CN113671058B - Method for evaluating degradation performance of high polymer material - Google Patents
Method for evaluating degradation performance of high polymer material Download PDFInfo
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- CN113671058B CN113671058B CN202010411993.7A CN202010411993A CN113671058B CN 113671058 B CN113671058 B CN 113671058B CN 202010411993 A CN202010411993 A CN 202010411993A CN 113671058 B CN113671058 B CN 113671058B
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/96—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation using ion-exchange
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Abstract
The invention discloses a method for evaluating degradation performance of a high polymer material, which comprises the following steps: (1) Providing a high molecular material sample to be evaluated, and measuring the initial molecular weight and the initial weight of the high molecular material sample; (2) Placing a high polymer material sample in a preset environment for degradation for a preset time; (3) Molecular weight change and weight change after the degradation of the high molecular material sample are detected, and total organic carbon content change in the degradation process is detected; (4) Judging whether the molecular weight change, the weight change and the total organic carbon content change in the degradation process are larger than respective preset thresholds according to a designated sequence, and giving a degradation performance evaluation conclusion based on the judgment result. The evaluation method provided by the invention can distinguish biodegradation from non-enzymatic hydrolysis, dissolution and the like in the simplest steps, and the degradation performance obtained by evaluation is related to the actual test environment.
Description
Technical Field
The invention relates to a method for evaluating material performance, in particular to a method for evaluating degradation performance of a high polymer material in a preset environment.
Background
The degradation of the polymer material is classified into photodegradation, oxidative degradation, hydrolysis, biodegradation, and the like according to a degradation mechanism. The biodegradation is the most interesting and widely used degradation mode, and the degradation mode refers to that plastics are finally mineralized to form environmental pollution-free carbon dioxide and water under the action of environmental microorganisms, and usually, a core evaluation standard is formed by finally generating carbon dioxide in a medium by using a high polymer material, and the carbon dioxide released by the high polymer material in the degradation process is judged by using a respirometer and other instruments.
Under the combined action of the structural performance of the polymer material and environmental factors, the degradation difference of the polymer material in the same environment is huge, and the same polymer material may show different degradation performances in different environments. However, the degradation performance concept of the polymer material at home and abroad is fuzzy at present, the evaluation method is not sound enough, the degradation evaluation standard is not unified enough, some photodegradable polymer materials, hydrolytic polymer materials and even water-soluble polymer materials are often mixed with the biodegradable polymer materials together, and the actual degradation environment cannot be connected when the degradation performance conclusion of the polymer material is given.
Particularly in marine environments, because the marine environments have differences in temperature and microorganisms from the composting environments and the soil environments with more researches, the degradation performance of the high polymer materials in the marine environments is changed much compared with other environments, and some traditional biodegradable materials such as PLA and the like cannot be degraded quickly in seawater, so that a new evaluation method and standard are needed to be provided for the degradation performance of the high polymer materials in the marine special environments.
The existing evaluation standard for degradation performance of a polymer material in a marine special environment, such as ASTM D7081-05, gives a standard specification for biodegradable plastics in a marine environment (whether the polymer material is biodegradable or not is judged by observing whether the material is decomposed, carbon dioxide is released and no adverse effect is caused to the environment within a certain period of time), but this evaluation standard does not give a detailed division for other possible non-biodegradable properties such as hydrolyzability or water solubility, etc.
Disclosure of Invention
In view of the problems of the existing degradation performance evaluation methods for high polymer materials, the invention aims to provide a comprehensive evaluation method for degradation performance of high polymer materials, which can distinguish between biodegradation performance and non-biodegradation performance in the simplest steps and is related to actual testing environment.
The invention relates to a method for evaluating degradation performance of a polymer material, which comprises the following steps:
(1) Providing a high molecular material sample to be evaluated, and measuring the initial number average molecular weight and the initial weight of the high molecular material sample;
(2) The high polymer material sample is placed in a preset environment to be degraded for a preset time;
(3) Molecular weight change and weight change after the degradation of the high molecular material sample are detected, and total organic carbon content change in the degradation process is detected;
(4) Judging whether the molecular weight change, the weight change and the total organic carbon content change in the degradation process are larger than respective preset thresholds according to a designated sequence, and giving a degradation performance evaluation conclusion based on the judgment result.
In some embodiments of the invention, the predetermined sequence comprises: firstly, judging whether the molecular weight change is larger than a preset threshold value; and selecting whether the carbon content change is larger than a preset threshold value or not or whether the weight change is larger than the preset threshold value or not according to the judgment result of the molecular weight change. And if the total organic carbon content change is selected to be judged to be greater than the preset threshold value, an evaluation conclusion is given according to the judging result. If the weight change is judged to be larger than the preset threshold value, the judgment result of the weight change is selected to give an evaluation conclusion, or the total organic carbon content change is judged to be larger than the preset threshold value, and the evaluation conclusion is given according to the judgment result of the total organic carbon content change.
In some embodiments of the invention, step (4) comprises:
I. judging whether the molecular weight change is larger than a preset threshold value;
if the molecular weight change is greater than the preset threshold, judging whether the total organic carbon content change is greater than the preset threshold;
i. if the total organic carbon content change is greater than a preset threshold value, determining that the high polymer material sample can be biodegraded;
if the total organic carbon content is not changed to be larger than the preset threshold value, determining that the high polymer material sample can only be subjected to non-enzymatic hydrolysis;
III, if the molecular weight change is not larger than the preset threshold value, judging whether the weight change is larger than the preset threshold value;
i. if the weight change is greater than the preset threshold, further judging whether the total organic carbon content change is greater than the preset threshold;
if the total organic carbon content change is not greater than the preset threshold value, determining that the high polymer material sample is dissolved;
if the total organic carbon content change is greater than a preset threshold value, determining that the high polymer material sample can be biodegraded;
and if the weight change is not more than the preset threshold value, determining that the high polymer material sample is difficult to degrade or is not degradable.
In some embodiments of the invention, wherein the molecular weight change is measured by GPC gel permeation chromatography, characterized by a rate of molecular weight decrease; the weight change is measured by a balance and is characterized by a weight loss rate; the total organic carbon content change is directly measured through a total organic carbon analyzer and an elemental analyzer and is characterized as the total organic carbon content reduction rate, or the total organic carbon content change is indirectly calculated through the carbon dioxide release amount under the aerobic condition and is characterized as the carbonization rate. Wherein the predetermined threshold value of the molecular weight reduction rate is 10%, and when the molecular weight reduction rate is >10%, the molecular weight reduction is regarded as molecular weight reduction; the preset threshold value of the weight loss rate is 10%, and when the weight loss rate is more than 10%, the weight loss is considered; the preset threshold value of the total organic carbon content reduction rate or mineralization rate is 5%, and when the total organic carbon content reduction rate is more than 5% or mineralization rate is more than 5%, the carbon dioxide is regarded as being released.
In some embodiments of the invention, the predetermined environment may be a simulated marine environment, e.g., a temperature of 30.+ -. 2 ℃ and a microorganism of 10 3 ～10 7 CPU·mL -1 Is a simulated marine environment. Optionally, the preset environment can be any one of a simulated river water environment, a simulated lake water environment, a PBS buffer solution, a simulated soil environment and a simulated composting environment according to the requirement.
In some embodiments of the invention, the sample may be in the form of a film, powder, or block.
In some embodiments of the invention, the evaluation conclusion is associated with a preset environment and a predetermined length of time. In further embodiments, the evaluation of degradation performance may also show changes in molecular weight, and/or total organic carbon content during degradation.
In some embodiments of the invention, the change in total organic carbon content during degradation can be deduced by measuring the content of carbonate ions generated after carbon dioxide released under aerobic conditions during degradation is absorbed by the alkaline solution absorption trap. For example, absorbing the carbon dioxide released during degradation with at least one alkaline solution to react to form carbonate ions; measuring the content of carbonate ions in the alkali solution by adopting an ion chromatograph; the total organic carbon content change is calculated based on the measured carbonate ion content.
Compared with the prior art, the invention has the following beneficial technical effects:
based on the deep analysis of various degradation mechanisms of the high polymer material, the invention selects the molecular weight change, the weight change and the total organic carbon content change in the degradation process as the measurement indexes, designs the unique judgment logic based on the indexes, and can comprehensively evaluate the degradation performance of the high polymer material only by the simplest steps.
Drawings
Fig. 1 shows a schematic flow chart of an evaluation method according to an embodiment of the present invention.
Detailed Description
The present invention will be described in detail with reference to the following specific examples, which are only for illustrating the present invention, and do not limit the scope of the present invention in any way.
In an exemplary embodiment of the present invention, any polymer material sample in the form of powder, film or bulk, such as a resin, a resin composition, a resin alloy, or the like, may be selected. The sample was placed in a reaction tank containing seawater/river/lake/PBS buffer/soil/compost (forming a simulated marine environment/simulated river environment/simulated lake/PBS buffer/simulated soil environment/simulated compost environment) for degradation, and a reaction tank containing only seawater/river/lake/PBS buffer/soil/compost/was used as a blank control.
In an exemplary embodiment of the present invention, seawater in a simulated marine environment may be extracted from natural seawater, and then the amount of microorganisms in the extracted seawater is regulated by enrichment, culture or dilution through filtration, which is adjusted to 10 3 -10 7 CPU/mL. Inorganic salts in seawater, microorganisms and inorganic nutrients required by the microorganisms can be prepared according to the existing standard (for example ASTM D6691-2009) and can be correspondingly adjusted according to the number of the microorganisms. Microorganism counting may be carried out by conventional methods known in the art, such as plate counting.
In an exemplary embodiment of the invention, the temperature in the simulated marine environment is chosen to be 30 ℃, but can also float within a suitable range (e.g. + -2 ℃) which on the one hand can simulate the marine environment and on the other hand can be controlled within a reasonable range, e.g. within 6 months. In addition, temperature conditions for accelerating degradation may be set to improve the evaluation efficiency.
In an exemplary embodiment of the present invention, the degradation process may be performed under aerobic conditions, with either direct introduction of oxygen into the reaction tank or CO removal 2 Air for the gas, e.g. an air compressor may be used to blow air into the CO 2 Hydrazine absorption to remove CO 2 Gas, CO removal 2 The air of the gas is slowly introduced into the reaction tank, and a gas buffer tank and an air flow meter may be provided in the gas flow path as needed in order to appropriately control the flow rate of the gas. In addition, CO 2 The amount of the hydrazine can be set according to the requirement, and can be single CO 2 Hydrazine is absorbed, or a plurality of CO 2 The hydrazine hydrate is used in series.
The total organic carbon content change of the system in the degradation process can be directly characterized by testing the total organic carbon content change of the sample and the water before and after degradation, for example, the organic carbon in the sample is measured by an elemental analyzer, the dissolved organic carbon in the water is tested by the total organic carbon analyzer, and the total organic carbon content and the dissolved organic carbon are added to form the total organic carbon content of the system. The change in total organic carbon content can also be indirectly characterized by measuring the amount of carbon dioxide released by the system under aerobic conditions by the respiratory apparatus.
In an exemplary embodiment of the invention, CO released during degradation of the polymeric material 2 The gas is collected and absorbed by at least one alkali solution with a certain concentration to absorb hydrazine, and CO can be added if necessary to improve the absorption efficiency 2 The contact area of the gas with the absorbing solution, or the use of multiple hydrazine absorbers in series. Use of alkali solution in hydrazine absorption for CO absorption 2 The gas generates carbonate ions, and the alkali solution is preferably NaOH solution or KOH solution with proper concentration, which is easy to quickly generate water-soluble carbonate ions with carbon dioxide.
Periodically measuring the content of carbonate ions in the solution in the hydrazine absorption by adopting an anion chromatograph, and calculating CO generated by degradation 2 When multiple suction is usedWhen hydrazine is connected in series, the sum of the absorption amounts of each hydrazine absorption in the same degradation period should be calculated.
In an exemplary embodiment of the present invention, the concentration of carbonate ions is measured using an anion chromatograph. The invention measures the content of the carbonate ions generated in the degradation process, calculates the corresponding accumulated release amount of carbon dioxide, and finally calculates the mineralization rate (i.e. degradation rate) of the detected high polymer material to represent the change of the carbon content of the sample. The percent of the carbon dioxide release amount generated according to the degradation accumulation to the total content of the carbon dioxide generated by the sample theory is the mineralization rate.
The mineralization rate of a sample can be calculated according to the following equation 1:
wherein Dt (%) is the mineralization rate (%) of the sample (CO) 2 ) T Cumulative carbon dioxide release (mg) for the sample (CO) 2 ) B Accumulated carbon dioxide release (mg), thCO, for the blank group 2 Theoretical CO production for samples 2 Is contained in the total amount (mg) (see formula 2).
Wherein M is TOT To test the total dry solids weight (mg) of the material (i.e., the initial weight of the sample), C TOT To test the total organic carbon content (%) of the material.
In exemplary embodiments of the present invention, carbon dioxide released during degradation may also be detected using other detection means known in the art, such as respirators, infrared spectrometers, gas chromatographs, acid-base titrators, and the like.
In an exemplary embodiment of the present invention, the molecular weight of the sample is a number average molecular weight, measured by GPC gel permeation chromatography, and the weight of the sample is measured by a balance.
The method for evaluating the biodegradability of a polymer material according to the present invention will be described below by taking a plurality of polymer materials as examples with reference to the accompanying drawings.
Example 1:
example 1 provides a method for evaluating degradation performance of PET (polyethylene terephthalate) in a simulated marine environment, comprising the steps of:
(1) A PET (polyethylene terephthalate) sample (sample 1) was provided. The morphology of sample 1 is film morphology. The initial number average molecular weight of sample 1 was 56,130 by GPC measurement, and the initial weight of sample 1 was 0.5g by balance measurement.
(2) Taking 3L natural seawater (the microorganism content in seawater is 9,000CPU mL by detecting with plate counting method) -1 The inorganic nutrient comprises 0.5g/L NH 4 Cl and 0.1g/L KH 2 (PO) 4 ) Placed in a 5L reaction tank, and the reaction tank was placed in a water bath or a vibration device set at a temperature of 30℃to maintain the temperature of seawater in the reaction tank at 30 ℃. Sample 1 was placed in the reaction tank for degradation under light-shielding conditions for 6 months.
(3) In the degradation process, carbon dioxide generated by degradation in a reaction tank is continuously introduced into hydrazine absorption containing 0.1mol/L NaOH aqueous solution so as to enable the carbon dioxide to react with the NaOH to generate carbonate ions, after expiration of 6 months, the hydrazine absorption solution is extracted from the hydrazine absorption solution, and the content of the carbonate ions in the extracted hydrazine absorption solution is measured by an IC940 type ion chromatograph. Wherein the IC940 type ion chromatograph uses MetroSep Organic Acids-250/7.8 chromatographic column, and the eluent is 0.5mM H 2 SO 4 The flow rate was 0.5mL/min, the column temperature was 30℃and the quantitative loop was 100. Mu.L, and sample was injected by 858 autosampler and analyzed by conductivity detector. The amount of carbon dioxide released was estimated based on the content of carbonate ions, and the mineralization rate of sample 1 was converted from the amount of carbon dioxide released.
It was found that sample 1 did not release carbon dioxide during degradation and the mineralization rate was 0.
Meanwhile, after expiration of 6 months, the degraded sample 1 was taken out of the reaction tank, separated, and dried, the number average molecular weight of the degraded sample 1 was 55,569 by GPC measurement, and the weight of the degraded sample 1 was 0.5g by balance measurement, thereby calculating the molecular weight decrease rate of the sample 1 to 1% and the weight loss rate to 0.
The preset thresholds of the molecular weight reduction rate, the weight loss rate and the total organic carbon content reduction rate or the mineralization rate in the degradation process are set as follows: the preset threshold value of the molecular weight reduction rate is 10%, and when the molecular weight reduction rate is more than 10%, the molecular weight reduction rate is regarded as molecular weight reduction; the preset threshold value of the weight loss rate is 10%, and when the weight loss rate is more than 10%, the weight loss is considered; the predetermined threshold for the total organic carbon content reduction rate or mineralization rate is 5%, and when the total organic carbon content reduction rate is >5% or mineralization rate is >5%, the release of carbon dioxide is considered.
(4) Judging whether the molecular weight reduction rate, the weight loss rate and the total organic carbon content reduction rate or the mineralization rate in the degradation process are larger than respective preset thresholds according to the following sequence:
as shown in fig. 1, it is first determined whether the molecular weight reduction rate is greater than a preset threshold, and the molecular weight reduction rate of sample 1 is 1% and is not greater than the preset threshold; and judging whether the weight loss rate is larger than the preset threshold value or not because the molecular weight reduction rate is not larger than the preset threshold value, wherein the weight loss rate of the sample 1 is 0 and is not larger than the preset threshold value.
From this, it was concluded that degradation performance was evaluated: PET (polyethylene terephthalate) in a simulated marine environment (natural sea water, 30 ℃ C., microorganism 9,000CPU. ML) -1 ) The polymer is not degraded in 6 months, the weight loss rate is 0, and the molecular weight reduction rate is 1%.
Example 2:
example 2 provides a method for evaluating degradation performance of a PLA/PLGA (polylactic acid/polylactic acid-glycolic acid copolymer) blend in a simulated marine environment, comprising the steps of:
(1) A sample of PLA/PLGA (polylactic acid/polylactic acid-glycolic acid copolymer) blend (sample 2) was provided. Sample 2 was in the form of a film. The initial number average molecular weight of sample 2 was 61,240 by GPC measurement, and the initial weight of sample 2 was 0.5g by balance measurement.
(2) Taking 3L of natural seawater sediment (the microorganism content in seawater is 1,900CPU mL by detecting with plate counting method) -1 The inorganic nutrient comprises 0.5g/L NH 4 Cl and 0.1g/L KH 2 (PO) 4 ) Placed in a 5L reaction tank, and the reaction tank was placed in a water bath or a vibration device set at a temperature of 30℃to maintain the temperature of seawater in the reaction tank at 30 ℃. Sample 2 was placed in the reaction tank for degradation under light-shielding conditions for 3 months.
(3) During degradation, sample 2 was tested for mineralization rate during degradation according to the carbon dioxide release detection and conversion method described in example 1. The detection shows that the sample 2 has no carbon dioxide release in the degradation process, and the mineralization rate is 0.
Meanwhile, after expiration of 3 months, the degraded sample 2 was taken out of the reaction tank, separated, and dried, the number average molecular weight of the degraded sample 2 was 9,186 by GPC measurement, and the weight of the degraded sample 2 was 0.15g by balance measurement, whereby the molecular weight decrease rate of the sample 2 was 85% and the weight loss rate was 70% were calculated.
The preset thresholds of the molecular weight reduction rate, the weight loss rate and the total organic carbon content reduction rate or the mineralization rate in the degradation process are set as follows: the preset threshold value of the molecular weight reduction rate is 10%, and when the molecular weight reduction rate is more than 10%, the molecular weight reduction rate is regarded as molecular weight reduction; the preset threshold value of the weight loss rate is 10%, and when the weight loss rate is more than 10%, the weight loss is considered; the predetermined threshold for the total organic carbon content reduction rate or mineralization rate is 5%, and when the total organic carbon content reduction rate is >5% or mineralization rate is >5%, the release of carbon dioxide is considered.
(4) Judging whether the molecular weight reduction rate, the weight loss rate and the total organic carbon content reduction rate or the mineralization rate in the degradation process are larger than respective preset thresholds according to the following sequence:
as shown in fig. 1, it is first determined whether the molecular weight reduction rate is greater than a preset threshold, and the molecular weight reduction rate of sample 2 is 85% greater than the preset threshold; and judging whether the total organic carbon content reduction rate or the mineralization rate is larger than a preset threshold value or not because the molecular weight reduction rate is larger than the preset threshold value, wherein the mineralization rate of the sample 2 is 0 and is not larger than the preset threshold value.
From this, it was concluded that degradation performance was evaluated: PLA/PLGA (polylactic acid/polylactic acid-glycolic acid copolymer) blend in simulated marine environment (natural seawater sediment, 30 ℃ C., microorganism 1,900CPU. ML -1 ) Non-enzymatic hydrolysis occurred in 3 months, the weight loss rate was 70%, and the molecular weight reduction rate was 85%.
Example 3:
example 3 provides a method for evaluating degradation performance of PCL (polycaprolactone) in a simulated marine environment, comprising the following steps:
(1) A PCL (polycaprolactone) sample (sample 3) was provided. The morphology of sample 3 was powder morphology. The initial number average molecular weight of sample 3 was 51,235 by GPC measurement, and the initial weight of sample 3 was 0.5g by balance measurement.
(2) Taking 3L natural seawater (the microorganism content in seawater is 90,000CPU mL by detecting with plate counting method) -1 The inorganic nutrient comprises 0.5g/L NH 4 Cl and 0.1g/L KH 2 (PO) 4 ) Placed in a 5L reaction tank, and the reaction tank was placed in a water bath or a vibration device set at a temperature of 30℃to maintain the temperature of seawater in the reaction tank at 30 ℃. Sample 3 was placed in the reaction tank for degradation under light-shielding conditions for 3 months.
(3) During degradation, sample 3 was tested for mineralization rate during degradation according to the carbon dioxide release detection and conversion method described in example 1. The detection shows that the sample 3 releases carbon dioxide in the degradation process, and the mineralization rate of the sample 3 is 20% after conversion.
Meanwhile, after expiration of 3 months, the degraded sample 3 was taken out of the reaction tank, separated, and dried, the number average molecular weight of the degraded sample 3 was 5,124 by GPC measurement, and the weight of the degraded sample 3 was 0.15g by balance measurement, whereby the molecular weight decrease rate of the sample 3 was 90% and the weight loss rate was 80%.
The preset thresholds of the molecular weight reduction rate, the weight loss rate and the total organic carbon content reduction rate or the mineralization rate in the degradation process are set as follows: the preset threshold value of the molecular weight reduction rate is 10%, and when the molecular weight reduction rate is more than 10%, the molecular weight reduction rate is regarded as molecular weight reduction; the preset threshold value of the weight loss rate is 10%, and when the weight loss rate is more than 10%, the weight loss is considered; the predetermined threshold for the total organic carbon content reduction rate or mineralization rate is 5%, and when the total organic carbon content reduction rate is >5% or mineralization rate is >5%, the release of carbon dioxide is considered.
(4) Judging whether the molecular weight reduction rate, the weight loss rate and the total organic carbon content reduction rate or the mineralization rate in the degradation process are larger than respective preset thresholds according to the following sequence:
as shown in fig. 1, it is first determined whether the molecular weight reduction rate is greater than a preset threshold, and the molecular weight reduction rate of sample 3 is 90% greater than the preset threshold; and judging whether the total organic carbon content reduction rate or the mineralization rate is larger than a preset threshold value or not because the molecular weight reduction rate is larger than the preset threshold value, wherein the mineralization rate of the sample 3 is 20% and larger than the preset threshold value.
From this, it was concluded that degradation performance was evaluated: PCL (polycaprolactone) in simulated marine environment (natural seawater, 30deg.C, microorganism 90,000CPU mL) -1 ) Biodegradation occurred in 3 months, and the molecular weight decrease rate was 90%, the weight loss rate was 70%, and the mineralization rate was 20%.
Example 4:
example 4 provides a method for evaluating the degradation performance of PVA1788 (polyvinyl alcohol) in a simulated marine environment, comprising the steps of:
(1) A PVA1788 (polyvinyl alcohol) sample (sample 4) was provided. The morphology of sample 4 was powder morphology. The initial number average molecular weight of sample 4 was 62,460 by GPC measurement, and the initial weight of sample 4 was 0.5g by balance measurement.
(2) Taking 3L natural seawater (the microorganism content in the seawater is 600 CPU.mL by detecting with plate counting method) -1 The inorganic nutrient comprises 0.5g/L NH 4 Cl and 0.1g/L KH 2 (PO) 4 ) Placed in a 5L reaction tank, and the reaction tank was placed in a water bath or a vibration device set at a temperature of 30℃to maintain the temperature of seawater in the reaction tank at 30 ℃. Will beSample 4 was placed in the reaction tank for degradation under light protection for 2 months.
(3) During degradation, sample 4 was tested for mineralization rate during degradation according to the carbon dioxide release detection and conversion method described in example 1. It was found that sample 4 did not release carbon dioxide during degradation and the mineralization rate was 0.
Meanwhile, after expiration of 2 months, the degraded sample 4 was taken out of the reaction tank, separated, and dried, the number average molecular weight of the degraded sample 4 was 62,460 by GPC measurement, and the weight of the degraded sample 4 was 0.05g by balance measurement, whereby the molecular weight decrease rate of the sample 4 was 0 and the weight loss rate was 90% was calculated.
The preset thresholds of the molecular weight reduction rate, the weight loss rate and the total organic carbon content reduction rate or the mineralization rate in the degradation process are set as follows: the preset threshold value of the molecular weight reduction rate is 10%, and when the molecular weight reduction rate is more than 10%, the molecular weight reduction rate is regarded as molecular weight reduction; the preset threshold value of the weight loss rate is 10%, and when the weight loss rate is more than 10%, the weight loss is considered; the predetermined threshold for the total organic carbon content reduction rate or mineralization rate is 5%, and when the total organic carbon content reduction rate is >5% or mineralization rate is >5%, the release of carbon dioxide is considered.
(4) Judging whether the molecular weight reduction rate, the weight loss rate and the total organic carbon content reduction rate or the mineralization rate in the degradation process are larger than respective preset thresholds according to the following sequence:
as shown in fig. 1, it is first determined whether the molecular weight reduction rate is greater than a preset threshold, and the molecular weight reduction rate of sample 4 is 0 and not greater than the preset threshold; since the molecular weight reduction rate is not greater than the preset threshold, judging whether the weight loss rate is greater than the preset threshold, wherein the weight loss rate of the sample 4 is 90% and greater than the preset threshold; and judging whether the total organic carbon content reduction rate or the mineralization rate is larger than a preset threshold value or not because the weight loss rate is larger than the preset threshold value, wherein the mineralization rate of the sample 4 is 0 and is not larger than the preset threshold value.
From this, it was concluded that degradation performance was evaluated: PVA1788 (polyvinyl alcohol) in simulated marine environment (natural sea water, 30 ℃ C., microorganism 600 CPU.mL -1 ) Dissolution occurred for 2 months and no biodegradation occurred,the molecular weight reduction rate was 0 and the weight loss rate was 90%.
Example 5:
example 5 provides a method for evaluating degradation performance of PLA (polylactic acid) in PBS buffer solution environment, comprising the steps of:
(1) A PLA (polylactic acid) sample (sample 5) was provided. The morphology of sample 5 was film morphology. The initial number average molecular weight of sample 5 was 60,120 by GPC measurement, and the initial weight of sample 5 was 0.5g by balance measurement.
(2) 3L of PBS buffer solution (the microorganism content in the PBS buffer solution is 600 CPU.mL) was taken -1 pH 8.5) was placed in a 5L reaction tank, and the reaction tank was placed in a water bath or a shaking apparatus set at a temperature of 60℃to maintain the PBS buffer solution temperature in the reaction tank at 60 ℃. Sample 5 was placed in the reaction tank for degradation under light-shielding conditions for 3 months.
(3) During degradation, the mineralization rate of sample 5 during degradation was measured according to the carbon dioxide release detection and conversion method described in example 1. It was found that sample 5 did not release carbon dioxide during degradation and the mineralization rate was 0.
Meanwhile, after expiration of 3 months, taking out the degraded end product from the reaction tank, separating and drying, obtaining a degraded sample 5 with a number average molecular weight of 9,018 by GPC measurement, obtaining a degraded sample 5 with a weight of 0.15g by balance measurement, and obtaining a molecular weight reduction rate of 85% and a weight loss rate of 70% of the sample 5 by calculation.
The preset thresholds of the molecular weight reduction rate, the weight loss rate and the total organic carbon content reduction rate or the mineralization rate in the degradation process are set as follows: the preset threshold value of the molecular weight reduction rate is 10%, and when the molecular weight reduction rate is more than 10%, the molecular weight reduction rate is regarded as molecular weight reduction; the preset threshold value of the weight loss rate is 10%, and when the weight loss rate is more than 10%, the weight loss is considered; the predetermined threshold for the total organic carbon content reduction rate or mineralization rate is 5%, and when the total organic carbon content reduction rate is >5% or mineralization rate is >5%, the release of carbon dioxide is considered.
(4) Judging whether the molecular weight reduction rate, the weight loss rate and the total organic carbon content reduction rate or the mineralization rate in the degradation process are larger than respective preset thresholds according to the following sequence:
as shown in fig. 1, it is first determined whether the molecular weight reduction rate is greater than a preset threshold, and the molecular weight reduction rate of sample 5 is 85% greater than the preset threshold; and judging whether the total organic carbon content reduction rate or the mineralization rate is larger than a preset threshold value or not because the molecular weight reduction rate is larger than the preset threshold value, wherein the mineralization rate of the sample 5 is 0 and is not larger than the preset threshold value.
From this, it was concluded that degradation performance was evaluated: PLA (polylactic acid) in PBS buffer solution environment (60 ℃ C., microorganism 600 CPU.mL) -1 ) Non-enzymatic hydrolysis occurred in 3 months, the weight loss rate was 70%, and the molecular weight reduction rate was 85%.
Example 6:
example 6 provides a method for evaluating degradation performance of PHB (poly-beta-hydroxybutyric acid) in a simulated river water environment, comprising the following steps:
(1) PHB (poly-beta-hydroxybutyrate) sample (sample 6) was provided. The morphology of sample 6 was powder morphology. Sample 6 had an initial number average molecular weight of 68,926 as measured by GPC and an initial weight of 0.5g as measured by a balance.
(2) Taking 3L of natural river water (the microorganism content in the river water is 900,000CPU mL by detecting with plate counting method) -1 ) Placed in a 5L reaction tank, the reaction tank was placed in a water bath or a vibration device set at a temperature of 30℃to maintain the river temperature in the reaction tank at 30 ℃. Sample 6 was placed in the reaction tank for degradation under light-shielding conditions for 3 months.
(3) During degradation, sample 6 was tested for mineralization rate during degradation according to the carbon dioxide release detection and conversion method described in example 1. The detection shows that the sample 6 releases carbon dioxide in the degradation process, and the mineralization rate of the sample 6 is 40% after conversion.
Meanwhile, after expiration of 3 months, the degraded sample 6 was taken out of the reaction tank, separated, and dried, the number average molecular weight of the degraded sample 6 was 6,893 as measured by GPC, the weight of the degraded sample 6 was 0.1g as measured by balance, and the molecular weight decrease rate of the sample 6 was 90% and the weight loss rate was 80% as calculated.
The preset thresholds of the molecular weight reduction rate, the weight loss rate and the total organic carbon content reduction rate or the mineralization rate in the degradation process are set as follows: the preset threshold value of the molecular weight reduction rate is 10%, and when the molecular weight reduction rate is more than 10%, the molecular weight reduction rate is regarded as molecular weight reduction; the preset threshold value of the weight loss rate is 10%, and when the weight loss rate is more than 10%, the weight loss is considered; the predetermined threshold for the total organic carbon content reduction rate or mineralization rate is 5%, and when the total organic carbon content reduction rate is >5% or mineralization rate is >5%, the release of carbon dioxide is considered.
(4) Judging whether the molecular weight reduction rate, the weight loss rate and the total organic carbon content reduction rate or the mineralization rate in the degradation process are larger than respective preset thresholds according to the following sequence:
as shown in fig. 1, it is first determined whether the molecular weight reduction rate is greater than a preset threshold, and the molecular weight reduction rate of sample 6 is 90% and greater than the preset threshold; and judging whether the total organic carbon content reduction rate or the mineralization rate is larger than a preset threshold value or not because the molecular weight reduction rate is larger than the preset threshold value, wherein the mineralization rate of the sample 6 is 40% and larger than the preset threshold value.
From this, it was concluded that degradation performance was evaluated: PHB (Poly-beta-hydroxybutyric acid) was used in a simulated river water environment (30 ℃ C., microorganism 900,000CPU mL) -1 ) Biodegradation occurs in 3 months, the weight loss rate is 80%, the molecular weight reduction rate is 90%, and the mineralization rate is 40%.
The present invention has been described in detail with reference to specific embodiments thereof, which are merely illustrative, and not intended to limit the scope of the invention, and those skilled in the art can make various modifications, changes or substitutions without departing from the spirit and scope of the invention. Accordingly, various equivalent modifications are intended to be included within the scope of this invention.
Claims (9)
1. The method for evaluating the degradation performance of the high polymer material comprises the following steps:
(1) Providing a high molecular material sample to be evaluated, and measuring the initial molecular weight and the initial weight of the high molecular material sample;
(2) The high polymer material sample is placed in a preset environment to be degraded for a preset time;
(3) Molecular weight change and weight change after the degradation of the high molecular material sample are detected, and total organic carbon content change in the degradation process is detected;
(4) Judging whether the molecular weight change, the weight change and the total organic carbon content change in the degradation process are larger than respective preset thresholds according to a designated sequence, and giving a degradation performance evaluation conclusion based on a judgment result;
wherein the step (4) comprises:
I. judging whether the molecular weight change is larger than a preset threshold value;
if the molecular weight change is greater than the preset threshold, judging whether the total organic carbon content change is greater than the preset threshold;
i. if the total organic carbon content change is greater than a preset threshold value, determining that the high polymer material sample can be biodegraded;
if the total organic carbon content is not changed to be larger than the preset threshold value, determining that the high polymer material sample can only be hydrolyzed in a non-enzymatic way;
III, if the molecular weight change is not larger than the preset threshold value, judging whether the weight change is larger than the preset threshold value;
i. if the weight change is greater than the preset threshold, further judging whether the total organic carbon content change is greater than the preset threshold;
if the total organic carbon content change is not greater than the preset threshold value, determining that the high polymer material sample can only be dissolved;
if the total organic carbon content change is greater than a preset threshold value, determining that the high polymer material sample can be biodegraded;
and if the weight change is not more than the preset threshold value, determining that the high polymer material sample is difficult to degrade or is not degradable.
2. The method of claim 1, wherein the molecular weight change is characterized by a molecular weight reduction rate as measured by GPC gel permeation chromatography; the weight change is measured by a balance and is characterized by a weight loss rate; the total organic carbon content change is directly measured through a total organic carbon analyzer and an elemental analyzer and is characterized as the total organic carbon content reduction rate, or the total organic carbon content change is indirectly calculated through the carbon dioxide release amount under the aerobic condition and is characterized as the carbonization rate.
3. The method of claim 2, wherein the predetermined threshold for the rate of molecular weight reduction is 10%, the predetermined threshold for the rate of weight loss is 10%, and the predetermined threshold for the rate of total organic carbon content reduction or mineralization is 5%.
4. The method of claim 1, wherein the predetermined environment is a simulated marine environment at a temperature of 30+ -2deg.C and a microorganism content of 10 3 ～10 7 CPU·mL -1 。
5. The method of claim 1, wherein the pre-set environment is any one of a simulated river water environment, a simulated lake water environment, a PBS buffer, a simulated soil environment, a simulated composting environment.
6. The method of claim 1, wherein the polymer material sample is in the form of a powder or a film or a block.
7. The method of claim 1, wherein the evaluation conclusion is associated with a preset environment, a predetermined length of time, a molecular weight change, a weight change, and/or a change in total organic carbon content during degradation.
8. The method of claim 1, wherein the change in total organic carbon content during degradation is calculated by measuring the content of carbonate ions generated after carbon dioxide released under aerobic conditions during degradation is absorbed by the alkaline solution absorption trap.
9. The method of claim 8, wherein the carbon dioxide released during degradation is absorbed with at least one alkaline solution to react to form carbonate ions;
measuring the content of carbonate ions in the alkali solution by adopting an ion chromatograph;
the total organic carbon content change is calculated based on the measured carbonate ion content.
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