrifuge for 3 minutes, and the mass (g, W2) of the bag is measured. The same nonwoven bag that does not contain polymer is immersed in the same physiological saline solution. This state is maintained for about 30 minutes, and water is removed from the bag under the condition of 250G using a centrifuge for 3 minutes, and the mass (g, W1) of the bag is measured. CRC (g / g) is calculated by substituting the measurement result into the following equation A. This evaluation is carried out under constant temperature and humidity conditions (23 ± 1 ° C, relative humidity: 50 ± 10%).

[0129] [Equation A]

[0130] CRC(g / g)={[W2(g)-W1(g)] / W0(g)}-1

[0131] 2. Measurement of biodegradability

[0132] Biodegradability is measured in the manner specified in ISO 14855-1 (2005) standard. The above standard is a method for measuring the aerobic biodegradability of plastic materials under composting conditions, which is a method for quantitatively calculating the biodegradability of polymers by the amount of carbon dioxide discharged by the microorganisms that metabolize the relevant materials. When polymers are applied to composting conditions according to the standard, biodegradability is measured for 6 months, and biodegradability is obtained as the ratio of the theoretical carbon dioxide generation of the material and the actual carbon dioxide generation. Theoretical carbon dioxide generation and biodegradability are obtained according to equations C and D below, respectively.

[0133] [Equation C]

[0134] Theoretical carbon dioxide production (ThCO2, g / container) = M T O T ×C T O T ×(44 / 12)

[0135] In equation C, M T O T is the amount of total dry solid content (g) of the test material (polymer) added to the compost at the beginning of the measurement, and C T O T It means the ratio (g / g) of organic carbon contained in the total dry solid content of the test material.

[0136] [Equation D]

[0137] Biodegradability (%) = [{(CO2) T -(CO2) B} / ThCO2]×100

[0138] In equation D, (CO2) T is the cumulative amount of carbon dioxide produced from the compost container containing the test material (g / container), (CO2) B is the average cumulative amount of carbon dioxide produced from the inoculum source container (g / container), and ThCO2 is the theoretical carbon dioxide production determined in Equation C above.

[0139] Preparation Example 1.

[0140] A polysaccharide (modified starch) (Compound A) comprising a modified monosaccharide unit of the following formula A was prepared in the following manner. The modified monosaccharide unit of the following formula A is a monosaccharide unit into which a maleic acid group (M1 in Formula 1 is a substituent of a hydrogen atom) is introduced.

[0141] [Formula A]

[0142]

[0143] 15g starch and 50mL DMSO (dimethyl sulfoxide) are added to 500mL RBF (Round Bottom Flask, round bottom flask), and stirred at 65°C for 2 hours to gelatinize it. As starch, potato starch is used. About 30g maleic anhydride is added to the gelatinized starch, and reacted at 65°C for about 3 hours. After the reaction is completed, the temperature is lowered to room temperature (about 25°C), and acetone is added to produce a precipitate. The precipitate is recovered and dried in a vacuum drying oven at 40°C for one day to obtain a solid target product (Compound A).

[0144] Can be1 The substitution rate of the obtained target product (Compound A) was obtained by H NMR analysis. 1 H NMR analyses were performed at room temperature (about 25 °C) using a Varian Unity Inova (500 MHz) spectrometer with a triple resonance 5 mm probe. 1 HNMR spectroscopy was performed. 1 In the H NMR analysis, Bruker's Avance Neo instrument was used. Specifically, 50 mg of the obtained solid target product (Compound A) and 200 mg of a 30% DCl solution in D2O were mixed and stirred at 50°C for about 1 hour to induce a hydrolysis reaction, and the mixture was allowed to proceed. 1 H NMR analysis. 1 H NMR analysis was used to determine the substitution rate of starch by maleic acid groups. Figure 1 The above compound A is shown 1 The results of H NMR analysis showed that the substitution ratio was about 81%.

[0145] Preparation Example 2.

[0146] A polysaccharide (modified chitosan) (Compound B) comprising a modified monosaccharide unit of the following formula B was prepared in the following manner. The modified monosaccharide unit of the following formula B is a monosaccharide unit into which a maleic acid group (M1 in Formula 1 is a substituent of a hydrogen atom) is introduced.

[0147] [Formula B]

[0148]

[0149] 15 g of chitosan and 300 mL of DMSO (dimethyl sulfoxide) were added to a 500 mL RBF (round bottom flask) and stirred at 65° C. for 30 minutes to gelatinize. About 30 g of maleic anhydride was added to the gelatinized chitosan and reacted at 65° C. for about 3 hours. After the reaction was completed, the temperature was lowered to room temperature (about 25° C.), and acetone was added to produce a precipitate.

[0150] The precipitate was recovered and dried in a vacuum oven at 40° C. for one day to obtain a solid target product (Compound B).

[0151] Can be 1 The substitution rate of the obtained target product (Compound B) was obtained by H NMR analysis. 1 H NMR analyses were performed at room temperature (about 25 °C) using a Varian Unity Inova (500 MHz) spectrometer with a triple resonance 5 mm probe. 1 HNMR spectroscopy was performed. 1In the H NMR analysis, Bruker's Avance Neo instrument was used. Specifically, 50 mg of the obtained solid target product (Compound B) and 200 mg of a 30% DCl solution in D2O were mixed and stirred at 50°C for about 1 hour to induce a hydrolysis reaction, and the mixture was allowed to proceed. 1 H NMR analysis.

[0152] Depend on 1 H NMR analysis was used to determine the substitution rate of chitosan by maleic acid groups. Figure 2 The above compound B is shown 1 The result of H NMR analysis was used, and the substitution ratio calculated based on the result was about 94%.

[0153] Example 1.

[0154] The compound (A) of Preparation Example 1 and a crosslinking agent (citric acid) were mixed in distilled water at a weight ratio of 2.8:0.2 (compound (A): crosslinking agent), and ammonium cerium nitrate as an initiator was added thereto at a rate of about 2 mol% to prepare a polymer composition. Subsequently, the mixture was stirred at 35° C. for 2 hours to perform polymerization and crosslinking through double bonds, thereby preparing a biodegradable polymer having an absorption capacity. Ethanol was added to precipitate the polymer, and it was dried in a vacuum drying oven at 40° C.

[0155] Example 2.

[0156] A polymer material was prepared in the same manner as in Example 1, except that the ratio of the compound (A) and the crosslinking agent (citric acid) of Preparation Example 1 was changed to a weight ratio of 2.6:0.4 (compound (A):crosslinking agent).

[0157] Example 3.

[0158] A polymer material was prepared in the same manner as in Example 1, except that the ratio of the compound (A) and the crosslinking agent (citric acid) of Preparation Example 1 was changed to a weight ratio of 2.4:0.6 (compound (A):crosslinking agent).

[0159] Comparative Example 1.

[0160] The polymer material was prepared as in Example 1 by applying only compound (A) without using a cross-linking agent.

[0161] Comparative Example 2

[0162] The polymer material was prepared as in Example 1 by applying only citric acid without using compound (A).

[0163] Example 4.

[0164] Compound (B) of Preparation Example 2 and glutaraldehyde as 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 as an initiator was added thereto at a rate of about 2 mol% to prepare a polymer composition.

[0165] The polymer composition was stirred at 35°C for 2 hours to perform polymerization and crosslinking reactions through double bonds, thereby preparing a biodegradable polymer having absorption capacity. Ethanol was added to precipitate the polymer, and it was dried in a vacuum drying oven at 40°C.

[0166] Example 5.

[0167] A polymer material was prepared in the same manner as in Example 4, except that the ratio of the compound (B) of Preparation Example 2 and the crosslinking agent (glutaraldehyde) was changed to a weight ratio of 2.6:0.4 (compound (B):crosslinking agent).

[0168] Example 6

[0169] A polymer material was prepared in the same manner as in Example 4, except that the ratio of the compound (B) of Preparation Example 2 and the crosslinking agent (glutaraldehyde) was changed to a weight ratio of 2.4:0.6 (compound (B):crosslinking agent).

[0170] Comparative Example 3.

[0171] The polymer material was prepared as in Example 4 by applying only compound (B) without using a cross-linking agent.

[0172] Comparative Example 4

[0173] The polymer material was prepared as in Example 4 by using only glutaraldehyde without using compound (B).

[0174] The results of measuring the physical properties of the polymer materials of Examples and Comparative Examples are shown in Table 1 below.

[0175] [Table 1]

[0176]

[0177] When Examples 1 to 3 and Comparative Example 1 and Examples 4 to 6 and Comparative Example 3 were compared, it was confirmed that in the case of the Examples, they exhibited superior absorption capacity and / or biodegradability relative to Comparative Examples 1 and 3 using only the polysaccharide component.

Claims

1. A polymer composition comprising: a polysaccharide component having free radical polymerizable functional groups and non-free radical polymerizable functional groups; and A compound having two or more functional groups capable of reacting with the non-radical polymerizable functional group. 2 . The polymer composition according to claim 1 , wherein the non-free radical polymerizable functional group is a hydroxyl group, an amino group or a carboxyl group.

3. The polymer composition according to claim 1, wherein the free radical polymerizable functional group comprises one or more selected from an alkenyl group, an alkynyl group, an alkenylene group, and an alkynylene group.

4. The polymer composition according to claim 1, wherein the substitution rate of the free radical polymerizable functional groups in the polysaccharide component is in the range of 10% to 300%.

5. The polymer composition according to claim 1, wherein the free radical polymerizable functional group is a functional group of the following formula 1: [Formula 1] In Formula 1, M1 is hydrogen or a metal, and when M1 is the metal, the O—M1 bond is an ionic bond.

6. The polymer composition according to claim 1, wherein the polysaccharide component comprises a unit body of the following formula 2: [Formula 2] In Formula 2, R1 is a hydroxyl group, an amino group or an alkylcarbonylamino group, L1 is an alkylene group or an alkylidene group, M1 is hydrogen or a metal, and when M1 is the metal, the O-M1 bond is an ionic bond. 7 . 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. The polymer composition according to claim 7, wherein the molar mass of the organic acid is in the range of 90 g / mol to 300 g / mol, and the molar mass of the organic compound is in the range of 90 g / mol to 200 g / mol.

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

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

12. The polymer composition of claim 1, further comprising a free radical polymerization initiator.

13. A polymer comprising: a polysaccharide component having free radical polymerizable functional groups and non-free radical polymerizable functional groups; and A compound having two or more functional groups capable of reacting with the non-radical polymerizable functional group, wherein The free radical polymerizable functional groups of the polysaccharide component form polymer chains, and the non-free radical polymerizable functional groups of the polysaccharide component form covalent bonds with functional groups of the compound.

14. The polymer according to claim 13, wherein the covalent bond is an ester bond or a bond of the following formula 5: [Formula 5] -N＝-。 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. The polymer according to claim 15, wherein the molar mass of the organic acid is in the range of 90 g / mol to 300 g / mol, and the molar mass of the organic compound is in the range of 90 g / mol to 200 g / mol.

17. The polymer of claim 13, wherein the compound is citric acid, citric anhydride, succinic acid, succinic anhydride, pimelic acid, pimelic anhydride, adipic acid, adipic anhydride, or glutaraldehyde.

18. The polymer of claim 13, wherein the polymer has a centrifuge retention capacity according to EDANA (European Disposables and Nonwovens Association) method WSP 241.3 of 10 g / g or more.

19. The polymer of claim 13, wherein the biodegradability of the polymer is 60% or greater.

20. An absorbent material comprising the polymer according to claim 13.

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