CN108344762A - The detection method of polylactic acid content in a kind of degradable plastic product - Google Patents
The detection method of polylactic acid content in a kind of degradable plastic product Download PDFInfo
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- CN108344762A CN108344762A CN201810154905.2A CN201810154905A CN108344762A CN 108344762 A CN108344762 A CN 108344762A CN 201810154905 A CN201810154905 A CN 201810154905A CN 108344762 A CN108344762 A CN 108344762A
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- G01N24/00—Investigating or analyzing materials by the use of nuclear magnetic resonance, electron paramagnetic resonance or other spin effects
- G01N24/08—Investigating or analyzing materials by the use of nuclear magnetic resonance, electron paramagnetic resonance or other spin effects by using nuclear magnetic resonance
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Abstract
The present invention provides a kind of detection methods of polylactic acid content in degradable plastic product, including：Using the content of polylactic acid in the method detection degradable plastic product of nuclear magnetic resonance.Method provided by the invention, quantitative detection can be carried out to the content of polylactic acid in degradable plastic product, it need not carry out pretreatment process complicated, that condition is harsh, time-consuming, the present invention is directly dissolved sample to be tested using the method for nuclear magnetic resonance, and quantitative detection can be realized by adding internal standard.Detection method provided by the invention is simple and practicable, and a kind of easy, quick, accurate new method is provided for the sample detection of high-volume degradable plastic product.
Description
Technical field
The present invention relates to a kind of inspections of polylactic acid content in quantitative measurement technology field more particularly to degradable plastic product
Survey method.
Background technology
Since eighties of last century the seventies, " white pollution " this noun progresses into the sight of people, and becomes
One of the Important Problems of environment in recent years protection.As the industrialized progress in China is gradually recognized while rapid economic development
Know the harmfulness present in environmental pollution, administers " white pollution " into very urgent thing.2008, country was directed to
" white pollution " has prohibited limitation and has used Phthalates, and national " plastic limit " has been contained in vain to a certain extent
The aggravation of color pollution, Jilin Province in 2015 formally implement " prohibiting modeling to enable ", forbid production and sales in the whole province's range and provide disposable
Nondegradable plastics film bag product and tableware.This has been first province for " prohibiting modeling " comprehensively since China implements " plastic limit ",
New opportunity is provided for the development of degradable plastic product.
" white pollution " caused by nondegradable plastics product is primarily due to conventional plastic product and is difficult in nature
Middle degradation, thus produce can natural degradation plastic products become new era Material Field one of hot research content.Poly- breast
Acid is a kind of polyester material, has good biocompatibility and environment friendly, under field conditions (factors) can be complete by microorganism
Degradable, catabolite are that water and carbon dioxide are a kind of biomaterials of pure green, with polylactic acid system to zero environmental
At degradable plastic product, occupy very big proportion in the degradable plastic product currently on the market.
For the content of polylactic acid in specification degradable plastic product, Jilin Province has formulated provincial standard DB22/T 2105-
2014《The polylactic acid assay chromatography of ions in polylactic acid article》, to the measurement of polylactic acid content in degradable plastic product
Method has carried out Uniform provisions.According to this examination criteria, need to carry out pre-treatment to polylactic acid article, in high temperature, highly basic
Under the conditions of hydrolyze 4 hours, then filtering dilution carry out ion chromatography.Although the prior art provide detection method using
Range is big, but the processing of this method is cumbersome, time-consuming longer, is not easy to operate.Therefore it provides a kind of quickly detection degradable plastic
The method of the content of polylactic acid becomes the hot spot of this field research in material products.
Invention content
In view of this, the purpose of the present invention is to provide a kind of detection sides of polylactic acid content in degradable plastic product
Method, detection method provided by the invention being capable of the simple and efficient matter for accurately quantitatively detecting polylactic acid in degradable plastic product
Measure content.
The present invention provides a kind of detection methods of polylactic acid content in degradable plastic product, including：
Using the mass content of polylactic acid in the method detection degradable plastic product of nuclear magnetic resonance.
In the present invention, the detection method is preferably specially：
The sample to be tested of degradable plastic product is dissolved, lysate is obtained；
Internal standard compound is added into lysate, carries out magnetic resonance detection；
According to detection obtain as a result, measure polylactic acid displacement study characteristic peak area and internal standard compound chemical shift feature
The mass content of polylactic acid in degradable plastic product is calculated in the area ratio at peak.
In the present invention, the degradable plastic product can be the plastics system prepared by degradable high molecular material
Product；The method of the preparation such as can squeeze out, be molded, being blow molded at the processing methods.In the present invention, the degradable plastic product can
Think plastic film, polybag, plastic tubleware and drinking ware, medical supplies, auto parts machinery, household house ornamentation articles for use, ornament, craftwork,
The plastic products such as unmanned plane.In the present invention, the plastic film can be plastic film for wrapping and mulch, canopy film, bitter lid
The agricultural films such as film, green storage film；The polybag can be shopping bag, bag on roll, flat mouth bag, sealed bag, freshness protection package etc.；The plastics
Dining tool can be basin, bowl, cup, lid, disk, dish, knife, fork, spoon, suction pipe etc.；The medical supplies can be nail, bone plate, note
Emitter, infusion apparatus, diversion pipe, infusion bag, infusion bottle, holder, suture etc..
In the present invention, in the degradable plastic product polylactic acid mass content can be 0~100% between appoint
Meaning value.
In the present invention, the solvent of the dissolving is preferably deuterated reagent, more preferably deuterochloroform, deuterated DMSO (two
Methyl sulfoxide), deuterated acetone, deuterated DMF (N,N-dimethylformamide), deuterated trifluoroacetic acid, deuterated pyridine or deuterated isopropyl
Alcohol.
In the present invention, the method for the nuclear magnetic resonance is preferably hydrogen nuclear magnetic resonance spectroscopy.In the present invention, the poly- breast
Acid structure be：
In the present invention, the polylactic acid displacement study characteristic peak at least one not with other anyization in detection architecture
The chemical shift characteristic peak that substance generates is learned to overlap；The polylactic acid displacement study characteristic peak is preferably the chemical potential of the upper H of-CH-
Move characteristic peak, or-CH3The chemical shift characteristic peak of upper H.In the present invention, the chemical shift of the upper H of-CH- 5~
5.2ppm place.
In the present invention, the internal standard compound is not chemically reacted with other compounds in detection architecture, the internal standard
At least one chemical shift not generated with other any chemical substances in detection architecture of the chemical shift characteristic peak of object
Characteristic peak overlaps.In the present invention, the internal standard compound is preferably imidazoles.In the present invention, the chemical shift of the internal standard compound is special
Levy the chemical shift characteristic peak that peak is preferably H on carbon in-NH-CH=N-.In the present invention, H on carbon in the-NH-CH=N-
Chemical shift at 7.6~7.8ppm.
In the present invention, the mass ratio of the sample to be tested of the degradable plastic product and internal standard compound is preferably (1~3)：
1, more preferably (1.5~2.5)：1, most preferably 2:1.
In the present invention, the method for the calculating carries out according to the following equation：
Wherein, m is quality, and M is molecular weight, and A is chemical shift characteristic peak area, and N is of H at chemical shift characteristic peak
Number, i.e. mPolylactic acidRepresent the quality of polylactic acid, mInternal standard compoundRepresent the quality of internal standard compound, MInternal standard compoundRepresent the molecular weight of internal standard compound, APolylactic acidGeneration
Table polylactic acid displacement study characteristic peak area, AInternal standard compoundRepresent internal standard compound chemical shift characteristic peak area, NPolylactic acidRepresent polylactic acid
The number of H, N at displacement study characteristic peakInternal standard compoundRepresent the number of H at internal standard compound chemical shift characteristic peak, MPolylactic acidRepresent polylactic acid
Molecular weight.
Compared with prior art, the method that the present invention uses nuclear magnetic resonance, can be to polylactic acid in degradable plastic product
Content carry out quantitative detection, pretreatment process complicated, that condition is harsh, time-consuming need not be carried out, the present invention uses nuclear-magnetism
The method of resonance directly dissolves sample to be tested, and quantitative detection can be realized by adding internal standard.Detection side provided by the invention
Method is simple and practicable, and a kind of easy, quick, accurate new method is provided for the sample detection of high-volume degradable plastic product.
Description of the drawings
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technology description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
The embodiment of invention for those of ordinary skill in the art without creative efforts, can also basis
The attached drawing of offer obtains other attached drawings.
Fig. 1 is the hydrogen nuclear magnetic resonance spectrogram that the embodiment of the present invention 1 detects obtained polylactic acid；
Fig. 2 is the hydrogen nuclear magnetic resonance spectrogram that the embodiment of the present invention 2 detects obtained polylactic acid imidazole mixture；
Fig. 3 is the hydrogen nuclear magnetic resonance spectrogram that the embodiment of the present invention 3 detects obtained degradable plastic product.
Specific implementation mode
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation describes, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other
Embodiment shall fall within the protection scope of the present invention.
The nuclear magnetic resonance spectroscopy of 1 polylactic acid of embodiment
The polylactic acid for weighing 4mg, is dissolved in deuterochloroform, carries out nuclear magnetic resonance spectroscopy detection, determines polylactic acid
Chemical shift.
Testing result such as Fig. 1, Fig. 1 are the nucleus magnetic hydrogen spectrum figure of polylactic acid sterling (analysis is pure).
Embodiment 2：Nucleus magnetic hydrogen spectrum measures the error analysis of polylactic acid content
Weighing 4mg polylactic acid and 2.5mg imidazoles, (structural formula is), it is dissolved in deuterochloroform, carries out
Nuclear magnetic resonance spectroscopy detects.
Testing result is as shown in Fig. 2, in Fig. 2, and the chemical shift of H gathers at 7.72ppm on carbon in-NH-CH=N- structures
The chemical shift of the upper H of-CH- is at 5.165ppm in lactic acid, by following formula, utilizes the integral of chemical shift characteristic peak at two
Area ratio can calculate the quality of polylactic acid：
Wherein m, M, Ax, Ny respectively represent quality, the integral area that molecular weight, chemical shift are x, chemical shift are H at y
Number.
It calculates according to fig. 2, the characteristic peak area at 7.72 and 5.165ppm chemical shifts is respectively 1 and 1.53, is brought into
Above-mentioned formula is calculated, and the quality of polylactic acid is 4.05mg, compared with the polylactic acid actually weighed, error 1.25%.
The measurement of polylactic acid content in 3 degradable plastic bag of embodiment
Degradable plastic bag is cut into small pieces, 4mg is weighed and is dissolved in deuterochloroform, the imidazoles of 2mg is then added as core
Magnetic internal standard carries out nuclear magnetic resonance spectroscopy detection after dissolving.
Nucleus magnetic hydrogen spectrum testing result as shown in figure 3, according in embodiment 2 method and formula calculated, obtain poly- breast
The quality of acid is 1.71mg, and the mass content of polylactic acid is 1.71/4 × 100%=42.8% in degradable plastic bag.
According to DB22/T 2105-2014《The polylactic acid assay chromatography of ions in polylactic acid article》, detection is above-mentioned can
The mass content of polylactic acid in degradative plastic bag, testing result 42.9%.
As can be seen that the testing result that detection method provided by the invention obtains testing result and existing professional standard connects
Closely, detection method provided by the invention can accurately detect the mass content of polylactic acid in degradable plastic product.
The measurement of polylactic acid content in 4~16 degradable plastic product of embodiment
Degradable plastic product is cut into small pieces or is clayed into power, certain mass is accurately weighed and is dissolved in deuterated reagent, so
The imidazoles nuclear-magnetism internal standard of certain mass is added afterwards, carries out magnetic resonance detection.It calculates, obtains according to the method and formula of embodiment 3
To the content of polylactic acid in degradable plastic product.
The embodiment of the present invention 4~16 tests the mass content testing result of polylactic acid in obtained degradable plastic product such as
Shown in table 1：
The mass content of polylactic acid in the degradable plastic product of 1 embodiment of the present invention 4~16 of table test
17~21 nuclear magnetic resonance method of embodiment and the comparison of ion-chromatographic determination polylactic acid content are analyzed
Five kinds of typical polylactic acid articles, the nuclear magnetic resonance method the provided through the invention (side that embodiment 3 provides are provided
Method) and the chromatography of ions (DB22/T 2105-2014《The polylactic acid assay chromatography of ions in polylactic acid article》) gathered
Lactic acid content measures, and testing result is as shown in table 2：
The mass content for the polylactic acid that the detection method that 2 embodiment of the present invention 17~21 of table uses is tested
| Embodiment | Sample ID | Nuclear magnetic resonance method | The chromatography of ions | Deviation |
| Embodiment 17 | Polylactic acid plastic film | 35.1% | 35.2% | 0.28% |
| Embodiment 18 | Polylactic acid shopping bag | 35.2% | 35.2% | 0 |
| Embodiment 19 | Polylactic acid bag on roll | 34.8% | 34.9% | 0.29% |
| Embodiment 20 | Polylactic acid cutlery box | 76.1% | 76.3% | 0.26% |
| Embodiment 21 | Polylactic acid pallet | 78.0% | 78.2% | 0.26% |
From table 2 it can be seen that the result that two methods measure is close, deviation is minimum.Therefore nuclear-magnetism provided by the invention is total
The polylactic acid comparision contents that the method for shaking measures are accurate.
As seen from the above embodiment, the present invention provides a kind of detection sides of polylactic acid content in degradable plastic product
Method, including：Using the content of polylactic acid in the method detection degradable plastic product of nuclear magnetic resonance.Method provided by the invention,
Quantitative detection can be carried out to the content of polylactic acid in degradable plastic product, need not carry out that complicated, condition is harsh, time-consuming
Pretreatment process, sample to be tested directly dissolved using the method for nuclear magnetic resonance, be can be realized by adding internal standard by the present invention
Quantitative detection.Detection method provided by the invention is simple and practicable, and the sample detection for high-volume degradable plastic product provides
A kind of easy, quick, accurate new method.
The above is the preferred embodiment of the present invention, it is noted that for those skilled in the art
For, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications should also be as
It is considered as protection scope of the present invention.
Claims (10)
1. the detection method of polylactic acid content in a kind of degradable plastic product, including：It can using the method detection of nuclear magnetic resonance
The mass content of polylactic acid in degradative plastics product.
2. detection method according to claim 1, which is characterized in that the detection method is specially：
The sample to be tested of degradable plastic product is dissolved, lysate is obtained；
Internal standard compound is added into lysate, carries out magnetic resonance detection；
According to detection obtain as a result, measuring the area and internal standard compound chemical shift characteristic peak of polylactic acid displacement study characteristic peak
The mass content of polylactic acid in degradable plastic product is calculated in area ratio.
3. detection method according to claim 1, which is characterized in that the method for the nuclear magnetic resonance is nuclear magnetic resonance spectroscopy
Method.
4. detection method according to claim 2, which is characterized in that the polylactic acid displacement study characteristic peak is on-CH-
The characteristic peak of the chemical shift of H, or-CH3The characteristic peak of the chemical shift of upper H.
5. detection method according to claim 2, which is characterized in that the internal standard compound is imidazoles.
6. detection method according to claim 5, which is characterized in that the chemical shift characteristic peak of the internal standard compound is-NH-
In CH=N- on carbon H chemical shift characteristic peak.
7. detection method according to claim 4, which is characterized in that the chemical shift of the upper H of-CH- 5~
5.2ppm。
8. detection method according to claim 5, which is characterized in that in-the NH-CH=N- on carbon H chemical shift
In 7.6~7.8ppm.
9. detection method according to claim 2, which is characterized in that the method for the calculating is carried out according to the formula of Formulas I：
In Formulas I, m is quality, and M is molecular weight, and A is chemical shift characteristic peak area, and N is the number of H at chemical shift characteristic peak.
10. detection method according to claim 2, which is characterized in that the solvent of the dissolving is deuterated reagent.
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Cited By (4)
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| CN110554111A (en) * | 2019-09-11 | 2019-12-10 | 南开大学 | Quantitative detection method for trace polylactic acid micro-plastic in environmental sample |
| CN112782207A (en) * | 2020-12-14 | 2021-05-11 | 海南省产品质量监督检验所 | Nuclear magnetic resonance spectrum analysis method of biodegradable plastic |
| CN113267524A (en) * | 2021-05-14 | 2021-08-17 | 广东省中山市质量计量监督检测所 | Detection method of starch-based plastic component |
| CN113325025A (en) * | 2021-05-11 | 2021-08-31 | 宁波海关技术中心 | Identification method of polyformaldehyde |
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| CN112782207A (en) * | 2020-12-14 | 2021-05-11 | 海南省产品质量监督检验所 | Nuclear magnetic resonance spectrum analysis method of biodegradable plastic |
| CN113325025A (en) * | 2021-05-11 | 2021-08-31 | 宁波海关技术中心 | Identification method of polyformaldehyde |
| CN113325025B (en) * | 2021-05-11 | 2023-06-16 | 宁波海关技术中心 | Identification method of polyoxymethylene |
| CN113267524A (en) * | 2021-05-14 | 2021-08-17 | 广东省中山市质量计量监督检测所 | Detection method of starch-based plastic component |
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