KR20160126272A - Polymer for evaluation method of biodegradation and evaluation method of biodegradation using the same - Google Patents

Polymer for evaluation method of biodegradation and evaluation method of biodegradation using the same Download PDF

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KR20160126272A
KR20160126272A KR1020150057146A KR20150057146A KR20160126272A KR 20160126272 A KR20160126272 A KR 20160126272A KR 1020150057146 A KR1020150057146 A KR 1020150057146A KR 20150057146 A KR20150057146 A KR 20150057146A KR 20160126272 A KR20160126272 A KR 20160126272A
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standard specimen
biodegradability
biodegradable polymer
specimen
evaluation method
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이재춘
김보미
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(주) 웹스
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/44Resins; Plastics; Rubber; Leather
    • G01N33/442Resins; Plastics
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02Column chromatography
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/0004Gaseous mixtures, e.g. polluted air
    • G01N33/0009General constructional details of gas analysers, e.g. portable test equipment
    • G01N33/0027General constructional details of gas analysers, e.g. portable test equipment concerning the detector
    • G01N33/0036General constructional details of gas analysers, e.g. portable test equipment concerning the detector specially adapted to detect a particular component
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/0004Gaseous mixtures, e.g. polluted air
    • G01N33/0009General constructional details of gas analysers, e.g. portable test equipment
    • G01N33/0027General constructional details of gas analysers, e.g. portable test equipment concerning the detector
    • G01N33/0036General constructional details of gas analysers, e.g. portable test equipment concerning the detector specially adapted to detect a particular component
    • G01N33/004CO or CO2

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Abstract

The present invention relates to a polymer specimen for evaluating biodegradability and a method for evaluating biodegradability using the specimen. More particularly, the present invention relates to a standard specimen for standardization of various biodegradability evaluation methods, And a method for evaluating biodegradability using the same. BACKGROUND OF THE INVENTION 1. Field of the Invention [0002] The present invention relates to a biodegradability evaluation method,
In the standardization of the biodegradability evaluation method according to the present invention, the degree of biodegradation is evaluated by using a biodegradability evaluation method for measuring the change of the biodegradable polymer standard specimen, wherein the biodegradable polymer standard specimen includes the planar porosity . In addition, the size of the biodegradable polymer standard specimen is standardized.
The biodegradability evaluation method comprises measuring the gas generation rate of a gas generated after biodegrading the biodegradable polymer standard specimen with a microorganism, measuring the surface area of the biodegradable polymer standard specimen, and the biodegradability Calculate the rate of gas generation per unit area of the polymer standard specimen, and compare them to make a comparison.
In addition, the biodegradability evaluation method is characterized in that the biodegradable polymer standard specimen is placed on a soil, and the change in molecular weight is measured through gel permeation chromatography (GPC) analysis, and then indexed and compared.
In addition, the biodegradable polymer standard specimen is biodegraded in a solution having a different hydrogen ion concentration index (pH), and then the difference in weight change is measured, and then indexed and compared.

Description

TECHNICAL FIELD The present invention relates to a biodegradation evaluation method and a biodegradation evaluation method using the same,

The present invention relates to a polymer specimen for evaluating biodegradability and a method for evaluating biodegradability using the specimen. More particularly, the present invention relates to a standard specimen for standardization of various biodegradability evaluation methods, And a method for evaluating biodegradability using the same. BACKGROUND OF THE INVENTION 1. Field of the Invention [0002] The present invention relates to a biodegradability evaluation method,

Recently, environmental pollution has become a serious social problem both domestically and globally. Plastic materials have made a great contribution to the abundant daily life and industrial development, while various kinds of waste vinyl and waste plastics, which are released in large quantities according to the use of plastics, have become one of the main causes of environmental pollution. Environmental hormones generated by incineration or landfill of waste plastic and waste plastics, dioxins that are highly toxic, and air pollution caused by incomplete combustion of wastes cause serious environmental pollution.

Recently, since the problem of environmental pollution caused by the waste plastic has become a big problem in recent years, the environment-friendly biodegradable plastic resin, which is decomposed by microorganisms in the soil, have. Generally, "biodegradable" means the ability of a compound to be completely degraded into biological resources such as methane, carbon dioxide and water or inorganic salts by microorganisms and / or natural environmental factors. In order to protect the global environment, various international environmental conventions in various fields are being continuously implemented and implemented. In addition to the strengthening of environmental regulations, consumer awareness about chemical products and various consumer products has changed. Efforts are continuing. Already in developed countries such as Germany, Italy and the United States, it is obligatory to use biodegradable resins for shopping bags and plastic bottles.

In order to study and use biodegradable polymers, biodegradability measurement method and biodegradation criteria should be prioritized. However, in spite of the research on biodegradable polymers and the rapid increase of products made of biodegradable polymer compounds and the expansion of the market, a standardization work has been carried out to make the biodegradability of the biodegradable polymer compounds fast, quantitative and reproducible It is not.

The biodegradability of biodegradable polymer materials has been studied in the United States and Japan as a standardized method. However, in the United States, abandoned polymeric materials have a tendency to be biodegradable due to landfill There is a problem that it is difficult to evaluate the biodegradability quantitatively in a reproducible manner and there is a problem that the measurement time is very long. In addition, the biodegradation process based on the existing KSM 3100-1 is a biodegradation measurement method which is performed for at least 45 to 180 days at a temperature of 58 ° C and a humidity of 50%. In addition, the evaluation cost is very high, There is a limitation in research on efficient biodegradable polymers.

Korean Patent Publication No. 10-2012-0048405

SUMMARY OF THE INVENTION The present invention has been made in order to solve the above problems, and it is an object of the present invention to select standard specimens to be standard for standardizing and comparing various biodegradability evaluation methods, and to carry out the test method accordingly.

It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory and are not restrictive of the invention as set forth in the accompanying drawings. It will be possible.

In the standardization of the biodegradability evaluation method according to the present invention, the degree of biodegradation is evaluated by using a biodegradability evaluation method for measuring the change of the biodegradable polymer standard specimen, wherein the biodegradable polymer standard specimen includes the planar porosity . In addition, the size of the biodegradable polymer standard specimen is standardized.

The biodegradability evaluation method comprises measuring the gas generation rate of a gas generated after biodegrading the biodegradable polymer standard specimen with a microorganism, measuring the surface area of the biodegradable polymer standard specimen, and the biodegradability Calculate the rate of gas generation per unit area of the polymer standard specimen, and compare them to make a comparison.

In addition, the biodegradability evaluation method is characterized in that the biodegradable polymer standard specimen is placed on a soil, and the change in molecular weight is measured through gel permeation chromatography (GPC) analysis, and then indexed and compared.

In addition, the biodegradable polymer standard specimen is biodegraded in a solution having a different hydrogen ion concentration index (pH), and then the difference in weight change is measured, and then indexed and compared.

According to the solution of the above-mentioned problems, the standardization of the biodegradability test method of the present invention has the effect of standardizing a variety of biodegradability evaluation methods by producing reference standard specimens.

In addition, various biodegradability evaluation methods can be compared and standardized and analyzed.

1 is a perspective view showing a standard specimen produced according to the present invention;
Fig. 2 is a photograph showing the state of a standard specimen on a culture soil in a biodegradability test method using soil at a certain temperature
3 is a flowchart showing a test method of biodegradation using microorganisms using a standard specimen

The above and other objects, features and advantages of the present invention will be more apparent from the following detailed description taken in conjunction with the accompanying drawings, in which: FIG. BRIEF DESCRIPTION OF THE DRAWINGS The advantages and features of the present invention and the manner of achieving them will become apparent by reference to an embodiment which will be described in detail below with reference to the accompanying drawings.

The present invention relates to a method for evaluating biodegradability using standard specimens, more particularly, to select standard specimens for standardization of various biodegradability evaluation methods, And a method of evaluating biodegradability using a standard sample that standardizes the method so as to be comparable.

The standard specimen using the biodegradability evaluation method is prepared by including a flat surface porosity and its size being standardized. Specifically, the porosity is to maximize the surface area of the standard specimen, and the biodegradability evaluation reaction, which will be described later, is promoted through the maximized surface area, thereby increasing the efficiency of biodegradation measurement. Therefore, when the conventional biodegradability evaluation method was used, it took more than two years to evaluate the biodegradability of polylactic acid (PLA), which has the longest decomposition period of the biodegradable resin. However, The biodegradability test allows the evaluation method to be carried out with a period of time suitable for use in the actual industry.

Further, the standard specimen is characterized by being manufactured in a standardized flat surface. The standard specimen is provided in a standardized planar shape and it is easy to evaluate the degree of biodegradability.

Specifically, in the method for evaluating biodegradability by biodegradation as a microorganism among the biodegradability assessment methods of the present invention, the standard specimen is provided on a standardized flat surface, and it is easy to compare the surface area difference after biodegradation to facilitate indexing.

In the biodegradability evaluation method using the soil at a certain temperature among the biodegradability evaluation methods of the present invention, as shown in FIG. 2, the standard specimen is provided on a standardized flat surface, It is easy to measure the change of the molecular weight and to make the index.

In addition, a method for measuring a difference in weight change after biodegradation in a solution having a different hydrogen ion concentration index (pH) among the biodegradability assessment methods according to the present invention is characterized in that the standard specimen is provided on a standardized plane, And it is easy to measure the difference of weight change after biodegradation and to index it.

The volume and surface area of the standard specimen prepared in the present invention can be confirmed through FIG. 1 and the following examples.

Specimen Type Comparative Example 1 Example 1 Example 2 weight 8.370g 6.147 g 6.123 g Surface area 5.190㎠ 6.064 cm 2 6.080㎠

[Comparative Example 1]

In Comparative Example 1, polylactic acid (PLA) having the longest degradation rate was used as biodegradable resin, and 3001D grade of naturewokrs Co. was used. When the specimen was prepared with the polylactic acid (PLA) weighing 8.370 g, the surface area of the specimen was measured as 5.190 cm < 2 >.

[Example 1]

In Example 1, the same polylactic acid (PLA) as that of Comparative Example 1 was used and a standardized flat standard specimen having porosity was prepared.

As shown in FIG. 1, the standard specimen has a size of 90 mm X 25 mm (width X length) and the standard specimen has a diameter of 5 mm so as to have porosity.

When manufactured to the above standard, the surface area of the standard specimen is measured as 6.064 cm < 2 >.

[Example 2]

In Example 2, the same polylactic acid (PLA) as that in Comparative Example 1 was used, and a standard specimen having a porous structure was prepared.

As shown in FIG. 1, the standard specimen has a size of 90 mm X 25 mm (width X length) and the inside of the standard specimen has a diameter of 3 mm to have porosity.

When manufactured to the above standard, the surface area of the standard specimen is measured to be 6.080 cm < 2 >.

The biodegradability of the biodegradable resin can be measured, compared, and indexed by the following biodegradability test method using the standard specimen prepared through the above examples.

(1) Biodegradability test method using soil at a certain temperature

The biodegradability test method using the soil at the above-described temperature is characterized in that the biodegradable polymer standard specimen is placed on a soil and then the change of the molecular weight is measured by gel permeation chromatography (GPC) analysis, and then indexed and compared .

First, the molecular weight of the standard specimen prepared according to the present invention is measured, and the standard specimen of the present invention is buried in the culture soil of the thermo-hygrostat according to the conditions of Table 2.

58 ℃ condition Room temperature condition Temperature 58 ± 2 ° C 25 ± 2 ° C Culture soil component Bark, perlite, peat moss, vermiculite Bark, perlite, peat moss, vermiculite Content water content 40 ~ 60wt (%) 40 ~ 60wt (%) pH 7.0 to 9.0 7.0 to 9.0

Concretely, in the constant temperature and humidity bath having the conditions of pH of 7.0 to 9.0, temperature of 56 to 60 ° C and water content of 40 to 60 wt%, the culture soil was at least one of bark, perlite, peat moss and vermiculite ≪ / RTI >

In addition, the biodegradability test method using the soil is performed by checking the degree of biodegradation at room temperature, so that the reproducibility of the test method is obtained. As shown in Table 2, at the room temperature condition, the pH was 7.0 to 9.0, the temperature was 23 to 27 ° C, and the moisture content was 40 to 60 wt%. In the constant temperature and humidity bath, the culture soil was bark, perlite, peatmoss, vermiculite And at least one of the components.

Next, the standard specimen of the present invention is arranged as shown in Fig. Specifically, seven standard specimens are placed on the culture soil of the constant temperature and humidity bath to prepare experimental conditions.

Next, the standard specimen on the culture soil of the constant temperature and humidity bath is recovered and the molecular weight is measured by gel permeation chromatography (GPC) analysis. In the present invention, the biodegradability is standardized by measuring the molecular weight of the above-mentioned standard specimen by the Korea Polymer Research Institute. The gel permeation chromatography (GPC) analysis environment is shown in Table 3 below.

Measuring instrument Waters GPC system Pump Waters 515 Detector Waters 410 Differential Refractometer menstruum CHCl 3 Column (maker, model no.) 2 X Shodex LF-804 (7.8 X 300 nm) Temperature 35 ℃ Flow rate 1.0 ml / min Main adoption 100 μL Standard sample Polystyrene

(2) Biodegradability test method using hydrolysis promotion

The biodegradability test method using the hydrolysis promotion is characterized in that the biodegradable polymer standard specimen is biodegraded in a solution having a different hydrogen ion concentration index (pH), then the difference in weight change is measured, and the biodegradable polymer standard specimen is indexed and compared .

First, the weight of a standard specimen prepared according to the present invention is measured, and a buffer solution is prepared according to the conditions shown in Table 4.

pH Buffer solution preparation conditions 2 KH 2 PO 4 75.6 g + H 3 PO 4 60 mL 7 KH 2 PO 4 6.6 g + NaHPO 4 · 12H 2 O 30 g 12 NaHPO 4 192 g + NaOH 18.35 g

As shown in Table 4, the buffer solution of pH 2 is prepared by mixing 75.6 g of calcium phosphate (KH 2 PO 4 ) and 60 mL of phosphoric acid (H 3 PO 4 ). The buffer solution of pH 7 is prepared by mixing 6.6 g of potassium phosphate (KH 2 PO 4) and 30 g of phosphate hydrate (NaHPO 4 .12H 2 O). The buffer solution of pH 12 is prepared by mixing 192 g of phosphate (NaHPO 4 ) and 18.35 g of sodium chloride (NaOH).

Next, the buffer solution of pH 2, pH 7, and pH 12 is dissolved in distilled water to prepare a 1 L solution, and then the standard specimen prepared according to the present invention is placed in the solution. Specifically, the dissolved buffer solution is maintained at 37 ° C. and two buffer solutions of pH 2, pH 7, and pH 12 are prepared in order to improve the accuracy and reproducibility of the experiment.

Next, the standard specimens reacted in the buffer solution are taken out at intervals of 7 days, weighted and measured for reduction, and standardized. The result of the weight reduction amount takes an average value.

(3) Biodegradability test method using microorganisms

As shown in FIG. 3, the biodegradability test method using the microorganism is a method of measuring the rate of gas evolution of the biodegradable polymer standard specimen after biodegradation of the biodegradable polymer standard specimen into microorganisms, measuring the surface area of the biodegradable polymer standard specimen The gas generation rate per unit area of the biodegradable polymer standard specimen is calculated using the gas generation rate, and then indexed for comparison.

In addition, it is preferable that the gas generation rate is a gas generation rate of carbon dioxide (CO 2 ) under an aerobic condition and a gas generation rate of methane (CH 4 ) in an anaerobic condition.

Specifically, the gas generation rate per unit area of the reference sample, which is indexed in the biodegradation evaluation method using the microorganism, is defined by the following equation (1).

Figure pat00001

Hereinafter, a method for evaluating biodegradability using the microorganisms will be described in detail with reference to the drawings.

3 is a flowchart showing a flow of a method for evaluating biodegradability using microorganisms according to the present invention.

First, in a first step (S10), the standard specimen is introduced into a closed flask, and a culture medium for culture and an anaerobic sludge are introduced into the closed flask.

Specifically, 0.1 parts by weight of the anaerobic sludge was added to 1 part by weight of the microbial culture medium prepared according to the conditions of Table 5, after putting the standard specimen into a 500 mL closed flask.

ingredient content H 2 O ~ 1000mL NH 2 Cl 0.31 g NaH 2 PO 4 · H 2 O 2.69 g NaH 2 PO 4 4.33g KCl 0.31 g Minerals 12.5 mL Vitamins 12.5 mL Acetate 40 mL

As shown in Table 5, the microorganism culture medium was prepared by adding chloramine (NH 2 Cl), sodium monophosphate (NaH 2 PO 4 .H 2 O), sodium hydrogen phosphate (Na 2 HPO 4 ), potassium chloride KCl), vitamins and minerals, and the acetate is added to the initial microorganism growth substrate and the pH is titrated to neutral (pH 7.0) suitable for microbial growth.

The chemical composition of the microorganism culture medium can be adjusted depending on the inoculum, and the pH can be adjusted to a pH of 6.5 to 7.5 suitable for general microbial growth and metabolism.

In addition, the anaerobic sludge uses sludge that has been filtered by removing impurities from sewage sludge. The anaerobic sludge is used as a microorganism inoculation source containing various microorganisms at a high concentration and can be replaced with a mixed microorganism including pure microorganisms or anaerobic sludge. In the present invention, it was collected after being harvested from the sewage treatment plant of Haeundae-gu.

The amount of the microorganism culture medium and anaerobic sludge is adjusted according to the amount of the analytical sample.

Next, in the second step S20, the flask is closed and incubated in a thermostatic stirrer. Specifically, the standard specimen, the microorganism culture medium, and the flask containing the anaerobic sludge are sealed and fixed by a constant temperature stirrer.

The microorganisms of the microorganism culture medium and the anaerobic sludge are adhered to the surface of the particle of the biodegradable polymer standard specimen and cultured under microbial culture conditions using a constant temperature stirrer.

The stirrer may be replaced with a magnetic stirrer or a constant temperature water chamber.

The culturing conditions are incubated at a temperature of 20 to 50 DEG C and a rotation speed of 100 to 200 rpm, which is suitable for microbial growth. Optimal culture conditions using the above-mentioned constant temperature stirrer are most preferably incubated at a rotation speed of 160 rpm at 37 캜.

Through the above cultivation, microorganisms adhere to the surface of the biodegradable polymer standard specimen to initiate decomposition activity, and metabolism activities such as hydrolysis of polymer, generation of organic acid, and final gas production are performed through the metabolism of microorganisms.

In the second step (S20), the anaerobic condition is filled with nitrogen (N 2 ) to remove oxygen. Specifically, when analysis is performed under anaerobic conditions, the flask containing the analytical sample, the microbial culture medium, and the anaerobic sludge is purged with nitrogen (N 2 ) to remove oxygen, and the stopper is closed and sealed in a thermostatic stirrer Start culturing.

Next, in a third step (S30), the gas in the flask is sampled with a gas sample syringe, and the amount of produced gas is measured by analyzing the composition of the gas phase. Specifically, after the gas in the flask is sampled with a gas sample syringe while being cultured under the above conditions, the gas phase composition is analyzed by gas chromatography or the like to analyze carbon dioxide (CO 2 ) or methane (CH 4 ) produced in the gas phase Measure production.

The gas end products of the polymer through the mineralization in the aerobic condition is measured, and oxygen are abundantly supplied to the final degradation products of carbon dioxide (C0 2) or methane (CH 4) of the biodegradable polymer standard specimen is carbon dioxide (C0 2 ) Is measured, and it is preferable to measure it on the basis of methane (CH 4 ) under oxygen-poor anaerobic conditions.

The gas chromatography can be replaced with various analyzers capable of detecting the gas components of the carbon dioxide (CO 2 ) and methane (CH 4 ), such as a gas detector and a detector for measuring the final decomposition product of the biodegradable polymer standard specimen Do.

Next, in a fourth step S40, the specific surface area of the standard specimen and the gas generation rate are used to calculate the gas generation rate per specific surface area. Specifically, the gas generation rate per non-surface area is calculated in consideration of the specific surface area and time according to the standard specimen.

Next, in the fifth step (S50), the degree of biodegradation is evaluated using the gas generation rate per non-surface area. Specifically, the calculated rate of gas generation per surface area is indexed to evaluate the degree of biodegradation.

The standardization of the biodegradability test method according to the present invention standardizes the existing biodegradability assessment method which does not have a standard. Specimens are standardized for clear comparison of various test methods, and standardization of the surface area and volume of the standardized specimens enables comparison between biodegradation test methods.

As described above, it is to be understood that the technical structure of the present invention can be embodied in other specific forms without departing from the spirit and essential characteristics of the present invention.

Therefore, it should be understood that the above-described embodiments are to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than the foregoing description, All changes or modifications that come within the scope of the equivalent concept are to be construed as being included within the scope of the present invention.

S10. A first step of putting the standard specimen into a closed flask, and a microbial culture medium and anaerobic sludge are introduced into the closed flask
S20. A second step of incubating the flask in a sealed incubator,
S30. A third step of measuring the amount of gas produced by analyzing the composition of the gas phase after collecting the gas in the flask with a gas sample syringe,
S40. A fourth step of calculating the gas generation rate per non-surface area using the specific surface area of the standard specimen and the gas generation amount,
S50. A fifth step of evaluating the degree of biodegradation using the gas generation rate per non-surface area

Claims (6)

The degree of biodegradation is evaluated using the biodegradability evaluation method for measuring the change of the biodegradable polymer standard specimen,
Wherein the biodegradable polymer standard specimen includes planar porosity, and a biodegradability evaluation method using the standard specimen for biodegradability evaluation
The method according to claim 1,
The biodegradable polymer standard specimen is a standard specimen for biodegradability evaluation, characterized in that the size of the specimen is standardized, and a biodegradability evaluation method using the standard specimen
The method according to claim 1,
The biodegradation degree evaluation method includes:
The biodegradable polymer standard specimen is biodegraded as a microorganism, and the gas generation rate of the generated gas is measured.
Wherein the gas generating rate of the biodegradable polymer standard specimen is calculated using the measured surface area of the biodegradable polymer standard specimen and the gas generation rate, Specimen and method for evaluating biodegradability using the same
The method of claim 3,
Wherein the gas generation rate is a gas generation rate of carbon dioxide (CO 2 ) in an aerobic condition and a gas generation rate of methane (CH 4 ) in an anaerobic condition, and Biodegradability assessment method
The method according to claim 1,
The biodegradation degree evaluation method includes:
The biodegradable polymer standard specimens are immersed in soil, and the change in molecular weight is measured by gel permeation chromatography (GPC) analysis. The standard molecular weight of the biodegradable polymer specimen is compared with the standard molecular weight of the biodegradable polymer standard specimen. Assessment Methods
The method according to claim 1,
The biodegradation degree evaluation method includes:
The biodegradable polymer standard specimen is biodegraded in a solution having a different pH value, and then the difference in weight change is measured, and the biodegradable polymer standard specimen is indexed and compared for comparison. Rating Method
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Cited By (1)

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Publication number Priority date Publication date Assignee Title
KR20190031863A (en) * 2017-09-18 2019-03-27 주식회사 엘지화학 Apparatus and method for detacting properties of soil

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* Cited by examiner, † Cited by third party
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KR20120048405A (en) 2010-11-05 2012-05-15 채명해 Shredder

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20120048405A (en) 2010-11-05 2012-05-15 채명해 Shredder

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20190031863A (en) * 2017-09-18 2019-03-27 주식회사 엘지화학 Apparatus and method for detacting properties of soil

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