Polymer Composition

Abstract

The present specification discloses a polymer composition. Th polymer composition comprises a polysaccharide component, where the polysaccharide component contains a radically polymerizable functional group and a non-radically polymerizable functional group. Such a polysaccharide component can form a polymer including polymer chains formed by the polymerization of the radically polymerizable functional groups and covalent bonds formed by the reaction of the non-radically polymerizable functional groups. The polymer can form an absorbent material having excellent absorptivity, form a biodegradable material having excellent biodegradability, or form a material which is an absorbent material and simultaneously a biodegradable material. The present application can also provide a use of the polymer composition or the polymer.

Claims

1. A polymer composition comprising: a polysaccharide component having a radically polymerizable functional groups 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.

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

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

5. The polymer composition according to claim 1, wherein the radically polymerizable functional group is a functional group of Formula 1 below: ##STR00008## wherein, M.sub.1 is hydrogen or a metal, and when M.sub.1 is the metal, the O-M.sub.1 bond is an ionic bond.

6. The polymer composition according to claim 1, wherein the polysaccharide component comprises a unitary body of Formula 2 below: ##STR00009## wherein, R.sub.1 is a hydroxy group, an amino group, or an alkylcarbonylamino group, L.sub.1 is an alkylene group or an alkylidene group, M.sub.1 is hydrogen or a metal, and when M.sub.1 is the metal, the O-M.sub.1 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 organic acid has a molar mass in a range of 90 g/mol to 300 g/mol, and the organic compound has a molar mass in a range of 90 g/mol to 200 g/mol.

9. The polymer composition according to 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 part by weight 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 according to claim 1, further comprising a radical polymerization initiator.

13. A polymer comprising: 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, wherein the radically polymerizable functional group of the polysaccharide component forms polymer chains, and the non-radically polymerizable functional group of the polysaccharide component forms covalent bond with the functional groups of the compound.

14. The polymer according to claim 13, wherein the covalent bond is an ester bond or a bond of Formula 5 below: ##STR00010##

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 organic acid has a molar mass in a range of 90 g/mol to 300 g/mol, and the organic compound has a molar mass in a range of 90 g/mol to 200 g/mol.

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

19. The polymer according to claim 13, wherein the polymer has biodegradability of 60% or more.

20. An absorbent material comprising the polymer of claim 13.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0111] FIG. 1 is is an illustration of .sup.1H NMR analysis results of the modified polysaccharide prepared in Preparation Example 1.

[0112] FIG. 2 is an illustration of .sup.1H NMR analysis results of the modified polysaccharide prepared in Preparation Example 2.

DETAILED DESCRIPTION

[0113] Hereinafter, the present application will be described in detail through examples and comparative examples, but the scope of the present application is not limited by the following examples.

1. Centrifuge Retention Capacity (CRC) Evaluation

[0114] Centrifuge retention capacity (CRC) was measured according to EDANA (European Disposables and Nonwovens Association) WSP 241.3. About 0.2 g (W.sub.0) of the obtained polymer was placed in a non-woven bag, sealed, and then submerged in a physiological saline solution. As the physiological saline solution, an aqueous NaCl solution with a concentration of 0.9 wt % was used. The state was maintained for 30 minutes or so, water was removed from the bag for 3 minutes under a condition of 250 G using a centrifuge, and the mass (g, W.sub.2) of the bag was measured. The same nonwoven bag containing no polymer was submerged in the same physiological saline solution. The state was maintained for 30 minutes or so, water was removed from the bag for 3 minutes under a condition of 250 G using a centrifuge, and the mass (g, W.sub.1) of the bag was measured. The CRC (g/g) was calculated by substituting the measurement results into Equation A below. The evaluation was conducted under constant temperature and humidity conditions (231 C., relative humidity: 5010%).

[00001]$\begin{array}{cc}\mathrm{CRC}\left(g/g\right)=\left\{\left[W_2\left(g\right)-W_1\left(g\right)\right]/W_0\left(g\right)\right\}-1& \left[\mathrm{Equation}A\right]\end{array}$

2. Measurement of Biodegradability

[0115] Biodegradability was measured in the manner specified in ISO 14855-1 (2005) standard. The above standard is a method of measuring aerobic biodegradability of plastic materials under a composting condition, which is a method that the biodegradability of a polymer is calculated by quantifying the amount of carbon dioxide emitted by microorganisms metabolizing the relevant material. As the polymer was applied to the composting condition according to the standard, the biodegradability was measured for 6 months, and the biodegradability was obtained as the ratio of the theoretical carbon dioxide generation amount and the actual carbon dioxide generation amount of the material. The theoretical carbon dioxide generation amount and biodegradability are obtained according to the following equations C and D, respectively.

[00002]$\begin{array}{cc}\mathrm{Theoretical}\mathrm{carbon}\mathrm{dioxide}\mathrm{generation}\mathrm{amount}\left({\mathrm{Th}\mathrm{CO}}_2,g/\mathrm{container}\right)=M_T{O}_T{C}_T{O}_T\left(44/12\right)& \left[\mathrm{Equation}C\right]\end{array}$

[0116] In Equation C, M.sub.TO.sub.T is the amount (g) of total dry solid content in the test material (polymer) added to the compost at the start of the measurement, and C.sub.TO.sub.T means the ratio (g/g) of organic carbon contained in the total dry solid content of the test material.

[00003]$\begin{array}{cc}\mathrm{Biodegradability}\left(\%\right)=\left[\left\{{\left({\mathrm{CO}}_2\right)}_T-{\left({\mathrm{CO}}_2\right)}_B\right\}/{\mathrm{Th}\mathrm{CO}}_2\right]100& \left[\mathrm{Equation}D\right]\end{array}$

[0117] In Equation D, (CO.sub.2).sub.T is the accumulated amount (g/container) of carbon dioxide generated from the composting container containing the test material, (CO.sub.2).sub.B is the average (g/container) of carbon dioxide accumulated amounts generated from the inoculum source container, and ThCO.sub.2 is the theoretical carbon dioxide generation amount confirmed in Equation C above.

Preparation Example 1

[0118] A polysaccharide (modified starch) (Compound A) containing a modified monosaccharide unitary body of Formula A below was prepared in the following manner. The modified monosaccharide unitary body of Formula A below is a monosaccharide unitary body into which a maleic acid group (a substituent where M.sub.1 in Formula 1 is a hydrogen atom) is introduced.

##STR00006##

[0119] 15 g of starch and 50 mL of DMSO (dimethyl sulfoxide) were added to a 500 mL RBF (Round Bottom Flask), and stirred at 65 C. for 2 hours to be gelatinized. As the starch, potato starch was used. About 30 g of maleic anhydride was added to the gelatinized starch and reacted at 65 C. for 3 hours or so. After completion of the reaction, the temperature was lowered to room temperature (about 25 C.), and acetone was added to generate a precipitate. The precipitate was recovered and dried in a vacuum drying oven at 40 C. for one day to obtain a solid target product (Compound A).

[0120] The substitutional rate of the obtained target product (Compound A) can be obtained through a .sup.1H NMR analysis. The .sup.1H NMR analysis is performed at room temperature (about 25 C.) using a .sup.1H NMR spectrometer including a Varian Unity Inova (500 MHz) spectrometer with a triple resonance 5 mm probe. In the .sup.1H NMR analysis, Bruker's Avance Neo instrument was used. Specifically, 50 mg of the obtained solid target product (Compound A) and 200 mg of 30% DCl in D.sub.2O solution are mixed, stirred at 50 C. for 1 hour or so to induce a hydrolysis reaction, and the .sup.1H NMR analysis can be performed. The substitutional rate of the maleic acid group to the starch was confirmed by the .sup.1H NMR analysis. FIG. 1 shows the results of .sup.1H NMR analysis performed on Compound A above, and the substitutional rate calculated based on this was about 81% or so.

Preparation Example 2

[0121] A polysaccharide (modified chitosan) (Compound B) containing a modified monosaccharide unitary body of Formula B below was prepared in the following manner. The modified monosaccharide unitary body of Formula B below is a monosaccharide unitary body into which a maleic acid group (a substituent where M.sub.1 is a hydrogen atom in Formula 1) is introduced.

##STR00007##

[0122] 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 be gelatinized. About 30 g of maleic anhydride was added to the gelatinized chitosan, and reacted at 65 C. for 3 hours or so. After completion of the reaction, the temperature was lowered to room temperature (about 25 C.), and acetone was added to generate a precipitate.

[0123] The precipitate was recovered and dried in a vacuum drying oven at 40 C. for one day to obtain the solid target product (Compound B).

[0124] The substitutional rate of the obtained target product (Compound B) can be obtained through a .sup.1H NMR analysis. The .sup.1H NMR analysis is performed at room temperature (about 25 C.) using a .sup.1H NMR spectrometer including a Varian Unity Inova (500 MHz) spectrometer with a triple resonance 5 mm probe. In the .sup.1H NMR analysis, Bruker's Avance Neo instrument was used. Specifically, 50 mg of the obtained solid target product (Compound B) and 200 mg of 30% DCl in D.sub.2O solution are mixed, stirred at 50 C. for 1 hour or so to induce a hydrolysis reaction, and the .sup.1H NMR analysis can be performed.

[0125] The substitutional rate of the maleic acid group to the chitosan was confirmed by the .sup.1H NMR analysis. FIG. 2 shows the results of .sup.1H NMR analysis performed on Compound B above, and the substitutional rate calculated based on this was about 94% or so.

Example 1

[0126] The compound (A) of Preparation Example 1 and a cross-linking agent (citric acid) were mixed in distilled water in a weight ratio of 2.8:0.2 (compound (A): cross-linking agent), and ammonium cerium nitrate as an initiator was added thereto in a ratio of at about 2 mol % to prepare a polymer composition. Subsequently, the mixture was stirred at 35 C. for 2 hours to proceed with polymerization and cross-linking by 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.

Example 2

[0127] A polymer material was prepared in the same manner as in Example 1, except that the ratio of the compound (A) of Preparation Example 1 and a cross-linking agent (citric acid) was changed to a weight ratio of 2.6:0.4 (compound (A): cross-linking agent).

Example 3

[0128] A polymer material was prepared in the same manner as in Example 1, except that the ratio of the compound (A) of Preparation Example 1 and a cross-linking agent (citric acid) was changed to a weight ratio of 2.4:0.6 (compound (A): cross-linking agent).

Comparative Example 1

[0129] A polymer material was prepared as in Example 1 by applying only the compound (A) without applying the cross-linking agent.

Comparative Example 2

[0130] A polymer material was prepared as in Example 1 by applying only citric acid without applying the compound (A).

Example 4

[0131] The compound (B) of Preparation Example 2 and glutaraldehyde as a cross-linking agent were mixed in distilled water in a weight ratio of 2.8:0.2 (compound (B): cross-linking agent), and ammonium cerium nitrate as an initiator was added thereto in a ratio of about 2 mol % to prepare a polymer composition.

[0132] The polymer composition was stirred at 35 C. for 2 hours to proceed with polymerization and cross-linking reactions by 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.

Example 5

[0133] 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 a cross-linking agent (glutaraldehyde) was changed to a weight ratio of 2.6:0.4 (compound (B): cross-linking agent).

Example 6

[0134] 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 a cross-linking agent (glutaraldehyde) was changed to a weight ratio of 2.4:0.6 (compound (B): cross-linking agent).

Comparative Example 3

[0135] A polymer material was prepared as in Example 4 by applying only the compound (B) without applying the cross-linking agent.

Comparative Example 4

[0136] A polymer material was prepared as in Example 4 by applying only glutaraldehyde without applying the compound (B).

[0137] The physical property measurement results for the polymer materials of Examples and Comparative Examples are as shown in Table 1 below.

TABLE-US-00001 TABLE 1 Example Comparative Example 1 2 3 4 5 6 1 2 3 4 CRC(g/g) 17.4 16.3 16.0 23.1 22.0 22.3 15.2 1.2 23.3 1.0 Biodegradability (%) 85 81 72 71 73 72 80 43 68

[0138] When Examples 1 to 3 and Comparative Example 1, and Examples 4 to 6 and Comparative Example 3 are compared, it can be confirmed that in the case of Examples, they exhibit superior absorption capacity and/or biodegradability relative to Comparative Examples 1 and 3 in which only the polysaccharide component has been used.