CN106706791A

CN106706791A - Method for determining acrylic acid content in carbomer

Info

Publication number: CN106706791A
Application number: CN201611236555.1A
Authority: CN
Inventors: 沈惠; 洪怡; 母逸青
Original assignee: GUIZHOU XINZIHONG MEDICINAL MATERIALS Co Ltd
Current assignee: GUIZHOU XINZIHONG MEDICINAL MATERIALS Co Ltd
Priority date: 2016-12-28
Filing date: 2016-12-28
Publication date: 2017-05-24

Abstract

The invention relates to an acrylic acid detection technique, and particularly relates to a method for determining the acrylic acid content in carbomer. The method comprises the steps of firstly, mixing a to-be-determined product with an extraction agent according to the massic volume ratio of 1:(12 to 18), performing microwave extraction for 15 to 20 min at 120 to 140 DEG C, centrifugalizing, then filtering supernate so as to obtain filtrate, and then quantitatively determining the acrylic acid content in the carbomer with supercritical fluid chromatography and an external standard method, wherein chromatographic conditions include that a chromatographic column is an SFC capillary column, the stationary phase is silica gel, the column temperature is 36 to 38 DEG C, the injection volume is 20 to 30 muL, the moving phase is N2O, the detection wavelength is 290 to 320 nm, the constant pressure is 71.7*10<6> Pa, the split ratio is 10:1, a detection point is an FID (Flame Ionization Ditector) at 250 DEG C, and the supplementary gas is nitrogen. The method which is used for determining acrylic acid in the carbomer has the advantages of simplicity and convenience in operation and high sensitivity and precision.

Description

A kind of method of acrylic acid content in measure Carbomer

Technical field

The present invention relates to acrylic acid detection technique, more particularly to a kind of method for determining acrylic acid content in Carbomer.

Background technology

Carbomer also known as carbopol, chemical name：CP, be it is a kind of by acrylic acid and allyl saccharose or The high molecular polymer of acrylic pentaerythrite crosslinking, Carbomer has good gelation, viscous and property, thickening property, breast The property changed, suspending and film forming, and stable chemical nature safety, nonirritant and allergic reaction, under low pressure with good Compressibility, and good with other most of auxiliary material compatibilities, be widely used in household chemicals, weaving, coating, food, building, The fields such as medical treatment, electronics.

Acrylic acid is a kind of organic compound with intense irritation smell, is at normal temperatures colourless liquid, can be stimulated The eyes and respiratory tract of people, long-term high concentration contact can produce murder by poisoning to nervous system, immune system, liver organ etc..In recent years The research for coming shows that acrylic acid has certain toxicity, therefore, in the application process of Carbomer, control is contained acrylic acid Amount is most important, one of factor as influence Carbomer application.

At present, acrylic acid detection method is generally potentiometric titration in Carbomer, but the method is cumbersome, and sensitivity is low； With continuing to develop for science, risen using the research of gas chromatography, high performance liquid chromatography, for each detection method, High performance liquid chromatography is applied to measure volatile-resistant substance, and gas chromatography is applied to the volatile material of detection, but sensitivity And separating degree aspect is still undesirable, systematic error is still larger；In addition, directly using gas chromatography or high performance liquid chromatography pair Carbomer sample detected, the problems such as easily cause high polymer pollution chromatograph, further influences measurement result.

The content of the invention

In order to solve the above technical problems, the invention provides a kind of method for determining acrylic acid content in Carbomer.

The present invention is achieved by the following technical programs.

The method of acrylic acid content, comprises the following steps in a kind of measure Carbomer：

1) Microwave Extraction：Weigh product to be tested to be placed in microwave abstracting pipe, be by mass volume ratio with extractant by product to be tested 1:After the ratio of (12-18) is mixed, the Microwave Extraction 15-20min under the conditions of 120-140 DEG C after centrifugation, takes supernatant Liquid is filtered, and obtains filtrate, standby；

2) supercritical fluid chromatography condition：Chromatographic column：SFC capillary columns；Fixing phase：Silica gel；Column temperature：36-38℃；Sample introduction Volume：20-30μL；Mobile phase：N2O；Detection wavelength：290-320nm；Constant pressure：71.7×10⁶Pa；Split ratio：10:1；Detection Point：FID, 250 DEG C；Tonifying Qi：Nitrogen；

3) quantified by external standard method is determined.

Further, the filtering is filtered using 0.22 μm of organic filter membrane.

Further, the extractant is tetrahydrofuran, DMF, butanone, cyclohexanone, butyl acetate, ring Any one in hexane.

Further, the extractant is DMF.

Further, the centrifugation, rotating speed is 5000-8000r/min, and the time is 1-3min.

Further, the centrifugation, rotating speed is 6500r/min, and the time is 1min40s.

Further, the quantified by external standard method, its with acrylic acid area as ordinate, with acrylic acid Working Standard Solution Concentration is abscissa, draws standard curve；The concentration of Working Standard Solution is：10.0μg/mL、2.0μg/mL、1.0μg/mL、 0.4μg/mL、0.2μg/mL、0.1μg/mL。

In the present invention, acrylic acid content is calculated as follows formula and is calculated in Carbomer：

X=(C-C₀)×V×k/m

In formula：

C：Acrylic acid concentration in the Carbomer sample drawn by standard curve, unit is μ g/mL；

C₀：The blank value drawn by standard curve, unit is μ g/mL；

V：Extract volume, unit is mL；

k：Extension rate；

m：Sample quality.

The inventive method determines that acrylic acid detection is limited to 0.20 μ g/g, and lower limit of quantitation is 0.5 μ g/g.

The beneficial effects of the present invention are：

The invention provides a kind of assay method of acrylic acid content in accurate analysis, Carbomer easy to operate, overcome The defect such as conventional acrylic acid related detecting method is cumbersome, time-consuming, error is big, and assay method sensitivity of the present invention and essence Density is high, reproducible, it is adaptable to which acrylic acid carries out qualitative, quantitative measure in Carbomer, prevents because of residual acrylic acid in Carbomer Amount excessively causes potential hazard to the healthy of consumer.

Specific embodiment

Be described further below technical scheme, but claimed scope be not limited to it is described.

Embodiment 1

The preparation of S1, Working Standard Solution：

Acrylic acid (analysis is pure) is taken, is placed in 10mL color-comparison tubes, with methanol dilution to scale, after mixing, be placed in 10mL tool plug centrifuge tubes, 3min is centrifuged with the speed of 5000r/min, takes 0.22 μm of organic membrane filtration of supernatant, and filtrate is made It is standard liquid, the concentration of Working Standard Solution is as shown in table 1：

Table 1：

Standard liquid series	1#	2#	3#	4#	5#	6#
							Acrylic acid (μ g/mL)	10	2	1	0.4	0.2	0.1

S2, sample treatment：

1.0g samples are weighed, is placed in microwave abstracting pipe, 15mL DMFs are added, by microwave abstracting pipe It is placed in Microwave Extraction Apparatus, 20min is extracted under the conditions of 130 DEG C, after centrifugation, takes supernatant with 0.22 μm of organic filter membrane mistake Filter, obtains filtrate and makees sample solution；

S3, detection method：

Chromatographic column：SFC capillary columns；Fixing phase：Silica gel；Column temperature：37℃；Sampling volume：25μL；Mobile phase：N2O；Inspection Survey wavelength：300nm；Constant pressure：71.7×10⁶Pa；Split ratio：10:1；Test point：FID, 250 DEG C；Tonifying Qi：Nitrogen；

S4, drawing curve：

The acrylic acid Working Standard Solution series shown in table 1 is taken, is determined by the condition difference sample introduction under " detection method " item, With acrylic acid response peak area as ordinate, the concentration of Working Standard Solution is abscissa, draws standard curve, obtains and linearly returns Return equation：Y=87.25x-4.16, coefficient correlation is 0.9998, from regression equation：Curve linear coefficient R²＞ 0.99, it is linear good；Acrylic acid content is 45.15 μ g/g in Carbomer.

S5, sample determination：

Sample solution is taken, is determined by the condition sample introduction under " detection method " item, quantified by external standard method qualitative by retention time, According to acrylic acid response peak area in sample solution, acrylic acid concentration C in Carbomer sample solution is calculated by standard curve For：μg/mL

S6, precision test：

9 1.00g or so sample is weighed, is tested by the present embodiment " sample treatment " and " detection method " item, as a result As shown in table 2：

Table 2：

S7, replica test：

Sample size about 1.00g is weighed daily, is tested by the present embodiment " sample treatment " and " detection method " item, one Retest is carried out to same sample within week, as a result as shown in table 3：

Table 3：

S8, stability test：

Sample size about 1.00g is weighed, is tested by the present embodiment " sample treatment " and " detection method " item, in 24h Retest is carried out to same sample, it is as a result as shown in table 4 below：

Table 4：

S9, recovery test：

Using the rate of recovery of standard specimen addition method assay method, take two various concentrations samples be separately added into it is basic, normal, high 3 The acrylic acid standard liquid of concentration, is tested by the present embodiment " sample treatment " and " detection method ", and according to measured quantity, plus Enter amount and the former cubage rate of recovery, its result is as shown in table 5：

Table 5：

Embodiment 2

On the basis of the different places from embodiment 1 are " sample treatment " and " detection method ", to acrylic acid work Standard liquid series, sample solution are measured；

Its situation that do not exist together is as follows：

Sample treatment：1.0g samples are weighed, is placed in microwave abstracting pipe, 15mL tetrahydrofurans are added, by microwave abstracting pipe It is placed in Microwave Extraction Apparatus, 20min is extracted under the conditions of 120 DEG C, after centrifugation, takes supernatant with 0.22 μm of organic filter membrane mistake Filter, obtains filtrate and makees sample solution；

Detection method：Chromatographic column：SFC capillary columns；Fixing phase：Silica gel；Column temperature：36℃；Sampling volume：20μL；Flowing Phase：N2O；Detection wavelength：290nm；Constant pressure：71.7×10⁶Pa；Split ratio：10:1；Test point：FID, 250 DEG C；Tonifying Qi：Nitrogen Gas；

Its test result is as follows：

Equation of linear regression：Y=83.57x+1.43, coefficient correlation is 0.9999, from regression equation：Curve line Property coefficient R²＞ 0.99 is linear good；Acrylic acid content is 44.96 μ g/g in Carbomer.

Table 6：Precision test result

Table 7：Replica test result

Table 8：Stability test result

Table 9：Recovery test result

Embodiment 3

Its situation that do not exist together is as follows：

Sample treatment：1.0g samples are weighed, is placed in microwave abstracting pipe, add 15mL hexamethylenes, microwave abstracting pipe is put In Microwave Extraction Apparatus, 15min is extracted under the conditions of 140 DEG C, after centrifugation, take supernatant with 0.22 μm of organic filter membrane mistake Filter, obtains filtrate and makees sample solution；

Detection method：Chromatographic column：SFC capillary columns；Fixing phase：Silica gel；Column temperature：38℃；Sampling volume：30μL；Flowing Phase：N2O；Detection wavelength：320nm；Constant pressure：71.7×10⁶Pa；Split ratio：10:1；Test point：FID, 250 DEG C；Tonifying Qi：Nitrogen Gas；

Its test result is as follows：

Equation of linear regression：Y=85.12x-0.98, coefficient correlation is 0.9996, from regression equation：Curve line Property coefficient R²＞ 0.99 is linear good；Acrylic acid content is 45.08 μ g/g in Carbomer.

Table 10：Precision test result

Table 11：Replica test result

Table 12：Stability test result

Table 13：Recovery test result

Claims

1. it is a kind of determine Carbomer in acrylic acid content method, it is characterised in that：Comprise the following steps：

1) Microwave Extraction：Weigh product to be tested to be placed in microwave abstracting pipe, it is 1 to press mass volume ratio by product to be tested and extractant: After the ratio of (12-18) is mixed, the Microwave Extraction 15-20min under the conditions of 120-140 DEG C after centrifugation, takes supernatant Filtering, obtains filtrate, standby；

2) supercritical fluid chromatography：Chromatographic column：SFC capillary columns；Fixing phase：Silica gel；Column temperature：36-38℃；Sampling volume：20- 30μL；Mobile phase：N₂O；Detection wavelength：290-320nm；Constant pressure：71.7×10⁶Pa；Split ratio：10:1；Test point：FID, 250 ℃；Tonifying Qi：Nitrogen；

3) quantified by external standard method is determined.

2. the method for determining acrylic acid content in Carbomer as claimed in claim 1, it is characterised in that：The filtering is to use 0.22 μm of organic filter membrane is filtered.

3. the method for determining acrylic acid content in Carbomer as claimed in claim 1, it is characterised in that：The extractant is four Any one in hydrogen furans, DMF, butanone, cyclohexanone, butyl acetate, hexamethylene.

4. as described in claim 1 or 3 determine Carbomer in acrylic acid content method, it is characterised in that：The extractant It is DMF.

5. the method for determining acrylic acid content in Carbomer as claimed in claim 1, it is characterised in that：The centrifugation, Rotating speed is 5000-8000r/min, and the time is 1-3min.

6. as described in claim 1 or 5 determine Carbomer in acrylic acid content method, it is characterised in that：The centrifugation point From rotating speed is 6500r/min, and the time is 1min40s.

7. the method for determining acrylic acid content in Carbomer as claimed in claim 1, it is characterised in that：The external standard is legal Amount,, with acrylic acid area as ordinate, the concentration with acrylic acid Working Standard Solution draws standard curve as abscissa for it；Work The concentration for making standard liquid is：10.0μg/mL、2.0μg/mL、1.0μg/mL、0.4μg/mL、0.2μg/mL、0.1μg/mL.