CN103792307B - Measure phthalic acid ester content extract and application thereof in polrvinyl chloride product - Google Patents
Measure phthalic acid ester content extract and application thereof in polrvinyl chloride product Download PDFInfo
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- CN103792307B CN103792307B CN201210419415.3A CN201210419415A CN103792307B CN 103792307 B CN103792307 B CN 103792307B CN 201210419415 A CN201210419415 A CN 201210419415A CN 103792307 B CN103792307 B CN 103792307B
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Abstract
The invention discloses phthalic acid ester content extract in a kind of mensuration polrvinyl chloride product, it comprises ethyl acetate and C
1~ C
8alcohols.According to the present invention, compared to the methylene chloride single solvent extract adopted in prior art, the extract in the present invention have employed more hypotoxicity and the solvent of easily recycling, not only increases extraction efficiency, and has taken into account environmental protection principle; For the phthalic ester in Polyvinylchloride, extraction efficiency is high, and the recovery is good.According to method provided by the invention, not only can measure the phthalic ester in Polyvinylchloride efficiently, and whole testing process is simple to operate, the time is short, without the need to High Temperature High Pressure extraction, operational risk is low, can extend instrument serviceable life and reduce testing cost.
Description
Technical field
The present invention relates to detection field, be specifically related to one and be used for measuring phthalic ester extract and application thereof in polrvinyl chloride product.
Background technology
Polyvinylchloride has the outstanding features such as abundant raw material, manufacturing process be ripe, cheap, of many uses, has now become the second largest resins for universal use being only second to polyvinyl resin in the world, has accounted for 29% of World Synthetic Resin aggregate consumption.Polyvinylchloride is easily processed, and assigns to strengthen its thermotolerance, toughness, ductility etc. frequently by adding other one-tenth.Phthalic ester, also known as phthalate ester, is often added in Corvic, to increase its plasticity and pliability.
Phthalic ester is as a kind of adjuvant, and it is combined by means of only hydrogen bond or Van der Waals force with PVC base system resin, therefore in use can constantly to surface migration, loss transferring in surrounding environment.Along with the widespread use of plastic products, phthalic ester is prevalent in the environment of human lives: soil, water body, atmospheric dust etc.Phthalic ester is typical environmental estrogens pollutant, and Long Term Contact can affect human endocrine, can cause deformity, canceration and mutagenesis time serious, thus causes extensive concern both domestic and external in recent years.
Clearly show in American-European-Japanese regulation to forbid 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 USEPA (EPA) priority control in 190 kinds of noxious pollutant lists, phthalate has 4 kinds.The GB/T 21928-2008 bioassay standard of phthalic ester " in the food plastic wrappage " and the GB/T 22048-2008 bioassay standard of phthalate plasticizers " in toy and the articles for children igelite used " 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 soxhlet extraction, organic solvent dissolution-precipitation method extraction and microwave abstracting etc. are mainly contained to the extraction mode of adjuvant in plastic, rubber, wherein soxhlet extraction required time is long, operate comparatively loaded down with trivial details, organic solvent dissolution-precipitation method extraction specific aim is poor, major part adjuvant such as pigment etc. enters extract, interference detection results.Microwave abstracting efficiency is high, save solvent, operation semi-automation, preferablyly processes a large amount of sample.The selection of extract also directly affects extraction efficiency and effect.Select to be mainly single formula to the extract of phthalic ester at present, and solvent-oil ratio is large, extraction efficiency is not high, unfriendly to environment.
Summary of the invention
The present invention is intended to overcome prior art defect, the problem that the extraction efficiency solving in prior art phthalate compound in the Polyvinylchloride existed is low, reclaim rate variance, develop a kind of extract for phthalic ester in PVC samples, to reach simply, fast, accurately carry out the object of qualitative and quantitative detection, meet the requirement of environmental protection simultaneously.
According to an aspect of the present invention, provide phthalic acid ester content extract in a kind of mensuration polrvinyl chloride product, it comprises ethyl acetate and C
1~ C
5alcohols.
In above-mentioned extract, in described extract, the volume ratio of ethyl acetate and alcohols is 3:1 ~ 1: 1.Preferably, in described extract, the volume ratio of ethyl acetate and alcohols is 7:3 ~ 5:3.
In above-mentioned extract, described extract comprises ethyl acetate and C
1~ C
4alcohols.Described alcohols is as methyl alcohol, ethanol, propyl alcohol, butanols etc.Preferably, described extract comprises ethyl acetate and methyl alcohol.
In above-mentioned extract, described phthalic ester is selected from repefral, diethyl phthalate, dibutyl phthalate, diamyl phthalate, dihexylphthalate, butyl benzyl phthalate, dicyclohexyl phthalate, phthalic acid two (2-ethyl) own ester, diphenyl phthalate, di-n-octyl phthalate, diisobutyl phthalate, phthalic acid two (2-methoxyl) ethyl ester, dinonyl phthalate, phthalic acid two (2-ethoxy) ethyl ester, phthalic acid two (4-methyl-2-amyl group) ester, phthalic acid two (2-butoxy) ethyl ester, diisononyl phthalate and diisooctyl phthalate.
According to another aspect of the present invention, provide a kind of method measuring phthalic acid ester content in polrvinyl chloride product, comprise the following steps:
A) above-mentioned extract is configured;
B) microwave abstracting: polrvinyl chloride product is ground into particle, adds the extract in step a), extracts in microwave extracting apparatus;
C) constant volume: shift out the extract I after extraction in step b), leave residue, is extracted liquid II with the extract washing residue in step a), extract I and II is merged, obtain testing sample solution after constant volume;
D) standard solution and the drawing standard curve of phthalic ester is configured;
E) with gas phase-mass spectrography, the testing sample solution in step c) is tested.
In the above-mentioned methods, the temperature of described microwave abstracting is 30 DEG C ~ 110 DEG C, and the time is 10 ~ 30min.
In the above-mentioned methods, described phthalic ester is selected from repefral, diethyl phthalate, dibutyl phthalate, diamyl phthalate, dihexylphthalate, butyl benzyl phthalate, dicyclohexyl phthalate, phthalic acid two (2-ethyl) own ester, diphenyl phthalate, di-n-octyl phthalate, diisobutyl phthalate, phthalic acid two (2-methoxyl) ethyl ester, dinonyl phthalate, phthalic acid two (2-ethoxy) ethyl ester, phthalic acid two (4-methyl-2-amyl group) ester, phthalic acid two (2-butoxy) ethyl ester, diisononyl phthalate and diisooctyl phthalate.
In a specific embodiment of said method, the standard substance of 18 kinds of phthalate compounds take extract as the stock solution that solvent is mixed with 1000mg/L, be diluted to the standard solution that a series of concentration is 5mg/L, 10mg/L, 20mg/L, 40mg/L, 80mg/L further, then measure the standard solution of each concentration with gas phase-mass spectrography, draw out the typical curve of each phthalate compound.
According to the present invention, compared to the methylene chloride single solvent extract adopted in prior art, the extract in the present invention have employed more hypotoxicity and the solvent of easily recycling, not only increases extraction efficiency, and has taken into account environmental protection principle; For the phthalic ester in Polyvinylchloride, extraction efficiency is high, and the recovery is good.According to method provided by the invention, not only can measure the phthalic ester in Polyvinylchloride efficiently, and whole testing process is simple to operate, the time is short, without the need to High Temperature High Pressure extraction, operational risk is low, can extend instrument serviceable life and reduce testing cost.
Embodiment
Below the present invention be further described and describe, but not forming any limitation of the invention.
In the present invention, unless specially illustrated, otherwise the ratio of solvent is volume ratio.
In a specific embodiment, extract in the present invention is used for Microwave Digestion and carries out orientation extraction to the phthalate compound in Polyvinylchloride raw material and goods, go forward side by side promoting the circulation of qi phase-MS qualitative, quantitative measure, test process is divided into following step:
1) extract is prepared: pipette ethyl acetate and methyl alcohol to as in 250mL tool plug conical flask, mix, be mixed with extraction solution stand-by;
2) microwave abstracting: PVC samples is ground into the particle of diameter at below 0.5mm.Accurately take 0.1g sample, be accurate to 0.0001g, be placed in micro-wave diminishing pot, add 10ml extract, screw protective sleeve, put into microwave extracting apparatus and extract according to the condition of table 1.Program drops to after room temperature until temperature after performing and terminating, and takes out counteracting tank;
3) constant volume: take out extract I and move in 10mL volumetric flask, and be once extracted liquid II, combining extraction liquid I and II with fresh extract cleaning residue, constant volume, becomes testing sample solution;
4) 18 kinds of phthalate compound standard solution preparations and Specification Curve of Increasing: the standard substance of 18 kinds of phthalate compounds take extract as the stock solution that solvent is mixed with 1000mg/L, 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 typical curve of each phthalate compound;
5) sample test: test testing sample solution with gas phase-mass spectrography, analytical test result, obtains phthalate compound kind contained in PVC samples and content.
The temperature-time program of table 1 microwave abstracting
Table 2 gas chromatography heating schedule
Effect of extracting is weighed
Have employed the method that mark-on reclaims to verify, to weigh extract in the present invention to the extraction efficiency of phthalate material in PVC samples, get rid of the loss error of target substance in Polyvinylchloride process simultaneously.
Use the extract containing 100mL ethyl acetate and 50mL methyl alcohol.Make the PVC thin slice of known interpolation phthalic acid ester content of two roller extrusion molding, make the PVC sample that two other additionally adds 10g and 30g phthalic ester simultaneously, carry out analysis and detect, and 5 replicate determinations are carried out to each sample.Test result is as shown in table 3.
Table 3 tests recovery of standard addition and the relative standard deviation of PVC sample
As can be seen from Table 3, extract according to the present invention has extraordinary effect of extracting to the phthalic ester in Polyvinylchloride (PVC).
Extract compares
Adopting the identical different solvents of cumulative volume as extract, microwave abstracting being carried out to PVC samples, according to entering the analysis of gas chromatograph-mass spectrometer (GCMS) device after above-mentioned flow operations.With the content of the DEHP extracted for standard, Comparing extraction effect, result is as shown in table 4.
Table 4 effect of extracting compares
As can be seen from Table 4, adopt extract provided by the invention for measuring phthalic acid ester content in polrvinyl chloride product, not only improve about more than 20% than the extraction efficiency of methylene chloride of the prior art, and its volatility and toxicity are all low than methylene chloride of the prior art, therefore there is broad application prospect.
It should be noted that above-described embodiment only for explaining the present invention, not forming any limitation of the invention.By referring to exemplary embodiments, invention has been described, but to should be understood to word wherein used be descriptive and explanatory vocabulary, instead of limited vocabulary.Can modify the present invention by the scope being defined in the claims in the present invention, and the present invention be revised not deviating from scope and spirit of the present invention.Although the present invention wherein described relates to specific method, material and embodiment, and do not mean that the present invention is limited to particular case disclosed in it, on the contrary, easily extensible of the present invention is to other all methods and applications with identical function.
Claims (6)
1. measure a method for phthalic acid ester content in polrvinyl chloride product, comprise the following steps:
A) prepare extract, wherein, described extract comprises ethyl acetate and C
1~ C
5alcohols, in described extract, the volume ratio of described ethyl acetate and described alcohols is 3:1 ~ 1:1;
B) microwave abstracting: polrvinyl chloride product is ground into particle, add step a) in extract, extract in microwave extracting apparatus;
C) constant volume: shift out step b) in extract I after extraction, leave residue, extract in using step a) washing residue is extracted liquid II, extract I and II is merged, obtains testing sample solution after constant volume;
D) standard solution and the drawing standard curve of phthalic ester is prepared;
E) with gas phase-mass spectrography to step c) in testing sample solution test.
2. method according to claim 1, is characterized in that, the temperature of described microwave abstracting is 30 DEG C ~ 110 DEG C, and the time is 10 ~ 30min.
3. method according to claim 1 and 2, it is characterized in that, described phthalic ester is selected from repefral, diethyl phthalate, dibutyl phthalate, diamyl phthalate, dihexylphthalate, butyl benzyl phthalate, dicyclohexyl phthalate, phthalic acid two (2-ethyl) own ester, diphenyl phthalate, di-n-octyl phthalate, diisobutyl phthalate, phthalic acid two (2-methoxyl) ethyl ester, dinonyl phthalate, phthalic acid two (2-ethoxy) ethyl ester, phthalic acid two (4-methyl-2-amyl group) ester, phthalic acid two (2-butoxy) ethyl ester, diisononyl phthalate and diisooctyl phthalate.
4. method according to claim 1, is characterized in that, in described extract, the volume ratio of described ethyl acetate and described alcohols is 7:3 ~ 5:3.
5. method according to claim 1, is characterized in that, described extract comprises ethyl acetate and C
1~ C
4alcohols.
6. method according to claim 1, is characterized in that, described extract comprises ethyl acetate and methyl alcohol.
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| CN107982954A (en) * | 2016-10-26 | 2018-05-04 | 中国石油化工股份有限公司 | A kind of agent of tri compound microwave abstracting and its application |
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