CN105067727B - The assay method of polyethyleneglycol content in a kind of polycarboxylic acid water reducer macromer - Google Patents
The assay method of polyethyleneglycol content in a kind of polycarboxylic acid water reducer macromer Download PDFInfo
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- CN105067727B CN105067727B CN201510572430.5A CN201510572430A CN105067727B CN 105067727 B CN105067727 B CN 105067727B CN 201510572430 A CN201510572430 A CN 201510572430A CN 105067727 B CN105067727 B CN 105067727B
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Abstract
The invention discloses a kind of assay method of polyethyleneglycol content in polycarboxylic acid water reducer macromer.Detected using HPLC methods, using calibration curve method or quantified by external standard method, wherein, chromatographic column is C18 posts；Mobile phase is the mixed liquor of acetonitrile and water, and its weight percent is acetonitrile：Water=30~60:70~40.The present invention uses HPLC methods, with acetonitrile/water as mobile phase, to reduce the sample size of sample, the influence that solvent peak is detected to polyethyleneglycol content is eliminated, pointedly in polycarboxylic acid water reducer macromer polyethyleneglycol content provide detection method, with important practical usage.The method is accurate, easy, and round of visits is short, about half an hour, can provide reference for the quality control of water reducer macromer.
Description
Technical field
The present invention relates to a kind of method for determining polyethyleneglycol content in polycarboxylic acid water reducer macromer, and in particular to a kind of
Solvent peak can be effectively avoided to detect the method for influenceing to polyethyleneglycol content using HPLC.
Background technology
Polycarboxylate high performance water-reducing agent is that forefront, scientific and technological content highest, application prospect are best, comprehensive in the world at present
A kind of Concrete superplastizer (water reducer) of best performance.Polycarboxylate high performance water-reducing agent is carboxylic acids graft polyol copolymerization
The compound product of thing and other effective auxiliary agents.Show through with similar products at home and abroad Performance comparision, polycarboxylic acid series high-performance diminishing
Agent has all reached current international most advanced level in terms of technical performance index, cost performance.Polycarboxylic acid water reducer macromer includes alkene
Propyl alcohol APEO (APEG), isopentenol polyoxyethylene ether (TPEG), isobutene alcohol APEO (HPEG) and ethene
Base APEO (VPEG), poly glycol monomethyl ether (MPEG) and their mixture etc., are polycarboxylic-acid diminishings of new generation
The important source material of agent, it is free-radical polymerized by carrying out with acrylic acid etc., as terminal hydrophilic group, copolymer is formed, improve parent
It is aqueous, improve dispersiveness of the polymer in water.Synthesized water reducer has good particle dispersion and holding capacity, has
Water-reducing rate is high, good, cement usage amount is low to protect effect of collapsing, and enhancing effect is good, good endurance, not Corrosion Reinforcement and good to environment etc. excellent
Point.And the accessory substance that polyethylene glycol (PEG) is produced as water reducer macromer, the cost of its content production water reducer mother liquor higher
It is higher, can also allow the initial reduction of net slurry, loss increase that bubble can be also produced in concrete application in polymeric monomer application process,
Reduce the intensity of concrete, influence concrete it is attractive in appearance etc..
There is presently no the assay method for polyethyleneglycol content in polycarboxylic acid water reducer macromer.In non-ionic surface
In activating agent, using polyethyleneglycol content in chemical determination product, not only testing cost is high, and detection time is very long, single
Individual sample detection time 12 hours or so, can also use many poisonous and harmful reagents.And poly- second in existing measure surfactant
The HPLC methods methyl alcohol of glycol content easily produces solvent peak, and influence polyethyleneglycol content as mobile phase, the μ L of sample size 20
Detection, it is clear that there is open defect in the method.Size exclusion chromatography (GPC) is for detecting that polycarboxylic acids subtracts in current industry
A kind of common method of polyethyleneglycol content in aqua polymeric monomer, but peak due to PEG is often overlapped with the peak of polymeric monomer,
The data for being determined are extremely inaccurate, and content is seriously relatively low.
The content of the invention
High it is an object of the invention to provide a kind of sensitivity, specificity is strong, and detection cycle is short, and analysis result is accurately determined
The method of the polyethylene glycol in water reducer macromer, the method overcome polyethylene glycol method in existing measure surfactant
Defect.
The present invention is achieved through the following technical solutions：
The assay method of polyethyleneglycol content in polycarboxylic acid water reducer macromer, the assay method is examined using HPLC methods
Survey, using calibration curve method or quantified by external standard method, wherein, chromatographic column is C18 posts.
Mobile phase is the mixed liquor of acetonitrile and water, and its weight percent is acetonitrile：Water=30~60:70~40.
It is acetonitrile that mobile phase acetonitrile is further chosen with its weight percent of water：Water=45:55.
Using differential refraction detector, EISD or chemical detector.
Determination step includes：
(1) preparation of sample solution：Accurately weighed water reducer macromer is in volumetric flask, plus flows phased soln and be diluted to
Scale, is filtered with filter membrane, and gained filtrate is sample solution；
(2) preparation of reference substance solution：In accurately weighed polyethylene glycol standard items to volumetric flask, plus flowing phased soln and dilute
Release to scale, obtain final product reference substance solution；
(3) high performance liquid chromatography is determined：Reference substance solution and sample solution are carried out into high performance liquid chromatography measure, chromatographic column
C18, mobile phase is the mixed liquor of acetonitrile and water, and weight percent is acetonitrile：Water=30~60:70~40；
(4) calculate：Using calibration curve method or quantified by external standard method, chromatogram record is completed with place's reason work station, theoretical
The number of plates is calculated by polyethylene glycol and is not less than 2000.
The present invention determines content using HPLC methods, and as a result polyethylene glycol and water reducer macromer reached baseline in 15 minutes
Separate, and separating degree is more than 2.0, theoretical cam curve is calculated by polyethylene glycol and is not less than 2000, and polyethylene glycol is in concentration range
It is linear good, correlation coefficient r >=0.9999, the rate of recovery is between 90.0%-110.0%.This method can be used for the big list of water reducer
The quality analysis of polyethyleneglycol content in body, the method degree of accuracy and sensitivity are high, favorable reproducibility.
The present invention uses HPLC methods, with acetonitrile/water as mobile phase, to reduce the sample size of sample, eliminates solvent
The influence that peak is detected to polyethyleneglycol content, pointedly in polycarboxylic acid water reducer macromer polyethyleneglycol content provide inspection
Survey method, with important practical usage.The method is accurate, easy, and round of visits is short, about half an hour, can be the big list of water reducer
The quality control of body provides reference.
Brief description of the drawings
Fig. 1 is, using 45% acetonitrile water as mobile phase, to enter the μ L collection of illustrative plates of mobile phase 5；
Fig. 2 is, using methyl alcohol as mobile phase, to enter the μ L collection of illustrative plates of mobile phase 5；
Fig. 3 is, using 45% acetonitrile water as mobile phase, to enter the μ L collection of illustrative plates of sample solution 5 diluted with 45% aqueous acetonitrile solution；
Fig. 4 is, using methyl alcohol as mobile phase, to enter with the μ L collection of illustrative plates of sample solution 5 of methyl alcohol dissolved dilution.
In Fig. 3, the retention time peak of 2.111 minutes is salt peak, and the retention time peak of 2.651 minutes is polyethylene glycol peak,
The retention time peak of 5.572 minutes is polymeric monomer peak.
In Fig. 4, the retention time peak of 1.896 minutes is salt peak, and the retention time peak of 2.631 minutes is polyethylene glycol peak,
The retention time peak of 5.366 minutes is polymeric monomer peak.
Specific embodiment
The present invention is specifically described below by embodiment, embodiment is served only for carrying out further the present invention
Explanation, it is impossible to be interpreted as limiting the scope of the invention, those skilled in the art's content of the invention is made
Some nonessential modifications and adaptations fall within the scope of protection of the invention.
Embodiment 1
Method validation is tested
1st, instrument and reagent：
Shimadzu LC-20AT type liquid chromatographs, labsolutions LC work stations；ME204E type electronic analytical balance (plums
Teller support benefit)
Water reducer macromer sample；Macrogol 4000 reference substance (Agilent)；Acetonitrile (the silent winged generation that of match)；Laboratory
It is ultra-pure water with water
2nd, method and result
2.1 chromatographic conditions：Chromatographic column is GLInterSutain-C18(4.6mm*250mm*5 μm), mobile phase is acetonitrile：Water
(45:55), flow velocity is 1mL/min, column temperature：35 DEG C, the μ L of sample size 5, theoretical cam curve is calculated by polyethylene glycol and is not less than 2000.
It is prepared by 2.2 reference substance solutions：It is accurately weighed in weighing 20mg Macrogol 4000s to 50ml measuring bottles, plus mobile phase
Scale is dissolved and be diluted to, reference substance solution is obtained final product.
The preparation of 2.3 sample solutions：Water reducer macromer 1.0g is weighed in 50ml measuring bottles, it is accurately weighed, respectively plus stream
Dynamic phased soln is simultaneously diluted to scale, is filtered with 0.22 μm of filter membrane respectively, takes subsequent filtrate as sample solution.
2.4 linear relationships are investigated：Reference substance solution is taken, stepwise dilution obtains control series product solution, by 2.1 lower chromatostrips
Part sample introduction is determined, and with peak area as ordinate, concentration is abscissa, draws standard curve, the equation of linear regression of polyethylene glycol
For：Y=45782X+8567, coefficient correlation：0.9999, the concentration range of linearity 0.0472-1.416 ㎎/L.
2.5 precision tests：Reference substance solution is taken, by 2.1 lower chromatographic condition continuous sample introductions 6 times, peak area is determined.Knot
Really its RSD is 0.86%.Result shows that the method precision is good.
2.6 stability tests：Water reducer macromer sample solution is taken, is placed at room temperature 0,2,4,6,8,12,24 hours, pressed
Specify chromatographic condition sample detection peak area under 2.1.As a result polyethylene glycol peak area RSD is：1.42%, as a result show sample
Solution is basicly stable in 24 hours, meets analysis test requirements document.
2.7 serviceability tests：45% ± 5 acetonitrile water mobile phase is prepared respectively, and remaining analysis condition is constant, same sample
It is as follows by 2.1 lower chromatographic condition sample introduction measurement results respectively：
| Mobile phase ratio (acetonitrile：Water) | Polyethyleneglycol content % |
| 30% | 4.51 |
| 45% | 4.47 |
| 60% | 4.58 |
Result of the test shows the method good tolerance.
2.8 replica tests：6 parts are prepared by sample solution compound method is parallel, by 2.1 lower chromatographic condition sample introductions point
Analysis, calculates peak area.The RSD of polyethylene glycol is 0.93%.Result shows that the method has good repeatability.
2.9 sample-adding recovery tests：9 parts of the water reducer macromer of known content is weighed, every part of about 0.5g is accurate respectively to add
The polyethylene glycol reference substance solution of about 80%, 100%, the 120% of polyethyleneglycol content in water reducer macromer, by sample solution
Prepared by preparation method, analyzed by 2.1 lower chromatographic condition sample introductions, and the average recovery rate of polyethylene glycol is for 95.21%, RSD
1.87%.Result shows that the method has good reliability and accuracy.
Embodiment 2
With chemical method contrast test
1st, instrument and reagent：
Shimadzu LC-20AT type liquid chromatographs, labsolutions LC work stations；ME204E type electronic analytical balance (plums
Teller support benefit).
5 water reducer macromer samples of different company；Macrogol 4000 reference substance (Agilent)；(match is silent to fly acetonitrile
Generation that)；Use for laboratory water is ultra-pure water.
2nd, method and result
2.1 chromatographic conditions：Chromatographic column is GLInterSutain-C18(4.6mm*250mm*5 μm), mobile phase is acetonitrile：Water
(45:55), flow velocity is 1mL/min, column temperature：35 DEG C, the μ L of sample size 5, theoretical cam curve is calculated by polyethylene glycol and is not less than 2000.
It is prepared by 2.2 reference substance solutions：It is accurately weighed in weighing 20mg Macrogol 4000s to 50ml measuring bottles, plus mobile phase
Scale is dissolved and be diluted to, reference substance solution is obtained final product.
The preparation of 2.3 sample solutions：5 water reducer macromer 1.0g of different company are weighed respectively in 50ml measuring bottles,
It is accurately weighed, flowing phased soln is added respectively and scale is diluted to, filtered with 0.22 μm of filter membrane respectively, subsequent filtrate is taken respectively is 5
Individual different company's sample solution.
Polyethyleneglycol content is as follows with chemical determination content results in 2.4 5 water reducer macromers of different manufacturers
Table：
| Sample | 1 | 2 | 3 | 4 | 5 |
| The present invention surveys polyethyleneglycol content % | 4.51 | 7.89 | 3.87 | 9.23 | 8.68 |
| Chemical method surveys polyethyleneglycol content % | 4.44 | 7.95 | 3.76 | 9.18 | 8.49 |
Result shows the method measurement result and existing national standard method results contrast, unanimously.
Embodiment 3
Blank sample contrast test
1st, instrument and reagent：
Shimadzu LC-20AT type liquid chromatographs, labsolutions LC work stations；ME204E type electronic analytical balance (plums
Teller support benefit)
Water reducer macromer, acetonitrile (match is silent to fly generation that), methyl alcohol (the silent winged generation that of match) use for laboratory water are ultra-pure water
2nd, method and result
2.1 chromatographic conditions 1：Chromatographic column is GLInterSutain-C18(4.6mm*250mm*5 μm), mobile phase is acetonitrile：
Water (45:55), flow velocity is 1mL/min, column temperature：35 DEG C, the μ L of sample size 5, theoretical cam curve is calculated by polyethylene glycol and is not less than
2000。
2.2 chromatographic conditions 2：Chromatographic column is GLInterSutain-C18 (4.6mm*250mm*5 μm), and mobile phase is methyl alcohol：
Water (45:55), flow velocity is 1mL/min, column temperature：35 DEG C, the μ L of sample size 5, theoretical cam curve is calculated by polyethylene glycol and is not less than
2000。
The preparation of 2.3 sample solutions：Water reducer macromer 1.0g is weighed respectively in 50ml measuring bottles, it is accurately weighed, respectively
Plus flow phased soln and be diluted to scale, filtered with 0.22 μm of filter membrane respectively, subsequent filtrate as sample solution is taken respectively.
2.4 are walked baseline by chromatographic condition 1 and 2 flat, and each mobile phase and each 5 microlitres of each sample solution are entered respectively, obtain figure
1st, Fig. 2, Fig. 3 and Fig. 4.Fig. 1 is, using 45% acetonitrile water as mobile phase, to enter the μ L collection of illustrative plates of mobile phase 5；Fig. 2 is using methyl alcohol as stream
Dynamic phase, enters the μ L collection of illustrative plates of mobile phase 5；Fig. 3 is, using 45% acetonitrile water as mobile phase, to enter the sample diluted with 45% aqueous acetonitrile solution
The μ L collection of illustrative plates of solution 5；Fig. 4 is, using methyl alcohol as mobile phase, to enter with the μ L collection of illustrative plates of sample solution 5 of methyl alcohol dissolved dilution.Result shows：
Solvent peak is also easy to produce as mobile phase with methyl alcohol, so as to influence the detection of polyethyleneglycol content, but with acetonitrile water as mobile phase then
The generation of solvent peak, testing result more accurate, science can well be avoided.
Claims (4)
1. a kind of polycarboxylic acid water reducer macromer measuring method, it is characterised in that：The assay method is examined using HPLC methods
Polyethyleneglycol content in water reducer macromer is surveyed, using calibration curve method or quantified by external standard method, wherein, chromatographic column is C18 posts；Stream
Dynamic is mutually acetonitrile and the mixed liquor of water, and its weight percent is acetonitrile：Water=30~60:70~40.
2. polycarboxylic acid water reducer macromer measuring method according to claim 1, it is characterised in that：The mobile phase
Acetonitrile is acetonitrile with the weight percent of water：Water=45:55.
3. polycarboxylic acid water reducer macromer measuring method according to claim 2, it is characterised in that：Using showing poor folding
Photodetector, EISD or chemical detector.
4. the polycarboxylic acid water reducer macromer measuring method according to any one of claims 1 to 3, it is characterised in that bag
Include following steps：
(1) preparation of sample solution：Accurately weighed water reducer macromer is in volumetric flask, plus flows phased soln and be diluted to quarter
Degree, is filtered with filter membrane, and gained filtrate is sample solution；
(2) preparation of reference substance solution：In accurately weighed polyethylene glycol standard items to volumetric flask, plus flow phased soln and be diluted to
Scale, obtains final product reference substance solution；
(3) high performance liquid chromatography is determined：Reference substance solution and sample solution are carried out into high performance liquid chromatography measure, chromatographic column C18,
Mobile phase is the mixed liquor of acetonitrile and water, and weight percent is acetonitrile：Water=30~60:70~40；
(4) calculate：Using calibration curve method or quantified by external standard method, chromatogram record is completed with place's reason work station, theoretical tray
Number is calculated by polyethylene glycol and is not less than 2000.
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| CN105548423A (en) * | 2016-01-25 | 2016-05-04 | 北京工业大学 | Quantitative detection method for residual crylic acid in polycarboxylate superplasticizer synthetic process |
| CN106018698B (en) * | 2016-06-22 | 2019-02-15 | 科之杰新材料集团有限公司 | A kind of qualitative analysis detection method of polycarboxylate water-reducer residual small molecule monomer component |
| CN106290672A (en) * | 2016-09-13 | 2017-01-04 | 科之杰新材料集团有限公司 | The assay method of methylpropene sodium sulfonate content in a kind of polycarboxylate water-reducer |
| CN112903860B (en) * | 2021-01-25 | 2022-05-27 | 人福普克药业（武汉）有限公司 | Detection method of related substance MPEG in benzonatate |
| CN113176371B (en) * | 2021-04-29 | 2022-12-06 | 南京威尔生物科技有限公司 | Method for determining free polyethylene glycol in fatty alcohol-polyoxyethylene ether |
| CN114636773B (en) * | 2022-05-23 | 2022-08-23 | 广东国标医药科技有限公司 | Method for measuring content of polyethylene glycol monomethyl ether 2000 in pharmaceutic adjuvant |
| CN117723678A (en) * | 2024-02-01 | 2024-03-19 | 广东优凯科技有限公司 | Method for testing content of PEG200 in high-concentration detergent |
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Address after: Pengzhou City, Chengdu City, Sichuan Province, Fengzhen petrochemical 611939 Long Road East No. 718 Patentee after: Sichuan orksta chemical Limited by Share Ltd Address before: Pengzhou City, Chengdu City, Sichuan Province, Fengzhen petrochemical 611939 Long Road East No. 718 Patentee before: SICHUAN SEDAR CHEMICAL CO., LTD. |
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Address after: Pengzhou City, Chengdu City, Sichuan Province, Fengzhen petrochemical 611939 Long Road East No. 718 Patentee after: Sichuan Oak Chemical Co., Ltd. Address before: Pengzhou City, Chengdu City, Sichuan Province, Fengzhen petrochemical 611939 Long Road East No. 718 Patentee before: Sichuan orksta chemical Limited by Share Ltd |
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