CN108508109A - The detection method of content of acrylic acid high-carbon-alkyl - Google Patents
The detection method of content of acrylic acid high-carbon-alkyl Download PDFInfo
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Abstract
Present invention relates particularly to a kind of detection method of content of acrylic acid high-carbon-alkyl, the detection method of content is measured using high performance liquid chromatography, and specific detection method is as follows：(1) chromatographic condition, chromatographic column are using octadecylsilane chemically bonded silica as the chromatographic column of filler；Mobile phase is the mixed solvent of methanol, isopropanol and acetonitrile, isocratic elution；Detection wavelength is 200nm~220nm；(2) sample preparation weighs acrylic acid high-carbon-alkyl sample to be tested and standard items, is configured to certain density solution to be measured and standard solution；(3) sample detection detects solution and standard solution to be measured in liquid chromatograph, records chromatogram, and external standard method analyzes the content of acrylic acid high-carbon-alkyl sample to be tested.Detection method of content provided by the invention can effectively detect the content of acrylic acid high-carbon-alkyl class, and detection time is short, and have good linear relationship, and high sensitivity is suitable for the content detection of acrylic acid high-carbon-alkyl class.
Description
Technical field
The invention belongs to analytical chemistry detection method technical fields, and in particular to a kind of content of acrylic acid high-carbon-alkyl
Detection method.
Background technology
Alkyl acrylate is the major downstream product of acrylic acid, is generally divided into low-carbon alkyl and high-carbon-alkyl.Third
Olefin(e) acid low-carbon alkyl mainly has methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate and 2-ethyl hexyl acrylate,
Belong to conventional monomer, is the conventional products of acrylic acid industry, early has been achieved with large-scale industrial production.Acrylic acid high-carbon alkyl
Ester is primarily referred to as dodecyl acrylate, tetradecyl acrylate, Process Conditions of Cetane Acrylate and octadecyl acrylate etc., belongs to acrylic acid work
Function monomer in industry has a wide range of applications in field of fine chemical.
Contain polymerizable double bond and larger hydrophobic grouping in acrylic acid high-carbon-alkyl molecule, it can be utilized to it
He carries out hydrophobically modified by polymer segment；Itself can also be copolymerized.Meanwhile by changing ester group in molecule
Type expands its application field to change the structure and performance of polymer molecule.Acrylic acid high-carbon-alkyl is as modified single
Body is modified coating, adhesive etc., can assign the low shrinkage of product and high flexibility；With maleic anhydride or styrene
The copolymer of equal monomers can be used as excellent diesel oil or pour point depressant for crude oil, hence it is evident that improves the low temperature fluidity of oil product, expands
The big application range of oil product.The copolymer and homopolymer of acrylic acid high-carbon-alkyl are in adhesive, plastic plasticizer, water process
Antisludging agent, emulsifier, coating thickener, antifriction resistance-reduction agent etc. are also widely used；In recent years it has also been found that propylene
The amphipathic polymer that the monomer crosslinked copolymerization such as sour high-carbon-alkyl and acrylic acid, methacrylic acid generates, in functional gels material
Material, intelligent polymer material, medical compatibility material and separation material etc. have unique performance.
As acrylic acid high-carbon-alkyl is using more and more extensive, the content of acrylic acid high-carbon-alkyl how is detected,
At a problem to be solved.
In the prior art for the detection method of acrylate, most commonly used is gas chromatography,《Chemical analysis meter
Amount》It discloses in 2016,25 (3) " esters of acrylic acid in Ambient Air by Gas Chromatography " using gas chromatography, with
DB-624 superelevation inertia capillary columns are as chromatographic column, activated carbon adsorption, dichloromethane desorption, may be implemented methyl acrylate,
The separation of ethyl acrylate, methyl methacrylate, propyl acrylate, butyl acrylate, Isooctyl acrylate monomer.However this point
Analysis method may be only available for the acrylic acid low-carbon alkyl for being easy gasification, not for the acrylic acid high-carbon-alkyl that is difficult to gasify
It is applicable in.
Currently, being mostly by ester-interchange method and direct esterification, instead for the preparation method of acrylic acid high-carbon-alkyl
After answering, thick ester obtains acrylic acid high-carbon-alkyl product through filtering, alkali cleaning, removing catalyst and polymerization inhibitor.It is synthesizing
To after high-carbon-alkyl, laboratory is identified or GC- using FT-IR Fourier Transform Infrared Spectrometer at present
MS is identified.The acrylic acid high-carbon-alkyl for still lacking simple and effective, such as dodecyl acrylate, tetradecyl acrylate, propylene
The quantitative detecting method of sour hexadecyl ester and octadecyl acrylate.
Invention content
In order to solve the acrylic acid high-carbon-alkyl for lacking simple and effective in the prior art, such as dodecyl acrylate, propylene
The problem of quantitative detecting method of sour 14 esters, Process Conditions of Cetane Acrylate and octadecyl acrylate, the present invention provides a kind of propylene
The detection method of content of sour high-carbon-alkyl.The technical problem to be solved in the present invention is achieved through the following technical solutions：
The detection method of content of acrylic acid high-carbon-alkyl, the detection method of content are carried out using high performance liquid chromatography
It measures, which is characterized in that specific detection method is as follows：
(1) chromatographic condition
Chromatographic column is using octadecylsilane chemically bonded silica as filler；
For mobile phase using methanol as mobile phase A, isopropanol is Mobile phase B, and acetonitrile is mobile phase D, isocratic elution；
Column temperature is 25 DEG C~35 DEG C；
Flow rate of mobile phase is 0.5mL/min~1.5mL/min；
The Detection wavelength of UV detector is 200nm~220nm；
(2) sample preparation
Acrylic acid high-carbon-alkyl sample to be tested and standard items are weighed, are configured to certain density wait for respectively with suitable solvent
Solution and standard solution are surveyed, the suitable solvent is at least one of methanol, isopropanol or acetonitrile；
(3) sample detection
Solution and standard solution to be measured are detected in liquid chromatograph, record chromatogram, it is high that external standard method analyzes acrylic acid
The content of carbon Arrcostab sample to be tested.
Further, in the detection method of content of acrylic acid high-carbon-alkyl of the present invention, the chromatographic condition
The volume ratio of mobile phase A, Mobile phase B and mobile phase D is 60~70 in mobile phase：15~25：15~5.
Further, in the detection method of content of acrylic acid high-carbon-alkyl of the present invention, the detection method
Chromatographic column is C in chromatographic condition18Reverse-phase chromatographic column, specification are 250mm × 4.6mm × 5 μm.
Further, in the detection method of content of acrylic acid high-carbon-alkyl of the present invention, the detection method
The flow velocity of mobile phase is 0.8mL/min~1.0mL/min in chromatographic condition.
Further, in the detection method of content of acrylic acid high-carbon-alkyl of the present invention, the detection method
The Detection wavelength of UV detector is 200nm~210nm in chromatographic condition.
Further, in the detection method of content of acrylic acid high-carbon-alkyl of the present invention, the sample preparation
Detailed process is：
(2-1) precision weighs quantitative acrylic acid high-carbon-alkyl standard items, is dissolved and is configured to a series of with suitable solvent
The standard solution of gradient concentration, the suitable solvent are at least one of methanol, isopropanol or acetonitrile, a series of ladders
The concentration range for spending the standard solution of concentration is 100mg/L~700mg/L；
(2-2) precision weighs quantitative acrylic acid high-carbon-alkyl sample to be tested, is dissolved and is configured to certain with suitable solvent
The solution to be measured of concentration, the suitable solvent are at least one of methanol, isopropanol or acetonitrile, wherein described a certain concentration
For 100mg/L~700mg/L.
Further, in the detection method of content of acrylic acid high-carbon-alkyl of the present invention, in the step (2-2)
After precision weighing acrylic acid high-carbon-alkyl sample to be tested, higher alcohols impurity first is removed with deep eutectic solvent washing sample, then
The solution to be measured of a concentration of 400mg/L is dissolved and is configured to suitable solvent, and the suitable solvent is methanol, isopropanol or acetonitrile
At least one of；The depth eutectic solvent is choline chloride and the deep eutectic solvent that glycerine mixing generates.
Further, in the detection method of content of acrylic acid high-carbon-alkyl of the present invention, take the standard items molten
Liquid injects liquid chromatograph, and it is about the 10% of recorder full scale to make principal component peak height.
Further, in the detection method of content of acrylic acid high-carbon-alkyl of the present invention, the sample detection
Detailed process is：
(3-1) prepares standard curve
Precision measures a series of standard solution of gradient concentrations, according to the chromatographic condition of setting, record standard after sample introduction
The chromatogram of product solution draws the linear of chromatographic signal and concentration then according to the chromatogram of the standard solution of series concentration
Relevant criterion working curve；
(3-2) detects sample to be tested
Precision measures in the solution to be measured injection high performance liquid chromatograph isometric with standard solution, records chromatogram,
Chromatographic signal is brought into the standard working curve obtained by step (3-1), obtains the concentration of sample to be tested, and then be calculated to be measured
The content of acrylic acid high-carbon-alkyl in sample.
Further, in the detection method of content of acrylic acid high-carbon-alkyl of the present invention, the detection method
Chromatographic condition is：
Chromatographic column is using octadecylsilane chemically bonded silica as filler；
The volume ratio of mobile phase methanol, isopropanol and acetonitrile is 70：25：5.
Column temperature is 30 DEG C；
Flow rate of mobile phase is 1mL/min；
The Detection wavelength of UV detector is 208nm；
Sample size is 20 μ of μ L~50 L；
Retention time is twice of main peak retention time.
" acrylic acid high-carbon-alkyl " of the present invention refers to higher alcohols and propylene at least 12 carbon atoms
The ester that acid is formed.For example, dodecyl acrylate, tetradecyl acrylate, Process Conditions of Cetane Acrylate and octadecyl acrylate.
" C of the present invention18Reverse-phase chromatographic column " refers to octadecylsilane chemically bonded silica column.
Compared with prior art, beneficial effects of the present invention：
Detection method of content provided by the invention can effectively detect the content of acrylic acid high-carbon-alkyl, detection time
It is short, and there is good linear relationship, high sensitivity, and with preferable repeatability and accuracy, it is suitable for acrylic acid high-carbon
The quick content detection of alkyl esters has filled up this field and has lacked effective acrylic acid high-carbon-alkyl detection method of content at present
Technological gap.
Specifically, the retention time of acrylic acid high-carbon-alkyl is 5~11 in detection method of content provided by the invention
In minute, detection time is short, and the related coefficient of standard working curve is all higher than 0.999, has preferable linear relationship；The inspection
The detection of survey method is limited to 0.000015~0.00627mg/L, has high sensitivity, is adapted for use in content detection；This hair
Average recovery of standard addition in the detection method of content of bright offer is 94.6%~115.7%, and testing result has compared with high precision
Degree；It repeats to detect, the relative standard deviation of experimental result is 0.054%~0.770%, it was demonstrated that this method has higher repetition
Property.This method is simple, accurate, the quick detection of acrylic acid high-carbon-alkyl class suitable for real work.
Description of the drawings
Fig. 1 is the HPLC collection of illustrative plates that embodiment 1 detects dodecyl acrylate standard items
Fig. 2 is the HPLC collection of illustrative plates that embodiment 1 detects dodecyl acrylate sample to be tested.
Fig. 3 is the HPLC collection of illustrative plates that embodiment 3 detects tetradecyl acrylate standard items.
Fig. 4 is the HPLC collection of illustrative plates that embodiment 3 detects tetradecyl acrylate sample to be tested.
Fig. 5 is the HPLC collection of illustrative plates that embodiment 5 detects Process Conditions of Cetane Acrylate standard items.
Fig. 6 is the HPLC collection of illustrative plates that embodiment 5 detects Process Conditions of Cetane Acrylate sample to be tested.
Fig. 7 is the HPLC collection of illustrative plates that embodiment 7 detects octadecyl acrylate standard items.
Fig. 8 is the HPLC collection of illustrative plates that embodiment 7 detects octadecyl acrylate sample to be tested.
Specific implementation mode
Further detailed description is done to the present invention with reference to specific embodiment, but embodiments of the present invention are not limited to
This.The embodiment of the present invention is merely to illustrate the present invention and provides, rather than limiting the invention, so, the present invention's
Any improvement in the present invention belongs to the scope of protection of the invention under the premise of method.
Acetonitrile, methanol and isopropanol are chromatographically pure rank in the mobile phase of efficient liquid phase in following embodiment.Acrylic acid
Dodecyl ester standard items, acrylic acid tetradecane base ester standard items, aliphatic acrylate standard items, octadecyl base
Ester standard items derive from Beijing lark prestige Science and Technology Ltd..
Without specified otherwise in embodiment, the temperature in embodiment is set temperature, and it is ± 3 DEG C to allow temperature error.
This detection method is the external standard method of analytical chemistry field, the mode of operation in following experimentation and test method,
It is not described in detail, is all made of Standard Operating Procedure, such as solution is prepared, solid concussion washing, system suitability examination
The operating method tested.
(1) acrylic acid high-carbon-alkyl content detection embodiment
Embodiment 1：The detection method of content of dodecylacrylate
(1) chromatographic condition
Instrument：Sai Mo flies LPG3400 high performance liquid chromatographs；
Chromatographic column：C18Reverse-phase chromatographic column (250mm × 4.6mm × 5 μm)
Mobile phase：Using methanol as mobile phase A, the isopropanol of chromatographically pure is Mobile phase B, and it is mobile phase D to compose pure acetonitrile, is pressed
According to mobile phase A：Mobile phase B：The volume ratio of mobile phase D is 70：25：5 carry out isocratic elution；
Column temperature：30℃；
The flow velocity 1.0mL/min of mobile phase；
The Detection wavelength of UV detector：208nm.
(2) sample preparation
(2-1) precision weighs quantitative dodecylacrylate standard items, is with methanol, isopropanol and acetonitrile volume ratio
70：25：5 mixed solvent dissolves and is configured to a series of standard solution of gradient concentrations, concentration be respectively 100mg/L,
The standard solution of 200mg/L, 300mg/L, 400mg/L, 500mg/L, 600mg/L, 700mg/L, specific mode of operation are pressed
According to analytical chemistry standard operation dissolved, constant volume.
(2-2) precision weighs quantitative dodecylacrylate sample to be tested 7mg, in molar ratio with choline chloride and glycerine
1:The deep eutectic solvent and sample in mass ratio 2 that 2 mixing generate:1 mixing, fully shaking, washing sample remove higher alcohols, fully
It stands, takes supernatant, then use methanol or methanol/isopropanol (v/v=70：Or methanol/isopropanol/acetonitrile (v/v/v=30)
70：25：5) mixed solvent dissolves and is configured to the solution to be measured of a concentration of 700mg/L.
Deep eutectic solvent belongs to ion solvent, can will be present in acrylic acid high-carbon-alkyl sample, in preparation process
The higher alcohols dissolving of introducing removes, and higher alcohols are easy to be trapped in liquid-phase chromatographic column, it is difficult to be removed, influence the follow-up of chromatographic column
It uses.
(3) sample detection
(3-1) prepares standard curve
A series of standard solution that precision measures gradient concentrations is recorded according to the chromatographic condition of setting after 20 μ L of sample introduction
The chromatogram of standard solution obtains chromatogram shown in Fig. 1 (concentration 700mg/L), dodecylacrylate retention time
For 5.352min.Then according to the chromatogram of the standard solution of series concentration, draw chromatographic signal (peak area mAU*min) with
The linearly related standard curve of concentration (mg/L).
Dodecylacrylate linear correlation standard curve y=1.3684x+0.9981, R1=0.9995；Standard works
The coefficient R of curve1More than 0.999, it was demonstrated that the method linear relationship within the scope of concentration 100mg/L~700mg/L is good.
(3-2) detects sample to be tested
Precision measures in 20 μ L injection high performance liquid chromatographs of solution to be measured, chromatogram is recorded, as shown in Fig. 2, acrylic acid
Dodecyl ester retention time is 5.325min.According to said method sample introduction in triplicate, obtained chromatogram baseline is steady, repeats
Property it is good, retention time be 5.348 ± 0.017min.
Chromatographic signal is brought into linearly related standard curve, according to the computational methods of external standard method, obtains the dense of sample to be tested
Degree is 711.278mg/L, passes through formula：N=CV, n=711.278*0.1L, obtain n=71.1278mol, and wherein n is exactly not
Dilute the amount of dodecylacrylate in dodecylacrylate sample.
Embodiment 2：The detection method of content of dodecylacrylate
The present embodiment is similar with 1 detailed process of embodiment, and difference place is (1) chromatographic condition
Instrument：Sai Mo flies LPG3400 high performance liquid chromatographs；
Chromatographic column：C18Reverse-phase chromatographic column (250mm × 4.6mm × 5 μm)；
Mobile phase：Using methanol as mobile phase A, the isopropanol of chromatographically pure is Mobile phase B, and it is mobile phase D to compose pure acetonitrile, is pressed
According to mobile phase A：Mobile phase B：The volume ratio of mobile phase D is 65：25：10 carry out isocratic elution；
Column temperature：25℃；
The flow velocity 1.8mL/min of mobile phase；
The Detection wavelength of UV detector：210nm.
Content according to the dodecylacrylate sample to be tested measured by the chromatographic condition is same as Example 1.
Embodiment 3：The detection method of content of acrylic acid tetradecane base ester
(1) chromatographic condition
Instrument：Sai Mo flies LPG3400 high performance liquid chromatographs；
Chromatographic column：C18Reverse-phase chromatographic column (250mm × 4.6mm × 5 μm)
Mobile phase：Using methanol as mobile phase A, the isopropanol of chromatographically pure is Mobile phase B, and it is mobile phase D to compose pure acetonitrile, is pressed
According to mobile phase A：Mobile phase B：The volume ratio of mobile phase D is 70：25：5 carry out isocratic elution；
Column temperature：30℃；
The flow velocity 1.0mL/min of mobile phase；
The Detection wavelength of UV detector：208nm.
(2) sample preparation
(2-1) precision weighs quantitative acrylic acid tetradecane base ester standard items, is with methanol, isopropanol and acetonitrile volume ratio
70：25：5 mixed solvent dissolves and is configured to a series of standard solution of gradient concentrations, concentration be respectively 100mg/L,
The standard solution of 200mg/L, 300mg/L, 400mg/L, 500mg/L, 600mg/L, 700mg/L, specific mode of operation are pressed
According to analytical chemistry standard operation dissolved, constant volume.
(2-2) precision weighs quantitative acrylic acid tetradecane base ester sample to be tested 7mg, in molar ratio with choline chloride and glycerine
1:The deep eutectic solvent and sample in mass ratio 2 that 2 mixing generate:1 mixing, fully shaking, washing sample remove higher alcohols, fully
It stands, takes supernatant, then use methanol or methanol/isopropanol (v/v=70：Or methanol, isopropanol and acetonitrile (v/v/v=30)
70：25：5) mixed solvent dissolves and is configured to the solution to be measured of a concentration of 700mg/L.
Deep eutectic solvent belongs to ion solvent, can dissolve higher alcohols and remove, higher alcohols are easy to be trapped in liquid chromatogram
In column, it is difficult to be removed, influence the follow-up use of chromatographic column.
(3) sample detection
(3-1) prepares standard curve
A series of standard solution that precision measures gradient concentrations is recorded according to the chromatographic condition of setting after 20 μ L of sample introduction
The chromatogram of standard solution, obtains chromatogram shown in Fig. 3 (concentration 700mg/L), when the reservation of acrylic acid tetradecane base ester
Between be 6.493min.Then according to the chromatogram of the standard solution of series concentration, chromatographic signal (peak area mAU*min) is drawn
With the linearly related standard curve of concentration (mg/L).
The acrylic acid tetradecane base ester linear correlation standard curve y=0.2748x+4.2317, R2=0.9992；Standard works
The coefficient R of curve2More than 0.999, it was demonstrated that the method linear relationship within the scope of concentration 100mg/L~700mg/L is good.
(3-2) detects sample to be tested
Precision measures in 20 μ L injection high performance liquid chromatographs of solution to be measured, chromatogram is recorded, as shown in figure 4, acrylic acid
The retention time of tetradecane base ester is 6.483min.According to said method sample introduction in triplicate, obtained chromatogram baseline is steady, weight
Renaturation is good, and retention time is 6.483 ± 0.015min.
Chromatographic signal is brought into linearly related standard curve, according to the computational methods of external standard method, obtains the dense of sample to be tested
Degree is 699.819mg/L, passes through formula：N=CV, n=699.819*0.1L, obtain n=69.9819mol, and wherein n is exactly not
Dilute the amount of acrylic acid tetradecane base ester in acrylic acid tetradecane base ester sample.
Embodiment 4：The detection method of content of acrylic acid tetradecane base ester
The present embodiment is similar with 3 detailed process of embodiment, and difference place is (1) chromatographic condition
Instrument：Sai Mo flies LPG3400 high performance liquid chromatographs；
Chromatographic column：C18Reverse-phase chromatographic column (250mm × 4.6mm × 5 μm)；
Mobile phase：Using methanol as mobile phase A, the isopropanol of chromatographically pure is Mobile phase B, and it is mobile phase D to compose pure acetonitrile, is pressed
According to mobile phase A：Mobile phase B：The volume ratio of mobile phase D is 60：25：15 carry out isocratic elution；
Column temperature：25℃；
The flow velocity 1.8mL/min of mobile phase；
The Detection wavelength of UV detector：220nm.
Content according to the acrylic acid tetradecane base ester sample to be tested measured by the chromatographic condition is same as Example 3.
Embodiment 5：The detection method of content of aliphatic acrylate
(1) chromatographic condition
Instrument：Sai Mo flies LPG3400 high performance liquid chromatographs；
Chromatographic column：C18 reverse-phase chromatographic columns (250mm × 4.6mm × 5 μm)
Mobile phase：Using methanol as mobile phase A, the isopropanol of chromatographically pure is Mobile phase B, and it is mobile phase D to compose pure acetonitrile, is pressed
According to mobile phase A：Mobile phase B：The volume ratio of mobile phase D is 70：25：5 carry out isocratic elution；
Column temperature：30℃；
The flow velocity 1.0mL/min of mobile phase；
The Detection wavelength of UV detector：208nm.
(2) sample preparation
(2-1) precision weighs quantitative aliphatic acrylate standard items, is with methanol, isopropanol and acetonitrile volume ratio
70:25:5 mixed solvent dissolves and is configured to a series of standard solution of gradient concentrations, concentration be respectively 100mg/L,
The standard solution of 200mg/L, 300mg/L, 400mg/L, 500mg/L, 600mg/L, 700mg/L, specific mode of operation are pressed
According to analytical chemistry standard operation dissolved, constant volume.
(2-2) precision weighs quantitative aliphatic acrylate sample to be tested 7mg, in molar ratio with choline chloride and glycerine
1:The deep eutectic solvent and sample in mass ratio 2 that 2 mixing generate:1 mixing, fully shaking, washing sample remove higher alcohols, fully
It stands, takes supernatant, then use methanol or methanol, isopropanol (v/v=70：Or methanol, isopropanol and acetonitrile (v/v/v=30)
70：25：5) mixed solvent dissolves and is configured to the solution to be measured of a concentration of 700mg/L.
Deep eutectic solvent belongs to ion solvent, can dissolve higher alcohols and remove, higher alcohols are easy to be trapped in liquid chromatogram
In column, it is difficult to be removed, influence the follow-up use of chromatographic column.
(3) sample detection
(3-1) prepares standard curve
A series of standard solution that precision measures gradient concentrations is recorded according to the chromatographic condition of setting after 20 μ L of sample introduction
The chromatogram of standard solution, obtains chromatogram shown in Fig. 5 (concentration 700mg/L), when the reservation of aliphatic acrylate
Between be 8.01min.Then according to the chromatogram of the standard solution of series concentration, chromatographic signal (peak area mAU*min) is drawn
With the linearly related standard curve of concentration (mg/L).
Aliphatic acrylate linear correlation standard curve y=0.2465x+5.6431, R3=0.9995；Standard works
The coefficient R of curve3More than 0.999, it was demonstrated that the method linear relationship within the scope of concentration 100mg/L~700mg/L is good.
(3-2) detects sample to be tested
Precision measures in 20 μ L injection high performance liquid chromatographs of solution to be measured, chromatogram is recorded, as shown in fig. 6, acrylic acid
The retention time of cetyl ester is 8.00min.According to said method sample introduction in triplicate, obtained chromatogram baseline is steady, weight
Renaturation is good, and retention time is 7.993 ± 0.02min.
Chromatographic signal is brought into linearly related standard curve, according to the computational methods of external standard method, obtains the dense of sample to be tested
Degree is 459.845mg/L, passes through formula：N=CV, n=459.845*0.1L, obtain n=45.9845mol, and wherein n is exactly not
Dilute the amount of aliphatic acrylate in aliphatic acrylate sample.
Embodiment 6：The detection method of content of aliphatic acrylate
The present embodiment is similar with 5 detailed process of embodiment, and difference place is (1) chromatographic condition
Instrument：Sai Mo flies LPG3400 high performance liquid chromatographs；
Chromatographic column：C18Reverse-phase chromatographic column (250mm × 4.6mm × 5 μm)；
Mobile phase：Using methanol as mobile phase A, the isopropanol of chromatographically pure is Mobile phase B, and it is mobile phase D to compose pure acetonitrile, is pressed
According to mobile phase A：Mobile phase B：The volume ratio of mobile phase D is 70：15：15 carry out isocratic elution；
Column temperature：25℃；
The flow velocity 1.8mL/min of mobile phase；
The Detection wavelength of UV detector：210nm.
Content according to the aliphatic acrylate sample to be tested measured by the chromatographic condition is same as Example 5.
Embodiment 7：The detection method of content of octadecyl acrylate
(1) chromatographic condition
Instrument：Sai Mo flies LPG3400 high performance liquid chromatographs；
Chromatographic column：C18Reverse-phase chromatographic column (250mm × 4.6mm × 5 μm)
Mobile phase：Using methanol as mobile phase A, the isopropanol of chromatographically pure is Mobile phase B, and it is mobile phase D to compose pure acetonitrile, is pressed
According to mobile phase A：Mobile phase B：The volume ratio of mobile phase D is 70：25：5 carry out isocratic elution；
Column temperature：30℃；
The flow velocity 1.0mL/min of mobile phase；
The Detection wavelength of UV detector：200nm.
(2) sample preparation
(2-1) precision weighs quantitative octadecyl acrylate standard items, is with methanol, isopropanol and acetonitrile volume ratio
70:25:5 mixed solvent dissolves and is configured to a series of standard solution of gradient concentrations, concentration be respectively 100mg/L,
The standard solution of 200mg/L, 300mg/L, 400mg/L, 500mg/L, 600mg/L, 700mg/L, specific mode of operation are pressed
According to analytical chemistry standard operation dissolved, constant volume.
(2-2) precision weighs quantitative octadecyl acrylate sample to be tested 7mg, in molar ratio with choline chloride and glycerine
1:The deep eutectic solvent and sample in mass ratio 2 that 2 mixing generate:1 mixing, fully shaking, washing sample remove higher alcohols, fully
It stands, takes supernatant, then use methanol or methanol, isopropanol (v/v=70：Or methanol, isopropanol and acetonitrile (v/v/v=30)
70：25：5) mixed solvent dissolves and is configured to the solution to be measured of a concentration of 700mg/L.
Deep eutectic solvent belongs to ion solvent, can dissolve higher alcohols and remove, higher alcohols are easy to be trapped in liquid chromatogram
In column, it is difficult to be removed, influence the follow-up use of chromatographic column.
(3) sample detection
(3-1) prepares standard curve
A series of standard solution that precision measures gradient concentrations is recorded according to the chromatographic condition of setting after 20 μ L of sample introduction
The chromatogram of standard solution, obtains chromatogram shown in Fig. 7 (concentration 700mg/L), when the reservation of octadecyl acrylate
Between be 10.140min.Then according to the chromatogram of the standard solution of series concentration, chromatographic signal (peak area mAU* is drawn
Min) with the linearly related standard curve of concentration (mg/L).
Octadecyl acrylate linear correlation standard curve y=0.2319x+4.0978, R4=0.9999；Standard works
The coefficient R of curve4More than 0.999, it was demonstrated that the method linear relationship within the scope of concentration 100mg/L~700mg/L is good.
(3-2) detects sample to be tested
Precision measures in 20 μ L injection high performance liquid chromatographs of solution to be measured, chromatogram is recorded, as shown in figure 8, acrylic acid
The retention time of stearyl line is 10.117min.According to said method sample introduction, obtained chromatogram baseline are flat in triplicate
Surely, reproducible, retention time is 10.145 ± 0.007min.
Chromatographic signal is brought into linearly related standard curve, according to the computational methods of external standard method, obtains the dense of sample to be tested
Degree is 447.739mg/L, passes through formula：N=CV, n=447.739*0.1L, obtain n=44.7739mol, and wherein n is exactly not
Dilute the amount of octadecyl acrylate sample octadecyl acrylate.
Embodiment 8：The detection method of content of octadecyl acrylate
The present embodiment is similar with 7 detailed process of embodiment, and difference place is (1) chromatographic condition
Instrument：Sai Mo flies LPG3400 high performance liquid chromatographs；
Chromatographic column：C18Reverse-phase chromatographic column (250mm × 4.6mm × 5 μm)；
Mobile phase：Using methanol as mobile phase A, the isopropanol of chromatographically pure is Mobile phase B, and it is mobile phase D to compose pure acetonitrile, is pressed
According to mobile phase A：Mobile phase B：The volume ratio of mobile phase D is 70：20：10 carry out isocratic elution；
Column temperature：25℃；
The flow velocity 1.8mL/min of mobile phase；
The Detection wavelength of UV detector：220nm.
Content according to the octadecyl acrylate sample to be tested measured by the chromatographic condition is same as Example 7.
It is found through experiments that, can reach impurity and acrylic acid high-carbon alkyl by isocratic elution according to above-mentioned chromatographic condition
Ester is precisely separating, in 0 to 20 minutes can appearance, detection rapidly and efficiently, and have good linear relationship, Ke Yiyong
In content detection.
(2) liquid chromatography carries out the methodology validation of acrylic acid high-carbon-alkyl content detection
Methodology validation is carried out to the detection method according to this field routine test mode, mainly investigates the detection method
Detection limit, precision and the rate of recovery determine and use detection method sample concentration range applicatory, the accuracy of experimental result
And reproducibility.
(1) detection limit
According to method detection limit calculation formula MDL=3.143 × δ specified in U.S. EPA SW-846, (δ is empty to detection limit
The standard deviation that white sample replication is 6 times).The experimental result for detecting limit is as shown in table 1.
The detection limit experimental result of 1 acrylic acid high-carbon-alkyl of table
| Serial number | Title | Retention time (min) | Detection limit (mg/L) |
| 1 | Dodecyl acrylate | 5.348±0.017 | 0.00627 |
| 2 | Tetradecyl acrylate | 6.483±0.015 | 0.00081 |
| 3 | Process Conditions of Cetane Acrylate | 7.993±0.02 | 0.000015 |
| 4 | Octadecyl acrylate | 10.145±0.007 | 0.00089 |
By 1 experimental result of table it is found that the detection of the detection method is limited to 0.000015~0.00627mg/L, there is height
Sensitivity is adapted for use in content detection.
(2) precision
To keep the data obtained representative, dodecyl acrylate, tetradecyl acrylate, acrylic acid 16 are prepared respectively
The 200mg/L sample solutions of ester, octadecyl acrylate, added in the range of linearity high (600mg/L), in (300mg/L), low
The standard solution of (100mg/L) three concentration, it is each to add in 0.1mL to 10mL volumetric flasks, then carry out constant volume with sample solution.Often
3 repetitions are arranged in a concentration, and the 20 μ L of sample introduction in high performance liquid chromatograph are carried out respectively according to the experimental method of Examples 1 to 4
It measures, records chromatogram, be utilized respectively and calculate separately recovery of standard addition, experimental result is as shown in table 2.
The recovery of standard addition of 2 method of table investigates experimental result (n=6)
By the experimental result of table 2 it is found that recovery of standard addition is between 94.6%~115.7%, it was demonstrated that detection side of the invention
Method testing result has high accuracy.
(3) repeated
It is molten accurately to weigh dodecyl acrylate, tetradecyl acrylate, Process Conditions of Cetane Acrylate, the standard items of octadecyl acrylate
Liquid is configured to the solution of a concentration of 100mg/L, 300mg/L, 600mg/L respectively, distinguishes according to the experimental method of Examples 1 to 4
It is measured, each sample parallel determination 6 times, the 20 μ L of sample introduction in high performance liquid chromatograph, records chromatogram, investigate main peak
Peak area changes, and calculates RSD, and experimental result is as shown in table 3.
The precision of 3 method of table investigates (n=6)
By the experimental result of table 3 it is found that the relative standard deviation (RSD) of this method is 0.054%~0.770%, show
This method acquired results repeatability is higher, and Detection accuracy is influenced smaller by enchancement factor.
System above usability the experiment proves that, acrylic acid high-carbon-alkyl in detection method of content provided by the invention
For retention time in 5~11 minutes, detection time is short, and the related coefficient of standard working curve is all higher than 0.999, has preferable
Linear relationship；The detection of the detection method is limited to 0.000015~0.00627mg/L, has high sensitivity, is suitable for using
In content detection.
Recovery of standard addition in detection method of content provided by the invention is 94.6%~115.7%, and testing result has
High accuracy；It repeats to detect, the relative standard deviation (RSD) of experimental result is 0.054%~0.770%, it was demonstrated that this method
With higher precision.This method is simple, accurate, the quick content of acrylic acid high-carbon-alkyl class suitable for real work
Detection.
The above content is a further detailed description of the present invention in conjunction with specific preferred embodiments, and it cannot be said that
The specific implementation of the present invention is confined to these explanations.For those of ordinary skill in the art to which the present invention belongs, exist
Under the premise of not departing from present inventive concept, a number of simple deductions or replacements can also be made, all shall be regarded as belonging to the present invention's
Protection domain.
Claims (9)
1. the detection method of content of acrylic acid high-carbon-alkyl, the detection method of content is surveyed using high performance liquid chromatography
It is fixed, which is characterized in that specific detection method is as follows：
(1) chromatographic condition
Chromatographic column is using octadecylsilane chemically bonded silica as filler；
For mobile phase using methanol as mobile phase A, isopropanol is Mobile phase B, and acetonitrile is mobile phase D, isocratic elution；
Column temperature is 25 DEG C~35 DEG C；
Flow rate of mobile phase is 0.5mL/min~1.5mL/min；
The Detection wavelength of UV detector is 200nm~220nm；
(2) sample preparation
Acrylic acid high-carbon-alkyl sample to be tested and standard items are weighed, are configured to respectively with suitable solvent certain density to be measured molten
Liquid and standard solution, the suitable solvent are at least one of methanol, isopropanol or acetonitrile；
(3) sample detection
Solution and standard solution to be measured are detected in liquid chromatograph, records chromatogram, and external standard method analyzes acrylic acid high-carbon alkane
The content of base ester sample to be tested.
2. the detection method of content of acrylic acid high-carbon-alkyl according to claim 1, which is characterized in that the detection side
The volume ratio of mobile phase A, Mobile phase B and mobile phase D is 60~70 in the chromatographic condition of method：15~25：15~5.
3. the detection method of content of acrylic acid high-carbon-alkyl according to claim 2, which is characterized in that the detection side
Chromatographic column is C in the chromatographic condition of method18Reverse-phase chromatographic column, specification are 250mm × 4.6mm × 5 μm.
4. the detection method of content of acrylic acid high-carbon-alkyl according to claim 1, which is characterized in that the detection side
The flow velocity of mobile phase is 0.8mL/min~1.0mL/min in the chromatographic condition of method.
5. the detection method of content of acrylic acid high-carbon-alkyl according to claim 1, which is characterized in that the detection side
The Detection wavelength of UV detector is 200nm~210nm in the chromatographic condition of method.
6. the detection method of content of acrylic acid high-carbon-alkyl according to claim 1, which is characterized in that the sample is matched
The detailed process of system is：
(2-1) precision weighs quantitative acrylic acid high-carbon-alkyl standard items, is dissolved with suitable solvent and is configured to a series of gradients
The standard solution of concentration, the suitable solvent are at least one of methanol, isopropanol or acetonitrile, and a series of gradients are dense
The concentration range of the standard solution of degree is 100mg/L~700mg/L；
(2-2) precision weighs quantitative acrylic acid high-carbon-alkyl sample to be tested, is dissolved with suitable solvent and is configured to a certain concentration
Solution to be measured, the suitable solvent is at least one of methanol, isopropanol or acetonitrile, wherein described a certain concentration is
100mg/L~700mg/L.
7. the detection method of content of acrylic acid high-carbon-alkyl according to claim 6, which is characterized in that the step
In (2-2) after precision weighing acrylic acid high-carbon-alkyl sample to be tested, it is miscellaneous first higher alcohols to be removed with deep eutectic solvent washing sample
Matter, then dissolves with suitable solvent and is configured to the solution to be measured of a concentration of 400mg/L, and the suitable solvent is methanol, isopropyl
At least one of alcohol or acetonitrile；The depth eutectic solvent is choline chloride and the deep eutectic solvent that glycerine mixing generates.
8. the detection method of content of the acrylic acid high-carbon-alkyl described according to claim 6 or 7, which is characterized in that the sample
Product examine survey detailed process be：
(3-1) prepares standard curve
Precision measures a series of standard solution of gradient concentrations, and it is molten that standard items are recorded according to the chromatographic condition of setting, after sample introduction
The chromatogram of liquid draws the linear correlation of chromatographic signal and concentration then according to the chromatogram of the standard solution of series concentration
Standard working curve；
(3-2) detects sample to be tested
Precision measures in the solution to be measured injection high performance liquid chromatograph isometric with standard solution, chromatogram is recorded, by color
Spectrum signal is brought into the standard working curve obtained by step (3-1), and the concentration of sample to be tested is obtained, and then sample to be tested is calculated
The content of middle acrylic acid high-carbon-alkyl.
9. the detection method of content of acrylic acid high-carbon-alkyl according to claim 8, which is characterized in that the detection side
The chromatographic condition of method is：
Chromatographic column is using octadecylsilane chemically bonded silica as filler；
The volume ratio of mobile phase methanol, isopropanol and acetonitrile is 70：25：5；
Column temperature is 30 DEG C；
Flow rate of mobile phase is 1mL/min；
The Detection wavelength of UV detector is 208nm；
Sample size is 20 μ of μ L~50 L；
Retention time is twice of main peak retention time.
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