KR20140130072A - The method of manufacturing cellulose and method of manufacturing a cellulose-based polymer having antimicrobial - Google Patents

Abstract

The present invention relates to a cellulose manufacturing method and a manufacturing method for cellulose-based polymer which can be used as an antibacterial agent includes: a) a step of pre-treating the biomass by emitting radiation rays to a biomass raw material; b) dissolving the pre-treated bio-mass to a ionic liquid represented by the formula 1; and c) obtaining the cellulose by extracting the cellulose from the biomass dissolved to the ionic fluid.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a method for producing a cellulose-based polymeric antimicrobial agent,

The present invention provides a method for producing cellulose from biomass and a method for producing a cellulosic polymeric antimicrobial agent obtained by grafting an ionic liquid onto cellulose produced according to the present invention. More particularly, A process for producing cellulose from a biomass such as cotton pulp, rice husk, and Empty Fruit Bunch (EFB) using a gaseous liquid, and a method for producing a cellulosic polymer antibacterial agent obtained by grafting an ionic liquid onto cellulose prepared according to the present invention .

Cellulose is a major component of trees and plants, and vast amounts of cellulose are naturally synthesized in trees and plants. Nonetheless, biomass such as rice hulls containing cellulose and Empty Fruit Bunch (EFB) have limited applications in their applications because cellulose has a highly crystalline structure, which makes it difficult to access enzymes such as morphology, It is low.

As proposed in Korean Patent Publication No. 2012-0093430, commercial use of lignocellulose resources for ethanol production requires a so-called "pretreatment" process of lignocellulose resources to increase accessibility to biomass, enzymes or chemical solvents do.

The pretreatment process is based on conventional organic or alkaline organic solvents. Despite the efficiency of the pretreatment process, the existing cellulose separation and manufacturing processes represented by the kraft pulping process can be reused and used And many complementary technologies have been developed and applied in various environmental aspects, but they are still regarded as pollution inducing and high energy industries.

In recent years, new eco-friendly technologies capable of overcoming the separation and purification technology of cellulose, which has been carried out under high temperature and pressure conditions based on existing organic solvents such as acid or alkali, have been mainly performed in advanced countries, Research on economical and effective processes with yields is required.

Especially, biodegradable biomass such as rice hull and EFB have low solubility and it is very difficult to extract cellulose from them.

On the other hand, various antimicrobial polymers are manufactured by immobilizing a low molecular weight antimicrobial agent on a polymer for the past several centuries. Compared to conventional low molecular weight antimicrobial agents, polymeric antimicrobial agents have advantages such as improved antibacterial activity, reduced residual toxicity, increased antimicrobial activity and selectivity, and longer life span. However, cellulose having a high crystal structure still has a lot of limitations in applying cellulose as a matrix and applying it to an antimicrobial agent due to low solubility and difficulty of accessibility with a chemical solvent.

Korean Patent Publication No. 2012-0093430

The present invention provides a method for producing cellulose from biomass.

The present invention also provides a method for producing a cellulosic polymeric antimicrobial agent in which an ionic liquid is graft-reacted with cellulose prepared according to the present invention.

The present invention also provides a cellulosic polymeric antimicrobial agent prepared according to the process for producing a cellulosic polymeric antimicrobial agent of the present invention.

      The Applicant has used an ionic liquid, which is a solvent used for effectively producing cellulose from biomass, in order to achieve the above-mentioned problems. Furthermore, the relatively high molecular weight and crystallinity of the cellulose itself have been solved by solubility in an ionic liquid It has been determined that the biodegradation of cellulose may be caused by cutting high-energy waves such as X-rays, gamma rays and electron beams to cut the cellulose main chain in the biomass, thereby completing the present invention .

That is, the present invention processes cellulose with an ionic liquid and radiation, especially an electron beam, in the production of cellulose from biomass to produce cellulose of surprisingly high purity and yield.

More specifically, in order to improve the dissolution efficiency of an ionic liquid, the present invention evaluates the effect of radiation, particularly electron beam treatment, on poorly soluble biomass such as cotton pulp, rice husk, and EFB (Empty Fruit Bunch) . The changes of the dissolution rate by the degree of electron beam treatment were evaluated and the structural characteristics of the regenerated cellulose were compared and analyzed by re - precipitation of the cellulose from the ionic liquid after actual dissolution. Through these studies, we intend to expand the applicability of ionic liquids as a cellulose dissolution technology for the production of new cellulose high value added materials in the future.

   The present invention provides a method for producing cellulose which can be applied to various applications,

a) pre-treating the biomass by irradiating the biomass with radiation;

b) dissolving the pretreated biomass in an ionic liquid of formula

and c) extracting cellulose from the biomass dissolved in the ionic liquid to obtain cellulose.

[Chemical Formula 1]

X ⁺ Y ^-

Wherein X ⁺ is an imidazolium ion, a pyridinium ion, an ammonium ion, a phosphonium ion, a sulfide ion, a pyrazolium ion, or a pyrrolidium ion; Y ^- is BF ₄ ^- , PF ₆ ^- , AlCl ₄ ^- , halogen ^- , CH ₃ CO ₂ ^- , CF ₃ CO ₂ ^- , CH ₃ SO ₄ ^- , CF ₃ SO ₃ ^- , (CF ₃ SO ₂ ) N ^- , NO ₃ ^- , SbF ₆ ^- , Sb ₂ F 11 ^- , MePhSO ₃ ^- , (CF ₃ SO ₂ ) ₂ N ^- or (CF ₃ SO ₂ ) ₃ C ^- .]

The biomass according to an embodiment of the present invention may be one selected from the group consisting of rice hull, cotton fiber, kenaf, bamboo, mulberry, cornstarch, rice straw, flax, hemp, hemp, jute and EFB, The electron beam may have a total dose of 10 to 1000 KGy.

The ionic liquid represented by Chemical Formula 1 according to an embodiment of the present invention specifically includes 1-allyl-3-methylimidazolium chloride, 1,3-dimethylimidazolium chloride, 1-butyl- Butyl-3-methylimidazolium dicyanamide, 1-butyl-3-methylimidazolium hexafluoroantimonate, 1-butyl-3-methylimidazoium Butyl-3-methylimidazolium hydrogensulfate, 1-butyl-3-methylimidazolium hydrogensulfate, 1-butyl-3-methylimidazolium methylsulfate, Butyl-3-methylimidazolium tetrachloroaluminate, 1-butyl-3-methylimidazolium tetrachloroborate, 1-butyl-3-methylimidazolium thiocyanate, 1-dodecyl Methylimidazolium iodide, 1-ethyl-2,3-dimethylimidazolium chloride, 1-ethyl-3-methylimidazoium bromide Ethyl-3-methylimidazolium hexafluorophosphate, 1-ethyl-3-methylimidazolium tetrafluoroborate, 1- Hexyl-3-methylimidazolium tetrafluoroborate, and 1-butyl-4-methylpyridinium chloride.

The extraction in step c) according to one embodiment of the present invention may be carried out with water, acetonitrile or mixtures thereof.

The present invention also provides a method for producing biomass, comprising the steps of: A) irradiating biomass material with radiation to pre-treat the biomass;

B) adding an ionic liquid represented by the following formula (2) to the pretreated biomass to prepare a cellulosic polymeric antimicrobial agent in which an ionic liquid is grafted to cellulose in the pretreated biomass;

(C) separating the cellulose-based polymeric antibacterial agent prepared above from the cellulosic polymeric antimicrobial agent.

(2)

X ⁺ Y ₁ ^-

Wherein X ⁺ is an imidazolium ion, a pyridium ion, an ammonium ion, a pyrazolium ion, or a pyrrolidium ion; Y ₁ ^- (R ₁ ) (R ₂ ) PO ₂ ^- wherein R ₁ is hydrogen, hydroxy (C ₁ -C 5) alkyl or (C 1 -C 5) R < _{2 >} is hydroxy or (C1-C5) alkoxy.

Separation according to one embodiment of the method for producing a cellulosic polymeric antibacterial agent of the present invention can be carried out using acetonitrile as a solvent.

The ionic liquid according to one embodiment of the method for producing a cellulosic polymeric antimicrobial agent of the present invention may be 1,3-dimethylimidazolium methyl-phosphite or 1-butyl-3-methylimidazolium dibutylphosphate have.

The biomass raw material according to one embodiment of the method for producing a cellulosic polymeric antimicrobial agent of the present invention may be one or more selected from the group consisting of rice hull, cotton fiber, kenaf, bamboo, mulberry, cornstarch, rice straw, flax, Or mixtures thereof.

The present invention also provides a cellulosic polymeric antimicrobial agent prepared according to the process for producing a cellulosic polymeric antimicrobial agent of the present invention.

The method of producing cellulose according to the present invention can dissolve the biomass pretreated with radiation using a specific ionic liquid to easily dissolve the poorly soluble biomass such as rice hull, EFB and the like, as well as the conventional heat or alkali extraction It is more environmentally friendly, and is a very effective way to obtain high purity cellulose with economical and high yield with reduced use of chemicals.

The method for producing a cellulose-based polymeric antibacterial agent of the present invention is a simple process in which a biomass pretreated with radiation is grafted to a specific ionic liquid by reacting cellulose present in the biomass pretreated with a specific ionic liquid. It is possible to manufacture a cellulose-based polymer antibacterial agent.

In addition, the cellulosic polymeric antimicrobial agent of the present invention has higher activity and selectivity, lower residual toxicity and longer life than conventional low molecular weight antimicrobial agents, and can be used as a food processing, a medical instrument, an antibacterial fiber, a disinfectant, and a medicine preservative.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a graph showing the hot water extraction contents of cotton pulp, rice hull and EFB according to the total irradiation dose of the electron beam of Example 1 of the present invention,
2 is a graph showing alkali extraction contents of cotton pulp, rice hull and EFB according to the total irradiation dose of the electron beam of Example 1 of the present invention,
3 is a graph showing a TGA graph of a surface fiber according to the total irradiation dose of the electron beam of Example 1 of the present invention,
4 is a view showing a dissolution image over time obtained by dissolving a cotton pulp pretreated with an electron beam in Example 3 of the present invention in 1-allyl-3-methylimidazolium chloride (hereinafter referred to as AC)
5 is a view showing a dissolution image according to time after dissolving the rice husks pretreated with the electron beam in Example 4 of the present invention in 1,3-dimethylimidazolium phosphite (hereinafter referred to as Me)
6 is a view showing a dissolution image over time of dissolving the rice husk pretreated with the electron beam in 1-allyl-3-methylimidazolium chloride (hereinafter referred to as AC) of Example 5 of the present invention,
FIG. 7 is a graph showing a dissolution image according to time after dissolving the rice husk pretreated with the electron beam in Example 6 of the present invention in 1,3-dimethylimidazolium methyl-phosphite (hereinafter referred to as Me)
FIG. 8 is a graph showing an image of dissolution of EFB pretreated with an electron beam in Example 7 of the present invention in 1-allyl-3-methylimidazolium chloride (hereinafter referred to as AC)
9 is a graph showing an image of dissolution of EFB pretreated with an electron beam in Example 8 of the present invention in 1,3-dimethylimidazolium methyl-phosphite (hereinafter referred to as Me)
10 is a view showing an image of a cellulose-based polymeric antibacterial agent prepared according to Example 10 of the present invention,
11 is a graph showing a TGA graph of a cellulose-based polymeric antibacterial agent prepared according to Example 10 of the present invention.
12 is a diagram showing a ¹³ C NMR spectrum of a cellulose-based polymeric antimicrobial agent prepared according to Example 10 of the present invention.
13 shows FT-IR spectra of cellulose and phosphated cellulose prepared according to Example 10 of the present invention.
FIG. 14 is a photograph showing a material precipitated primarily from rice husks using Me according to Example 11 of the present invention. FIG.
FIG. 15 is a photograph showing a material precipitated secondarily from rice hulls using Me according to Example 11 of the present invention. FIG.
16 is a photograph showing the results of the antibacterial test of Example 12 of the present invention.

The present invention provides a method for economically and efficiently producing cellulose from biomass, and the method for producing cellulose of the present invention comprises:

a) pre-treating the biomass by irradiating the biomass feedstock with radiation;

b) dissolving the pretreated biomass in the ionic liquid of Formula 1;

and c) extracting cellulose from the biomass dissolved in the ionic liquid to obtain cellulose.

[Chemical Formula 1]

X ⁺ Y ^-

Wherein X ⁺ is an imidazolium ion, a pyridinium ion, an ammonium ion, a phosphonium ion, a sulfide ion, a pyrazolium ion, or a pyrrolidium ion; Y ^- is BF ₄ ^- , PF ₆ ^- , AlCl ₄ ^- , halogen ^- , CH ₃ CO ₂ ^- , CF ₃ CO ₂ ^- , CH ₃ SO ₄ ^- , CF ₃ SO ₃ ^- , (CF ₃ SO ₂ ) N ^- , NO ₃ ^- , SbF ₆ ^- , Sb ₂ F 11 ^- , MePhSO ₃ ^- , (CF ₃ SO ₂ ) ₂ N ^- or (CF ₃ SO ₂ ) ₃ C ^- .]

In the method for producing cellulose of the present invention, a high yield of cellulose can be obtained by destroying the chain structure of cellulose having a high crystal structure by pretreating biomass containing cellulose with radiation.

In addition, it is possible to easily extract cellulose with high yield by increasing the solubility of cellulose by dissolving the pretreated and biomass in a specific ionic liquid.

The biomass of the present invention means a raw material including cellulose, and is not limited thereto. And may be selected from among wood flour, cotton fiber, kenaf, bamboo, mulberry, cornstarch, rice straw, flax, hemp, hemp, jute and EFB Or a mixture thereof, and more preferably may be rice hull or EFB, more preferably cotton fiber, rice hull or EFB, more preferably rice hull or EFB.

The radiation of the present invention is not limited, but it may be an X-ray, a gamma ray or an electron ray, and preferably an electron ray.

The radiation dose according to one embodiment of the present invention may be 10 to 1000 KGy and preferably 25 to 700 KGy in order to produce cellulose with high purity at a high yield while lowering the concentration of byproducts other than cellulose .

The method for producing cellulose according to an embodiment of the present invention may further include a step of pulverizing the biomass raw material before the step a) in order to increase the yield of cellulose and shorten the production process of cellulose.

In the step of dissolving the biomass raw material pretreated in step a) according to an embodiment of the present invention into a specific ionic liquid, the dissolution may be performed at room temperature (15 to 35 ° C), but in order to shorten the dissolution time of the cellulose Heat can also be applied.

The ionic liquid represented by Formula 1 according to an embodiment of the present invention specifically includes 1-allyl-3-methylimidazolium chloride, 1,3-dimethylimidazolium chloride, 1-butyl- 3-methylimidazolium dicyanamide, 1-butyl-3-methylimidazolium hexafluoroantimonate, 1-butyl-3-methylimidazolium hexa Butyl-3-methylimidazolium hydrogensulfate, 1-butyl-3-methylimidazolium hydrogensulfate, 1-butyl-3-methylimidazolium methylsulfate, 1 Butyl-3-methylimidazolium tetrachloroaluminate, 1-butyl-3-methylimidazolium tetrachloroborate, 1-butyl-3-methylimidazolium thiocyanate, 1- Methylimidazolium iodide, 1-ethyl-2,3-dimethylimidazolium chloride, 1-ethyl-3-methylimidazole Methylimidazolium hexafluorophosphate, 1-ethyl-3-methylimidazolium tetrafluoroborate, 1-ethyl-3-methylimidazolium chloride, -3-methylimidazolium tetrafluoroborate, and 1-butyl-4-methylpyridinium chloride, and may be at least one selected from biomass raw materials pretreated with an electron beam, a side surface for obtaining cellulose having higher purity and yield, Lt; RTI ID = 0.0 > 1-allyl-3-methylimidazolium < / RTI > chloride.

The extraction of step c) according to an embodiment of the present invention may be water, acetonitrile or a mixture thereof, although the solvent used may be different depending on the kind of the ionic liquid used, Water is preferred in terms of obtaining a yield of cellulose.

The present invention also provides a method for producing a cellulosic polymeric antimicrobial agent by reacting cellulose contained in a biomass raw material with an ionic liquid having a specific ionic liquid, preferably a phosphite group, as an anion, A method for producing a polymeric antimicrobial agent,

A) pre-treating the biomass by irradiating the biomass feedstock with radiation;

B) adding an ionic liquid represented by the following formula (2) to the pretreated biomass to prepare a cellulosic polymeric antimicrobial agent in which an ionic liquid is grafted to cellulose in the pretreated biomass;

C) separating the prepared cellulosic polymeric antimicrobial agent.

(2)

X ⁺ Y ₁ ^-

Wherein X ⁺ is an imidazolium ion, a pyridium ion, an ammonium ion, a pyrazolium ion, or a pyrrolidium ion; Y ₁ ^- (R ₁ ) (R ₂ ) PO ₂ ^- wherein R ₁ is hydrogen, hydroxy (C ₁ -C 5) alkyl or (C 1 -C 5) R < _{2 >} is hydroxy or (C1-C5) alkoxy.

The method for producing a cellulosic polymeric antimicrobial agent of the present invention can be produced by a simple process from extracting cellulose from a raw material of biomass and producing a cellulosic polymeric antimicrobial agent and manufacturing a cellulose-based polymeric antibacterial agent from a raw material of biomass It is a very economical and efficient method.

In addition, the cellulose-based polymeric antibacterial agent prepared according to the method for producing a cellulosic polymeric antibacterial agent of the present invention has a long antimicrobial life, low residual toxicity, and high antimicrobial activity.

The cellulosic polymeric antimicrobial agent according to an embodiment of the present invention may be represented by the following general formula (3).

(3)

또는

이다.][In Formula 3, and, X ⁺ is imidazolium ion, pyridinium Stadium ion, an ammonium ion, a pyrazolium ion, or lithium ion pyrrole, Z ^_ is

or

to be.]

From the viewpoint of having an excellent antibacterial activity, X ^& lt ^{; +} > in the above formula (3) may be an imidazolium ion.

In the chemical formulas described in the present invention, n may vary depending on the dose of radiation, preferably electron beam, and may be an integer of 1 to 10000, preferably 1 to 5000. [

The separation according to one embodiment of the method for producing a cellulose-based polymeric antibacterial agent of the present invention is not limited to a solvent, but can be carried out using acetonitrile as a solvent in terms of effective separation, specifically using acetonitrile And the separation can proceed by solvent exchange with the ionic liquid used.

The ionic liquid represented by Formula 2 according to one embodiment of the method for producing a cellulosic polymeric antimicrobial agent of the present invention is preferably 1,3-dimethylimidazolium methyl-phosphite or 1-butyl- And may be 1,3-dimethylimidazolium methyl-phosphite in view of higher activity and easiness of separation, and more preferably 1,3-dimethylimidazolium methyl-phosphite.

The grafting reaction in step B) according to an embodiment of the present invention may be performed at room temperature (15 to 35 DEG C).

The biomass according to one embodiment of the method for producing a cellulosic polymeric antimicrobial agent of the present invention refers to a raw material containing cellulose and is preferably selected from the group consisting of rice hull, cotton fiber, kenaf, bamboo, mulberry, cornstarch, rice straw, , Hemp, jute and EFB, or a mixture thereof, more preferably cotton fiber, rice hull or EFB.

The present invention also provides a cellulosic polymeric antimicrobial agent prepared according to the process for producing a cellulosic polymeric antimicrobial agent of the present invention.

The cellulosic polymeric antimicrobial agent of the present invention has low pesticide residue due to high purity of cellulose, and can be produced by a simple process using only a specific ionic liquid without extra crosslinking process, and its antibacterial activity is very high.

Hereinafter, specific examples of the present invention will be described in detail, but the present invention is not limited thereto.

The cotton pulp samples used in the following Examples were obtained from KOMIPO Co., Ltd., which was produced through the selection of cotton linters.

[Example 1] Hot water and alkali extraction according to electron beam irradiation amount

50, 75, and 100 KGy at room temperature under an atmosphere of an electron beam accelerator (ELV-8 Type, EB-TECH CO., 2.5 MeV) in cotton pulp, rice husk and EFB. The conveyor speed of the electron beam accelerator was adjusted so that the irradiation amount of 25 KGy was irradiated once at a current of 23 mA at 10 m / sec. Since the electron beam pretreatment is affected by the density of the raw material, it is dispersed in a zipper bag for uniform treatment conditions. The pulp, rice husk, and EFB irradiated with electron beam were dried in the air, pulverized with a knife mill, and sifted through a sieve of 40 mesh to conduct hot water extraction and alkali extraction. Experiments were conducted according to TAPPI Standard T207 cm-99 for hot water extraction and TAPPI Standard T212 om-02 for alkali extraction. The results are shown in FIGS. 1 and 2. FIG.

As shown in FIGS. 1 and 2, it was found that the amount of cellulose extracted according to the total dose of electron beam was varied. Particularly, in the case of cotton pulp, the extraction amount was significantly low when the alkali extraction was not performed with the electron beam. It is judged that the hydroxyl radical of cellulose is generated and the extraction amount is increased.

Also is rapidly degraded in the determination of the surface of pulp is not an electron beam process cellulose is 300 ^o C, as shown in Figure 3 the thermal property changes in the surface of pulp according to the electron beam irradiation dose TGA shown in graphic, Figure 3 at 500 ^o C It was reduced to the original 16%. As the electron beam dose was gradually increased from 50 to 200 kGy, the temperature at which decomposition began was lowered, and the residual amount at 500 ^° C was also remarkably reduced by about 10%. As shown in the TGA curve, the crystallinity due to the destruction of the cellulose chain structure of cotton pulp is remarkably reduced by the electron beam irradiation treatment.

[Example 2] Solubility characteristics of cotton pulp by mechanical pulverizing treatment

In order to investigate the solubility characteristics of cotton pulp by mechanical pulverization, pulverized cotton pulp and non-pulverized cotton pulp were mixed with ionic liquid 1-allyl-3-methylimidazolium chloride (hereinafter referred to as AC) A cotton pulp dissolution experiment was conducted with dimethylimidazolium methyl-phosphite (hereinafter referred to as Me). The solubility characteristics by the mechanical cutting treatment are shown in Table 1, and it can be confirmed that the dissolution efficiency of the cotton pulp is increased by the mechanical cutting treatment.

 [Example 3] Dissolution of pretreated cotton pulp with AC

Cotton pulp was irradiated at 25, 50, 75, and 100KGy at room temperature using an electron beam accelerator (ELV-8 Type, EB-TECH CO., 2.5 MeV). The conveyor speed of the electron beam accelerator was adjusted so that the irradiation amount of 25 KGy was irradiated once at a current of 23 mA at 10 m / sec. Since the electron beam pretreatment is affected by the density of the raw material, it is dispersed in a zipper bag for uniform treatment conditions. The cotton pulp irradiated with the electron beam was dried in air, pulverized with a knife mill, and then pulverized with a sieve of 40 mesh into 0.5 g of cotton pulp dissolved in 10 g of ionic liquid AC.

The results obtained by dissolving the electron beam pre-treated cotton pulp in AC were visually evaluated as images dissolving with time. In FIG. 4, images during the dissolution progress of AC were shown according to dissolution time. As shown in FIG. 4, AC was completely dissolved in 30 minutes, and it was confirmed that there was a difference in solubility according to irradiation dose in the electron beam.

[Comparative Example 1]

The same procedure as in Example 3 was carried out except that cotton pulp not subjected to electron beam treatment was used. However, it was confirmed that cotton pulp without electron beam treatment did not dissolve even after 1 hour, It can be seen that it affects.

 [Example 4] Dissolution of pretreated cotton pulp with Me

The procedure of Example 3 was repeated except that Me was used as the ionic liquid in Example 3, and the results are shown in FIG.

As shown in FIG. 5, when the ionic liquid was used as Me, it was completely dissolved in 40 minutes, and it was confirmed that the solubility of the electron beam differs according to the irradiation dose. It was also confirmed that the dissolution rate of cotton pulp appeared faster than that of AC.

[Comparative Example 2]

The same procedure as in Example 3 was carried out except that cotton pulp not subjected to electron beam treatment was used. However, it was confirmed that cotton pulp without electron beam treatment did not dissolve even after 1 hour, It can be seen that it affects.

 [Example 5] Dissolution of pretreated rice hull by AC

Example 3 was carried out in the same manner as in Example 3, except that 5 g of rice hull was irradiated at an irradiation dose of 100, 200, 300, 500, 700 KGy in Example 3, and 495 g of ionic liquid AC was dissolved. Respectively.

As shown in FIG. 6, the solubility was varied according to the irradiation dose (100 Kgy to 700 Kgy), and it was confirmed that the solubility was completely dissolved after 3 to 24 hours.

[Comparative Example 3]

The same procedure as in Example 5 was carried out except that the rice husk without the electron beam treatment was used. However, it was confirmed that the rice husk without electron beam treatment did not dissolve even after 24 hours, and the electron beam treatment greatly affected the solubility of the rice husk .

 [Example 6] Dissolving with Me of the rice husk pretreated

The procedure of Example 5 was repeated except that Me was used as an ionic liquid. The results are shown in FIG.

As shown in FIG. 8, the solubility was varied according to the irradiation dose (100 Kgy to 700 Kgy), and it was confirmed that it was completely dissolved after 3 to 24 hours.

[Comparative Example 4]

It was confirmed that the rice husk without electron beam treatment did not dissolve even after 24 hours, and that the electron beam treatment significantly affected the solubility of rice husk .

[Example 7] Dissolution of pretreated EFB in AC

The same procedure as in Example 5 was carried out except that the electron beam-treated EFB was used, and the results are shown in Fig.

As shown in FIG. 8, the solubility was varied according to the irradiation dose (100 Kgy to 700 Kgy), and it was confirmed that it was completely dissolved after 3 to 24 hours.

[Comparative Example 5]

The same procedure was performed as in Example 7 except that EFB not subjected to electron beam treatment was used. However, it was confirmed that the rice husk without electron beam treatment did not dissolve even after 24 hours, and the electron beam treatment significantly affected the solubility of rice husk .

[Example 8] Melting of pretreated EFB in Me

The same procedure as in Example 5 was carried out except that E-beam treated EFB was used instead of Ac as Me. The results are shown in FIG.

As shown in FIG. 9, the solubility was varied according to the irradiation dose (100 Kgy to 700 Kgy), and it was confirmed that it was completely dissolved after 3 to 24 hours.

[Comparative Example 6]

EFB without electron beam treatment was used in the same manner as in Example 8 except that the electron beam treatment did not dissolve even after 24 hours and the electron beam treatment had a large effect on the solubility of EFB .

[Example 9] Method for producing cellulose from cotton pulp using AC

A solution was prepared by dissolving 1.5 g of cotton pulp in 10 g of ionic liquid AC and 50 kGy and 100 KGy electron beam treatment samples, respectively, and the solvent was exchanged with ionic liquid by addition of distilled water. Cellulose was precipitated by adding 10 ml of distilled water to each vial containing ionic liquid, and the supernatant was separated and then 10 g of distilled water was further applied three times to remove residual ionic liquid to obtain cellulose.

[Example 10] Method for producing cellulose-based polymer antibacterial agent using Me from cotton pulp

A cellulosic polymeric antimicrobial agent obtained in the same manner as in Example 9, except that Me was used instead of AC as an ionic liquid in Example 9, and acetonitrile was used in place of distilled water, is shown in Fig.

The TGA graph of the cellulose-based polymer antibacterial agent precipitated in FIG. 11 is also shown.

FIG cellulose as shown in 11 (Microcrystalline Cellulose: MCC) and the surface of pulp is 300 ^o C and is rapidly decomposed in the vicinity of 350 ^o C was originally cellulose is not left out of 0 to 12% by weight of at 600 ^o C. On the other hand, the cellulosic polymeric antimicrobial agent precipitated from the cotton pulp dissolved by Me began to remarkably decompose in the vicinity of 250 ^° C, but the decomposition amount like MCC was not large. It can also be seen that the amount of decomposition is increased according to the amount of electron beam irradiation. This fact is considered to be due to the decrease in crystallinity of cellulose.

As shown in FIG. 12 a, the reproduced cellulose is a ¹³ C NMR spectrum measured by DMSO-d ₆ . Once an phosphite groups are bonded to the regenerated cellulose ¹³ C NMR spectrum, but can be seen only as indicated in the ¹³ C NMR spectrum of 12 b) it is also measured in D ₂ O as well as a peak at 62.3 ppm (6) 64.3 ppm ( 6 '), it is clear that the hydroxyl group substitution was carried out in C6. This result is the same as the ¹³ C spectral result of cellulose recovered by dissolving in MCC (microcrystalline powder) in Me [HT Vo, YJ Kim, EH Jeon, CS Kim, HS Kim, and H. Lee, Chem. Eur. J. 2012, 18, 9019-9023]. The results show that the hydroxyl group of the glucose unit is substituted by the interaction with methylphosphite cations of [Dmim] [(MeO) (H) PO ₂ ] as shown in the following reaction formula 2, and methanol is removed to obtain dimethyl imidazolium cellulose Fight is generated.

[Reaction Scheme 2]

As shown in FIG. 13, the FT-IR spectrum of cellulose and phosphated cellulose (cellulosic polymeric antimicrobial agent) was measured. Phosphorylated cellulose, dissolved in ionic liquid Me, showed a new absorption band at 2356 and 1576 cm ^-1 irrespective of the electron beam dose, indicating that both the PH stretching vibration of the phosphite and the C = N stretching of the imidazolium ring Vibration. It can be seen that the phosphorylated cellulose was formed.

      [Example 11] Method for producing cellulose-based polymeric antibacterial agent using Me from rice hulls

A solution prepared by dissolving 0.5 g of rice husk and 200 KGy electron beam in 49.5 g of ionic liquid Me was prepared and distilled water was added to perform solvent exchange with ionic liquid. Each of the vials containing the ionic liquid was charged with 200 ml of acetonitrile, and the precipitated substance was filtered. The filtered substance (upper layer) was subjected to Soxhlet extraction using acetone to precipitate a substance as shown in Fig. In addition, 200 ml of acetonitrile was added to 50 g of the translucent gel-like substance which had been settled over time, and the filtrate was stirred to produce a precipitate. After filtration, the filtered substance (lower layer) was subjected to Soxhlet extraction 15 was precipitated. As shown in FIGS. 14 and 15, TGA analysis was performed on the deposited material under conditions of 25 to 900.degree. C., 10.degree. C./minute and nitrogen atmosphere, and the results are shown in FIG. As a result of TGA analysis, the mineral content was 25.48% at the lower layer and 23.88% at the upper layer at 900 ℃. These results show that there is no significant difference in the composition of the upper and lower layers, but the relatively higher content of the lower layer is due to the lower solubility of the inorganic materials. As a result of EDAX analysis, it was confirmed that the Si component appeared as shown in Tables 14 and 15. The TGA analysis showed that the inorganic matter was silica, which was already known as a component of rice hulls.

[Example 12] Evaluation of antibacterial activity of cellulosic polymeric antimicrobial agent

The antibacterial activity of the cellulosic polymeric antibacterial agent prepared in Example 10 was evaluated by shaking flask method (KS J 4206: 2008). Staphylococcus (Gram-positive bacteria) (strain 1) and Escherichia coli (Gram-negative bacteria) (strain 2) were used for the test. All specimens of antimicrobial agents inoculated with Staphylococcus aureus ATCC 6538 and Escherichia coli ATCC 25922 at a sample concentration of 0.5% showed antimicrobial activity. As shown in Table 2 below, the number of viable microorganisms in the test piece after shaking culture (shaking count 120 times / minute) at 37 占 1 占 폚 for 24 hours was 99.9% or more, There was no reduction ratio in the case of non - existence of polymeric antimicrobial agent, blank).

16 shows an image of the antibacterial test result of Example 12 of the present invention.

 As shown in Table 2 and FIG. 16, the cellulosic polymeric antibacterial agent of the present invention shows high activity.

Claims (10)

a) pre-treating the biomass by irradiating the biomass feedstock with radiation;
b) dissolving the pretreated biomass in the ionic liquid of Formula 1;
c) extracting the cellulose from the biomass dissolved in the ionic liquid to obtain cellulose.
[Chemical Formula 1]
X ⁺ Y ^-
Wherein X ⁺ is an imidazolium ion, a pyridinium ion, an ammonium ion, a phosphonium ion, a sulfide ion, a pyrazolium ion, or a pyrrolidium ion; Y ^- is BF ₄ ^- , PF ₆ ^- , AlCl ₄ ^- , halogen ^- , CH ₃ CO ₂ ^- , CF ₃ CO ₂ ^- , CH ₃ SO ₄ ^- , CF ₃ SO ₃ ^- , (CF ₃ SO ₂ ) N ^- , NO ₃ ^- , SbF ₆ ^- , Sb ₂ F 11 ^- , MePhSO ₃ ^- , (CF ₃ SO ₂ ) ₂ N ^- or (CF ₃ SO ₂ ) ₃ C ^- .] The method according to claim 1,
Wherein the biomass raw material is one or a mixture thereof selected from rice hull, cotton fiber, kenaf, bamboo, mulberry, cornstarch, rice straw, flax, persimmon, hemp, jute and EFB. The method according to claim 1,
Wherein the radiation has a total dose of 10 to 1000 KGy. The method according to claim 1,
The ionic liquid may be selected from the group consisting of 1-allyl-3-methylimidazolium chloride, 1,3-dimethylimidazolium chloride, 1-butyl- 1-butyl-3-methylimidazolium hexafluoroantimonate, 1-butyl-3-methylimidazolium hexafluorophosphate, 1-butyl- Butyl-3-methylimidazolium hydrogensulfate, 1-butyl-3-methylimidazolium methylsulfate, 1-butyl-3-methylimidazolium tetrachloroaluminate Butylimidazolium iodide, 1-butyl-3-methylimidazolium tetrachloroborate, 1-butyl-3-methylimidazolium thiocyanate, Methylimidazolium bromide, 1-ethyl-3-methylimidazolium chloride, 1-ethyl-3-methylimidazolium chloride, Methylimidazolium hexafluorophosphate, 1-ethyl-3-methylimidazolium tetrafluoroborate, 1-hexyl-3-methylimidazolium tetrafluoroborate and 1-butyl- Pyridinium chloride. ≪ RTI ID = 0.0 > 21. < / RTI > The method according to claim 1,
Wherein the extraction in step c) is carried out with water, acetonitrile or a mixture thereof. A) pre-treating the biomass by irradiating the biomass feedstock with radiation;
B) adding an ionic liquid represented by the following formula (2) to the pretreated biomass to prepare a cellulosic polymeric antimicrobial agent obtained by grafting the ionic liquid onto cellulose in the pretreated biomass;
C) separating the cellulose-based high molecular weight antimicrobial agent.
(2)
X ⁺ Y ₁ ^-
Wherein X ⁺ is an imidazolium ion, a pyridium ion, an ammonium ion, a pyrazolium ion, or a pyrrolidium ion; Y ₁ ^- (R ₁ ) (R ₂ ) PO ₂ ^- wherein R ₁ is hydrogen, hydroxy (C ₁ -C 5) alkyl or (C 1 -C 5) R < _{2 >} is hydroxy or (C1-C5) alkoxy. The method according to claim 6,
Wherein the separation is carried out using acetonitrile as a solvent. The method according to claim 6,
Wherein the ionic liquid is 1,3-dimethylimidazolium methyl-phosphite or 1-butyl-3-methylimidazolium dibutyl phosphate. The method according to claim 6,
Wherein the biomass raw material is one or a mixture thereof selected from rice hull, cotton fiber, kenaf, bamboo, mulberry, cornstarch, rice straw, flax, jasmine, hemp, jute and EFB. A cellulosic polymeric antimicrobial agent produced according to any one of claims 6 to 9.

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