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national standards of People's Republic of China

GB1886.232—2016

National food safety standards

Food additive sodium carboxymethyl cellulose

Published on 2016-08-31 Implemented on 2017-01-01

National Health and Family Planning release

Commission of the People's Republic of China
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GB1886.232—2016

Preface

This standard replaces GB1904-2005 "Food Additive Sodium Carboxymethylcellulose". Compared

with GB1904-2005, the main changes in this standard are as follows: --- Added

the index requirements for content, sodium and sodium glycolate; ---

Modified the requirements for drying loss, viscosity, chloride (calculated as NaCl) and lead Indicator

requirements; ---Deleted the indicator requirements for iron and heavy metals.

ÿ
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GB1886.232—2016

National food safety standards

Food additive sodium carboxymethyl cellulose

1 Scope

This standard applies to the food additive sodium carboxymethylcellulose made from cellulose, sodium hydroxide and chloroacetic acid or its sodium salt as main raw materials.

2 Molecular formula, structural formula and relative molecular mass

2.1 Molecular formula

[C6H7O2(OH) : degree of x (OCH2COONa) y

]n
n polymerization

x :1.5~2.8

y :Degree of substitution, 0.2~1.5

x + y =3.0

2.2 Structural formula

R=H or CH2COONa

2.3 Relative molecular mass

n When about 100, >17000 (according to the 2013 international relative atomic mass)

3 Technical requirements

3.1 Sensory requirements

Sensory requirements should comply with Table 1.

Table 1 Sensory requirements

project Require Testing method

color white or yellowish Place an appropriate amount of sample evenly in a white porcelain plate and place it under natural light.

state Fibrous powder or granular form Observe its color and condition

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3.2 Physical and chemical indicators

The physical and chemical indicators should comply with the provisions of Table 2.

Table 2 Physical and chemical indicators

project index Testing method

Carboxymethyl cellulose sodium content, w /% ÿ 99.5 Appendix A, A.3

Viscosity (mass fraction: 2% aqueous solution) a/(mPa·s) ÿ 5.0 A.4 in Appendix A

Degree of substitution 0.20~1.50 Appendix A, A.5

pH (10g/L aqueous solution) 6.0~8.5 A.6 in Appendix A

drying loss, w /% ÿ 8.0 GB5009.3 Direct drying method b

sodium glycolate, w /% ÿ 0.4 A.7 in Appendix A

Chloride (as NaCl), w /% ÿ 0.5 Appendix A, A.8

sodium, w /% ÿ 12.4 A.9 in Appendix A

Arsenic (As)/(mg/kg) ÿ 2.0 GB5009.76

Lead(Pb)/(mg/kg) ÿ 2.0 GB5009.75

aWhen the viscosity (mass fraction of 2% aqueous solution) is ÿ2000mPa·s, the measurement should be made with a mass fraction of 1% aqueous solution.

b
The drying temperature is 105 ÿ ± 2 ÿ, and the drying time is 2 hours.

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GB1886.232—2016

Appendix A

Testing method

A.1 General provisions

Unless otherwise specified in this standard, the purity of the reagents used should be of analytical purity. The standard titration solutions, standard solutions for impurity determination,

preparations and products should be prepared and tested in accordance with the regulations of GB/T601, GB/T602 and GB/T603. The water used should comply with the provisions of Grade 3 water

in GB/T6682. The solutions used in the test refer to aqueous solutions unless the solvent used to prepare them is specified.

A.2 Identification test

A.2.1 Reagents and materials

A.2.1.1 Hydrochloric acid.

A.2.1.2 Potassium iodide-iodine solution: Dissolve 0.5g of iodine and 1.5g of potassium iodide in 25mL of water.

A.2.1.3 Copper sulfate (CuSO4·5H2O) solution: 20g/L.

A.2.2 Preparation of test solution

Take 2g of the sample, place it in 100mL of warm water, stir evenly, continue stirring until it becomes gelatinous, and cool to room temperature.

A.2.3 Identification method

A.2.3.1 Take about 30mL of the test solution and add 2 to 3 drops of potassium iodide-iodine solution. No blue color will appear.

A.2.3.2 Take about 50mL of the test solution and add 10mL of copper sulfate solution to produce a fluffy light blue precipitate.

A.2.3.3 Wet the platinum wire with hydrochloric acid, first burn it on a colorless flame until it is colorless, then dip a little of the test solution and burn it in the colorless flame, the

flame will turn bright yellow.

A.3 Determination of carboxymethyl cellulose sodium content

The sodium carboxymethyl cellulose content is equal to 100% minus the mass fraction of sodium glycolate ( w 1) and chloride mass fraction ( w 2).

A.4 Determination of viscosity

A.4.1 Instruments and equipment

A.4.1.1 Rotational viscometer: numerical or pointer type.

A.4.1.2 Glass cup: The diameter is about 90mm, the height is about 122mm, the upper and lower diameters are the same, and the capacity is about 500mL.

A.4.1.3 Constant temperature water bath.

A.4.1.4 Mechanical stirrer: made of stainless steel or glass, connected to a variable speed motor capable of rotating at 900r/min ±100r/min under different loads.

A.4.2 Analysis steps

Weigh 5.0g (preparing a test solution with a mass fraction of 1%) or 10.0g (preparing a test solution with a mass fraction of 2%) samples, accurately

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to 1mg. Add 495.0g (to prepare a test solution with a mass fraction of 1%) or 490.0g (to prepare a 2% mass fraction) into the glass.

Test solution) water, put the stirrer into the glass, keep the stirring blade about 10mm away from the bottom of the cup, start stirring and slowly add the sample, adjust the stirring

Increase the speed to 900r/min±100r/min and stir for 2h. If the sample is not completely dissolved, continue stirring for 0.5h. Remove the stirrer and remove the glass.

Place the cup into a constant temperature water bath at 25 ÿ ± 0.2 ÿ for 1 hour. If the solution does not reach 25 ÿ ± 0.2 ÿ, it needs to continue to be heated to 25 ÿ ± 0.2 ÿ.

Take it out, stir manually for 10 seconds, and measure the viscosity with a viscometer. First, immerse the viscometer rotor in the sample solution, then start the viscometer and rotate it for about 1 minute.

After the displayed value is stable, take the reading.

A.4.3 Result calculation

A.4.3.1 Numerical viscometer

Direct reading is the viscosity value of the sample.

A.4.3.2 Pointer viscometer

viscosity n , the value is expressed in millipaseconds (mPa·s) and is calculated according to formula (A.1):

= S × k ………………………(A.1)
n

In the formula:

S ———The pointer indication reading of the rotational viscometer, in milliPascal seconds (mPa·s);

k ———Coefficients of rotor and speed selected during measurement.

The test results should indicate the concentration of the test solution and the rotor number and speed of the rotor used.

The test results are based on the arithmetic mean of parallel measurement results and the absolute difference of two independent measurement results measured under repeatability conditions.

The value must not exceed 5%~10% of the arithmetic mean.

A.5 Determination of degree of substitution

A.5.1 Summary of methods

The sample is washed with ethanol to remove soluble salts, dried and burned at high temperature. The residue is sodium oxide. Add water to dissolve it to form sodium hydroxide. Add an excess amount.

Sulfuric acid standard titration solution, titrate excess sulfuric acid with sodium hydroxide standard titration solution, and calculate the carboxylic acid content of each anhydrous glucose unit

The average value of the methyl group is the degree of substitution.

A.5.2 Reagents and materials

A.5.2.1 Absolute ethanol.

A.5.2.2 Ethanol solution: Measure 90 mL of ethanol and add water to dilute to 100 mL.

æ 1 o
A.5.2.3 Sulfuric acid standard titration solution: c ç

H2SO4 ÷=0.1mol/L.
è 2 ø

A.5.2.4 Sodium hydroxide standard titration solution: c (NaOH)=0.1mol/L.

A.5.2.5 Methyl red indicator solution: 1g/L.

A.5.3 Instruments and equipment

A.5.3.1 Glass sand crucible: filter plate pore size 15ÿm~40ÿm.

A.5.3.2 Porcelain crucible: 20mL~25mL.

A.5.4 Analysis steps

Weigh about 1.5g of the sample, place it in a glass sand crucible, and wash it several times with an ethanol solution preheated to 50°C ~ 70°C (fill it up each time

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Glass sand crucible), until the filtrate after adding 1 drop of potassium chromate solution and 1 drop of silver nitrate solution turns brick red, the washing is completed, otherwise the washing should continue

Polyester, generally washed 5 times. Wash with absolute ethanol for the last time. Move the washed sample into a sand core crucible and dry it at 120ÿ±2ÿ for 2 hours.

(At about 1 hour, gently tap the sample in the sand core crucible to loosen it). Cover and transfer to a desiccator and cool to room temperature. Weigh about 1g of sample, accurate to

0.0002g, placed in a porcelain crucible, carbonized on an electric furnace until no smoke is emitted, placed in a 300 ÿ high temperature furnace, raised to 700 ÿ ± 25 ÿ, and kept warm

15min, turn off the power, cool to below 200 ÿ, transfer to a 250mL beaker, add 100mL water and 50mL±0.05mL sulfuric acid standard.

To quasi-titrate the solution, place the beaker on an electric stove and heat it, boil slowly for 10 minutes, add 2 to 3 drops of methyl red indicator solution, cool, and use sodium hydroxide

Titrate the standard titration solution until the red color just fades.

A.5.5 Result calculation

Degree of substitution x DS, calculated according to formula (A.2) and formula (A.3):

-
V 1
× c1 V × c2
cB =
2
……………………(A.2)
m

0.162 c B
x = ……………………(A.3)
DS
1-0.080 cB

In the formula:

c B ————The number of millimoles of carboxymethyl group in the sample, the unit is millimoles per gram (mmol/g);

V 1 ———The volume of sulfuric acid standard titration solution, in milliliters (mL);

c 1 ———The actual concentration of the sulfuric acid standard titration solution, in moles per liter (mol/L);

V 2 ———The volume of sodium hydroxide standard titration solution, in milliliters (mL);

c 2 ———The actual concentration of sodium hydroxide standard titration solution, in moles per liter (mol/L);

m ———The mass of the sample, in grams (g);

0.162——The millimole mass of one glucose unit in cellulose, in grams per millimole (g/mmol);

0.080——millimolar mass of sodium carboxymethyl group, unit is grams per millimole (g/mmol).

Calculation results are expressed to 2 decimal places. Take the arithmetic mean of the two parallel measurement results as the measurement result.

The absolute difference of the results is not greater than 0.02.

A.6 Determination of pH

Use potentiometric measurement or use pH test paper to measure the pH of the 10g/L sample aqueous solution. When measuring by potentiometric method, follow the regulations of GB/T9724

Carry out regularly, weigh about 1.0g of sample, accurate to 0.01g, add 100mL of carbon dioxide-free water, mix evenly and then measure.

A.7 Determination of sodium glycolate

A.7.1 Reagents and materials

A.7.1.1 Sulfuric acid.

A.7.1.2 Glycolic acid.

A.7.1.3 Acetone.

A.7.1.4 Sodium chloride.

A.7.1.5 Glacial acetic acid.

A.7.1.6 2,7-Dihydroxynaphthalene solution: Weigh 0.1g of 2,7-dihydroxynaphthalene and dissolve it in 1000 mL of concentrated sulfuric acid, and let the solution stand until the yellow color disappears.

The solution is stored in a brown reagent bottle and is valid for 1 month.

A.7.1.7 Aluminum foil.

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A.7.2 Instruments and equipment

A.7.2.1 Spectrophotometer.

A.7.2.2 Electronic balance, accuracy 0.0001g.

A.7.2.3 Water bath.

A.7.2.4 Volumetric flask: 25mL, 100mL.

A.7.3 Analysis steps

A.7.3.1 Sample handling

Accurately weigh 0.5g of the sample, add it to a 100mL beaker, thoroughly infiltrate it with 5mL of glacial acetic acid, then add 5mL of water, and use a glass rod to

Stir until completely dissolved (usually 15 minutes), slowly add 50mL acetone during the stirring process, then add 1g sodium chloride, stir

Stir for a few minutes to ensure that the sodium carboxymethylcellulose is completely precipitated. Filter with quantitative filter paper, moisten the filter paper with a small amount of acetone, and collect the filtrate into

in a 100mL volumetric flask. In addition, use 30 mL acetone to speed up the transfer of solids and rinse the filter cake, then use acetone to adjust the volume and shake well.

A.7.3.2 Preparation of glycolic acid standard solution

Accurately weigh 0.100g of glycolic acid (accurate to 1mg) that has been dried in a desiccator at room temperature for 24 hours, place it in a 100mL volumetric flask, and use

Dissolve in water and dilute to volume. This solution is valid for 1 month.

Take 0mL, 1.0mL, 2.0mL, 3.0mL, and 4.0mL of this solution and add them to five 100mL volumetric flasks.

Add water until the total volume is 5 mL, add 5 mL of glacial acetic acid, and dilute to volume with acetone, marked as No. 1 to No. 5.

Take 2.0 mL of the sample solution and the standard solution No. 1 to 5 and add them into a 25 mL volumetric flask respectively, and place the unsealed volumetric flask in a boiling water.

Remove the acetone in the water bath for 20 minutes, then remove from the boiling water bath and cool. Add 5 mL of 2,7-dihydroxynaphthalene to each volumetric flask and mix well.

After homogeneous, add 15mL of 2,7-dihydroxynaphthalene and mix evenly. Seal the mouth of each volumetric flask with aluminum foil. Place each volumetric flask in a boiling water bath

Medium for 20 minutes, then remove and cool, dilute to volume with sulfuric acid, and shake well.

A.7.4 Preparation of standard curve

Use a spectrophotometer, use solution No. 1 as the blank control, use a 1cm cuvette, and measure the absorbance of the standard series solutions at 540nm.

and the absorbance of the sample solution to develop a standard curve.

A.7.5 Result calculation

Mass fraction of sodium glycolate w 1. Calculate according to formula (A.4):

12.9× m 1
w = ………………………(A.4)
1
(100- b )× m 0

In the formula:

12.9——(molar mass of sodium glycolate/molar mass of glycolic acid)×10;

m 1 ——The mass of glycolic acid found in the standard curve, in milligrams (mg);

b ———Mass fraction of drying loss, %;

m 0 ————Sample mass, unit is grams (g).

A.8 Determination of chloride

A.8.1 Method summary

The sample is dissolved in water, titrated with silver nitrate standard titration solution, and the end point is indicated with a potentiometer. Hydrogen peroxide is added to the solution to degrade the solution

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viscosity.

A.8.2 Reagents and materials

A.8.2.1 Nitric acid.

A.8.2.2 Hydrogen peroxide.

A.8.2.3 Silver nitrate standard titration solution: c (AgNO3)=0.1mol/L.

A.8.3 Instruments and equipment

A.8.3.1 Potentiometric titrator: equipped with silver electrode and saturated calomel electrode (double salt bridge).

A.8.3.2 Microburette: 10mL.

A.8.4 Analysis steps

Weigh a 2g sample that has been dried at 105ÿ±2ÿ for 2h, accurate to 0.0002g, place it in a 250mL beaker, add 100mL of water and

5mL hydrogen peroxide. Place the beaker in a steam bath and heat, stirring occasionally to obtain a non-sticky solution. If the solution viscosity after 20 minutes

If it is not completely degraded, add 5 mL of hydrogen peroxide and heat until complete degradation. Cool the beaker, add 100mL water and 10mL nitric acid, and set aside

On the magnetic stirrer of the potentiometric titrator, use a microburette to dropwise add the silver nitrate standard titration solution to the potential endpoint.

A.8.5 Result calculation

Mass fraction of chloride content (calculated as NaCl) w 2 Calculate according to formula (A.5):

c × V × M
w = ×100% ………………………(A.5)
2
m

In the formula:

c ———Concentration of silver nitrate standard solution, in moles per liter (mol/L);

V ———The volume of silver nitrate standard titration solution, in milliliters (mL);

M --- The millimole mass of sodium chloride, in grams per millimole (g/mmol) M =0.05845);

m (--- The mass of the sample, in grams (g).

Calculation results are expressed to one decimal place. Take the arithmetic mean of the two parallel measurement results as the measurement result.

The absolute difference of the results is no more than 0.06%.

A.9 Determination of sodium

Mass fraction of sodium w 3. Calculate according to formula (A.6):

0.023× x DS
w = ×100%……………………(A.6)
3
0.162+0.080 x DS

In the formula:

x DS ———Degree of substitution of the sample;

0.023——millimolar mass of sodium, unit is grams per millimole (g/mmol);

0.162——The millimole mass of one glucose unit in cellulose, in grams per millimole (g/mmol);

0.080——millimolar mass of sodium carboxymethyl group, unit is grams per millimole (g/mmol).