CN104569218B - For extracting the compound extract of phthalic acid ester in polypropylene material - Google Patents
For extracting the compound extract of phthalic acid ester in polypropylene material Download PDFInfo
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Abstract
The present invention relates to a kind of for extracting the compound extract of phthalic acid ester in polypropylene material.This compound extract is R by general structure1COOR2Ester and C5-C7Linear paraffin composition, the synergism of two of which component so that this compound extract has good effect for the extraction of the phthalic acid ester of trace in polypropylene.The specific aim of this compound extract is relatively strong, and the extraction efficiency of the phthalic acid ester in polypropylene is high, and the response rate is good.The invention still further relates to and a kind of adopt above-mentioned compound extract to extract the method for phthalic acid ester in polypropylene material, the method is highly sensitive, simple to operate, with low cost.The qualitative, quantitative that above-mentioned compound extract and extracting process are applied to follow-up gas chromatography-mass spectrography measures, can accurately determine in polypropylene kind and the content of contained phthalate compound, simple to operate, quickly and the requirement of environmental protection can be met.
Description
Technical field
The present invention relates to phthalic acid ester analysis technical field in polypropylene material, relate to a kind of compound extract for extracting phthalic acid ester in polypropylene material and application thereof.
Background technology
Polypropylene (Polypropylene is called for short PP) is a kind of hemicrystalline thermoplastic.Having higher resistance to impact, engineering properties is tough, resists multiple organic solvent and acid and alkali corrosion.It is widely used in industrial quarters, is one of usually common macromolecular material, plastic, packaging material occupy extremely important position.
Phthalic acid ester (phthalateesters, PAEs) compounds has a wide range of applications in plastics industry, is often added in plastics.In polypropylene material, due to the use of certain class special catalyst, the trace P AEs contained in catalyst is also introduced in pp material, thus being present in polypropylene plastics products, penetrates in commercial production and daily life.Owing to PAEs is only combined by hydrogen bond or Van der Waals force with polymer body, therefore in use can constantly discharge and transfer in surrounding, become the organic pollution being widely present in air, water body, soil, thus being prevalent in the environment of human lives.PAEs is typical environmental estrogens pollutant, is entered in plant by plant absorption, it may occur that biological concentration, Long Term Contact can affect human endocrine, causes deformity, canceration and mutagenesis, thus caused extensive concern both domestic and external in recent years.
American-European-Japanese regulation has clearly indicated that disabling phthalic ester plasticizer in toy for children；The U.S., European Union (EU), the World Health Organization (WHO), Japan and China all successively propose " priority pollutants list " in water body, and wherein phthalate has 3 kinds；In the air of Environmental Protection Agency USA (EPA) priority control in 190 kinds of noxious pollutant lists, phthalate has 4 kinds.GB/T21928-2008 " in food plastic packaging material the mensuration of phthalic acid ester " has been formulated in China's amendment in recent years, defines using priciple and the standard of phthalate material to a certain extent.
At present the extraction mode of additive in plastic, rubber mainly there are soxhlet extraction, ultrasonic extraction and microwave extracting etc., wherein soxhlet extraction required time is long, operates relatively complicated, and microwave extracting specific aim is not strong, major part additive such as pigment etc. all can enter extract, interference detection results.Ultrasonic extraction is suitable for the extraction of the higher additive of content, and the extraction efficiency for micro constitutent is not high.Current emerging Accelerate solvent extraction method, extraction efficiency is high, save solvent, operation semi-automation, preferably a large amount of samples is processed.The selection of extract also directly affects extraction efficiency and effect.The extract of phthalic acid ester at present selects to be mainly single formula, and solvent-oil ratio is big, extraction efficiency is low, insufficient sensitivity, operating process is loaded down with trivial details, extraction efficiency is not high, environment is unfriendly.
The problem that presently, there are is that needs research and development one is highly sensitive, simple to operate, can efficiently extract phthalate compound in polypropylene, and can meet the technology of the requirement of environmental protection simultaneously.
Summary of the invention
The technical problem to be solved is for the deficiencies in the prior art, it is provided that a kind of for extracting the compound extract of phthalic acid ester in polypropylene material.This compound extract is R by general structure1COOR2Ester and C5-C7Linear paraffin composition, the specific aim of this compound extract is relatively strong, and the extraction efficiency of the phthalic acid ester in polypropylene is high, and the response rate is good.
Present invention also offers and a kind of adopt above-mentioned compound extract to extract the method for phthalic acid ester in polypropylene material, the method is highly sensitive, simple to operate, with low cost.
The qualitative, quantitative that above-mentioned compound extract and extracting process are applied to follow-up gas chromatography-mass spectrography measures, can accurately determine in polypropylene kind and the content of contained phthalate compound, simple to operate, quickly and the requirement of environmental protection can be met.
For this, first aspect present invention provides a kind of for extracting the compound extract of phthalic acid ester in polypropylene material, is R including general structure1COOR2Ester and C5-C7Linear paraffin, wherein, R1For H or C1Alkyl, R2For C1-C2Alkyl.
Heretofore described term " phthalic acid ester ", also known as phthalate ester, is abbreviated as PAE, is the general designation of the ester that phthalic acid is formed, is also known as " phthalate material ".When being used as plastic plasticizer, it is generally referred to as the ester that the alcohol of phthalic acid and 1～10 carbon is formed.Wherein dioctyl phthalate is most important kind.Phthalic acid ester is that a class can play the chemicals of emollescence and may also interfere with hormonal system.The general structure of phthalic acid ester is such as shown in formula I:
Wherein, R and R ' can be C1-C10Alkyl or aryl.
The phthalic acid ester that current polrvinyl chloride raw material and goods manufacturing commonly use most has: dimethyl phthalate (DMP), diethyl phthalate (DEP), dibutyl phthalate (DBP), diisobutyl phthalate (DIBP), phthalic acid two (2-methoxyl group) ethyl ester (DMEP), phthalic acid two (4-methyl-2-amyl group) ester (BMPP), phthalic acid two (2-ethyoxyl) ethyl ester (DEEP), diamyl phthalate (DPP), dihexylphthalate (DHXP), butyl benzyl phthalate (BBP), phthalic acid two (2-butoxy) ethyl ester (DBEP), dicyclohexyl phthalate (DCHP), phthalic acid two (2-ethyl) own ester (DEHP), diphenyl phthalate (DPhP), dinoctyl phthalate (DNOP), dinonyl phthalate (DNP) etc..
In the present invention term " trace " used refer to ten thousand/to 1/1000000th, it is simply that 1～100ppm, is exactly here 1～100 μ g/g.The inventive method is particularly suited for the Trace Phthalate Acid Esters class material efficiently extracting in polypropylene material.
The present invention adopts structure formula to be R1COOR2Ester and C5-C7Linear paraffin make a kind of efficiently extract, two kinds of component synergism so that this compound extract has good effect for the extraction of the phthalate material of trace in polypropylene by a certain percentage.
According to the present invention, in described compound extract, described general structure is R1COOR2Ester and C5-C7The volume ratio of linear paraffin be 2.5～10:1.Preferred described general structure is R1COOR2Ester and C5-C7The volume ratio of linear paraffin be 4～6.67:1.
In one embodiment of the invention, described general structure is R1COOR2Ester include one or more in methyl formate, Ethyl formate, methyl acetate and ethyl acetate, it is preferred to methyl acetate or ethyl acetate.
In another embodiment of the present invention, described C5-C7Linear paraffin include one or more in pentane, normal hexane and normal heptane, it is preferred to normal hexane.
Second aspect present invention provides and a kind of adopts compound extract as above to extract the method for phthalic acid ester in polypropylene material.
In method provided by the invention, described extraction conditions can be adjusted according to the different extracting process adopted.Such as, when using Accelerate solvent extraction method, extraction conditions is preferably: the temperature of described extraction is 85～110 DEG C.The time of described extraction is 3～7min.The flush volume of described extraction is 80%～120%.The purge time of described extraction is 100～130s.
Heretofore described term " flush volume " refers to that extraction process adopts fresh solvent to rinse thing to be extracted in abstraction pool after completing, and the solvent volume used accounts for the percentage ratio of abstraction pool volume.
After heretofore described term " purge time " refers to that extraction process is fully completed, adopt the time that the remaining liq in abstraction pool is purged by nitrogen.Purge step ensure that as far as possible many extracts are collected in receiving bottle.
Third aspect present invention provides a kind of analyzes the method for phthalic acid ester in polypropylene material, comprising:
(1) method of phthalic acid ester in extraction polypropylene material as above is adopted；With
(2) gas phase-MS is adopted to measure kind and the content of phthalic acid ester in polypropylene material.
In an embodiment of the invention, in above-mentioned analysis polypropylene material, the method for phthalic acid ester also includes adopting Accelerate solvent extraction method that phthalic acid ester in polypropylene material is oriented extraction.
16 kinds of phthalic acid esters that the phthalic acid ester standard substance used in the present invention is polrvinyl chloride raw material and goods manufacturing commonly uses most: dimethyl phthalate (DMP), diethyl phthalate (DEP), dibutyl phthalate (DBP), diisobutyl phthalate (DIBP), phthalic acid two (2-methoxyl group) ethyl ester (DMEP), phthalic acid two (4-methyl-2-amyl group) ester (BMPP), phthalic acid two (2-ethyoxyl) ethyl ester (DEEP), diamyl phthalate (DPP), dihexylphthalate (DHXP), butyl benzyl phthalate (BBP), phthalic acid two (2-butoxy) ethyl ester (DBEP), dicyclohexyl phthalate (DCHP), phthalic acid two (2-ethyl) own ester (DEHP), diphenyl phthalate (DPhP), dinoctyl phthalate (DNOP), dinonyl phthalate (DNP).
It is experimentally verified that, adopts the above-mentioned analysis method of the present invention can 16 kinds of phthalic acid esters be measured simultaneously.The extract formula of the present invention is good to the effect of extracting of object, and the response rate is high, and measurement result is accurate, favorable reproducibility.Test process is simple to operate, consuming time short, and solvent acquisition amount is low, and automaticity is high, reduces the interference of phthalic acid ester in test environment.
As it was previously stated, the extract of phthalic acid ester at present selects to be mainly single formula, and solvent-oil ratio is big, extraction efficiency is low, insufficient sensitivity, operating process is loaded down with trivial details, extraction efficiency is not high, environment is unfriendly.The present invention adopts structure formula to be R1COOR2Ester and C5-C7Linear paraffin make a kind of high efficiency composition extract for extracting phthalic acid ester in polypropylene material by a certain percentage, two of which component synergism so that this compound extract has good effect for the extraction of the phthalic acid ester of trace in polypropylene.Compared with single solvent extract in prior art, the specific aim of the compound extract of the present invention is relatively strong, and the extraction efficiency of the phthalic acid ester in polypropylene is high, and the response rate is good.
It is highly sensitive that the compound extract adopting the present invention extracts the method for phthalic acid ester in polypropylene material, whole extraction process is simple to operate, the saving time, High Temperature High Pressure is not needed to extract, reduce operational risk, extend instrument service life, reduce running cost, increase automatization's factor, reduce the interference that in environment, experimental result is caused by phthalic acid ester.
The qualitative, quantitative that the compound extract of the present invention and the method for phthalic acid ester in polypropylene material that extracts are used for being applied to follow-up gas chromatography-mass spectrography is measured, can accurately determine in polypropylene kind and the content of contained phthalate compound, simple to operate, quick and the requirement of environmental protection can be met.
Detailed description of the invention
For making the present invention easier to understand, describing the present invention in detail below in conjunction with embodiment, these embodiments only play illustrative effect, it is not limited to the range of application of the present invention, NM specific experiment method in the following example, generally conventionally experimental technique carries out.
Embodiment
Trace Phthalate Acid Esters compound in polypropylene is oriented extraction for Accelerate solvent extraction method by the compound extract in the present invention, and the qualitative, quantitative of circulation of qi promoting phase-MS of going forward side by side measures.
Choose the polypropylene powder of middle petrochemical iy produced as test sample.The instrument adopted in test process has: Agilent6890N-5975B gas chromatograph-mass spectrometer (GC-MS, Agilent company of the U.S.)；ASE350 Accelerate solvent extraction instrument (ThermoFisher company of the U.S.)；KD200 Nitrogen evaporator (Hangzhou Ao Sheng Instrument Ltd.).
In experimentation, all glass drying ovens use ultra-pure water drip washing 3 times, acetone soak 1 hour after cleaning, and toast 2 hours, be cooled to room temperature standby at 250 DEG C.
Test process is divided into following step:
1. prepare extract:
Pipette chromatographically pure ethyl acetate, methyl acetate and normal hexane respectively to three solvent bottles of Accelerate solvent extraction instrument, extraction procedures sets the mixed proportion of extractant.
2. Accelerate solvent extraction:
Prepare the diameter polypropylene specimen granule at below 0.5mm.Accurately weigh 4.0g polypropylene specimen, be accurate to 0.001g.Bottom Accelerate solvent extraction pond, place supporting 0.45 μm microporous filter membrane, polypropylene specimen is moved in abstraction pool, screw abstraction pool upper cover, relevant position in embedding device, extract according to the method for table 1.Program execution drops to after room temperature until temperature after terminating, and takes out the extract automatically receiving in receiving bottle.
Table 1 Accelerate solvent extraction method
3. nitrogen blows concentration:
Being concentrated into by extract in receiving bottle nitrogen at 60 DEG C near dry, be settled to 1mL by ethyl acetate, ultrasonic 1min makes it fully dissolve, and treats that GC-MS analyzes
4. 16 kinds of phthalate compound standard solution preparations and Specification Curve of Increasing:
The standard substance of 16 kinds of phthalate compounds is configured to the stock solution of 1000mg/L with extract for solvent, is diluted to the standard solution that a series of concentration is 5mg/L, 10mg/L, 20mg/L, 40mg/L, 80mg/L further.Measure the standard solution of each concentration with gas phase-mass spectrography with heating schedule in table 2, draw out the standard curve of each phthalate compound.
Table 2 gas chromatogram heating schedule
| Programming rate (DEG C/min) | Temperature (DEG C) | Retention time (min) |
| - | 50(initial temperature) | 1 |
| 15 | 180 | 4 |
| 10 | 280 | 4 |
| 5 | 290(final temperature) | 4 |
5. sample test:
With gas phase-mass spectrography, testing sample solution is tested, analyze test result, obtain phthalate compound kind contained in polypropylene specimen and content.
The polypropylene powder of centering petrochemical iy produced carries out Accelerate solvent extraction, selecting method 2, analyzes according to entering gas chromatograph-mass spectrometer device after above-mentioned flow operations.Classification and content to the phthalic acid ester extracted are analyzed, and result is as shown in table 3.
Table 3 compound extract is to the extraction results (unit: μ g/g) of PAEs in polypropylene
To the extraction efficiency of Trace Phthalate Acid Esters in polypropylene, precision and the accuracy of detection method has been weighed in this embodiment in order to weigh compound extract in the present invention.Choose two mark-on levels (2.5,20 μ g/g) and polypropylene specimen has been carried out recovery testu.It is as follows that polypropylene specimen adds calibration method: accurately weighs 20.0g polypropylene specimen, adds the high concentration PAEs hybrid standard storing solution of different volumes, adds 10mL normal hexane and make solid sample all be submerged.After vortex oscillation instrument is sufficiently mixed, dry up with nitrogen, namely obtain mark-on series polypropylene specimen, seal, put in exsiccator standby.
5 parallel sample are done respectively, according to sample analysis step replication 5 times to adding each concentration of target.The accuracy of method represents with the response rate, and precision represents with relative standard deviation RSD.Analysis experimental data draws, in polypropylene specimen, the average recovery rate of 16 kinds of PAEs is 90.2%～111.0%, and relative standard deviation (n=5) is 2.1%～10.8%.It is shown that the veracity and precision of method is better, meet the requirement of trace detection.
6. the effect of extracting of different formulations extract compares
Adopt same test implementation method, different solvents as extract, the two kinds of polypropylene specimen collected are carried out Accelerate solvent extraction, analyze according to entering gas chromatograph-mass spectrometer device after above-mentioned flow operations.Using the PAEs total amount that extracts as criterion, Comparing extraction effect, result is as shown in table 4.The volume of the extract owing to using in Accelerate solvent extraction method is determined by the size of abstraction pool, use the abstraction pool of same specification, and set identical extraction conditions (temperature, time, cycle-index etc.), only need to revise kind and the proportioning of extract in program setting, the extract of different formulations can be used to extract.In table 4, the single extract of indication is and adopts identical extraction conditions, and the extract of single kind carries out the result extracted.
The effect of extracting of table 4 different formulations extract compares
As can be seen from Table 4, adopt compound extract provided by the invention for measuring Trace Phthalate Acid Esters content in polypropylene, improve more than 20% than the extraction efficiency of single extract formula.And Accelerate solvent extraction method saves solvent-oil ratio, shorten the detection time, reduce running cost, increase automatization's factor, reduce interference.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all within the spirit and principles in the present invention, any amendment of making, equivalent replacement, improvement etc., should be included within protection scope of the present invention.
Claims (11)
1. adopting compound extract to extract a method for phthalic acid ester in polypropylene material, wherein, it is R that described compound extract includes general structure1COOR2Ester and C5-C7Linear paraffin, wherein, R1For H or C1Alkyl, R2For C1-C2Alkyl.
2. method according to claim 1, it is characterised in that the temperature of described extraction is 85～110 DEG C；The time of described extraction is 3～7min.
3. method according to claim 1, it is characterised in that the flush volume of described extraction is 80%～120%；The purge time of described extraction is 100～130s.
4. the method according to any one in claims 1 to 3, it is characterised in that in described compound extract, described general structure is R1COOR2Ester and C5-C7The volume ratio of linear paraffin be 2.5～10:1.
5. method according to claim 4, it is characterised in that described general structure is R1COOR2Ester and C5-C7The volume ratio of linear paraffin be 4～6.67:1.
6. the method according to any one in claims 1 to 3, it is characterised in that described general structure is R1COOR2Ester include one or more in methyl formate, Ethyl formate, methyl acetate and ethyl acetate.
7. method according to claim 6, it is characterised in that described general structure is R1COOR2Ester be methyl acetate or ethyl acetate.
8. the method according to any one in claims 1 to 3, it is characterised in that described C5-C7Linear paraffin include one or more in pentane, normal hexane and normal heptane.
9. method according to claim 8, it is characterised in that described C5-C7Linear paraffin be normal hexane.
10. analyze a method for phthalic acid ester in polypropylene material, comprising:
(1) adopt in claim 1 to 9 and to extract the method for phthalic acid ester in polypropylene material described in any one；With
(2) gas phase-MS is adopted to measure kind and the content of phthalic acid ester in polypropylene material.
11. the method for phthalic acid ester in analysis polypropylene material according to claim 10, it is characterised in that described method also includes adopting Accelerate solvent extraction method that phthalic acid ester in polypropylene material is oriented extraction.
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Non-Patent Citations (4)
| Title |
|---|
| Simultaneous screening and determination eight phthalates in plastic products for food use by sonication-assisted extraction/GC–MS methods;Hao-Yu Shen;《Talanta》;20051231;第66卷;第734-739页 * |
| 仿真饰品中邻苯二甲酸酯类增塑剂的含量测定和迁移风险考察;赖莺等;《色谱》;20120731;第30卷(第7期);第647-653页 * |
| 快速溶剂萃取气相色谱/质谱联用测定塑料桌布中的邻苯二甲酸酯;楼佳;《化学研究》;20110331;第22卷(第2期);第65-67页 * |
| 超声波提取－分散固相萃取净化－气相色谱法测定紫菜中三丁基锡和三苯基锡;毛雪金等;《分析科学学报》;20121231;第28卷(第6期);第758页第1.3节 * |
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