Some standard content:
Chemical Industry Standard of the People's Republic of China
HG2454-93
Polyurethane varnish (repackaging)
Published on June 29, 1993
Published by the Ministry of Chemical Industry of the People's Republic of China and implemented on April 1, 1994
Chemical Industry Standard of the People's Republic of China
Polyurethane varnish (repackaging)
1 Subject content and scope of application
HG2454-93
This standard specifies the technical requirements, test methods, inspection rules, marking, packaging, storage, transportation and other matters of polyurethane varnish (repackaging). This standard is applicable to repackaging coatings composed of prepolymer containing toluene diisocyanate as component one and alkyd resin containing hydroxyl as component two.
The products specified in this standard are applicable to the surface decoration and protection of wood, furniture and metal products. 2 Reference standards
GB1721
GB1727
GB1728
GB1764
GB1768
GB3186
GB5208
GB6682
GB6739
GB6742
GB6751
GB9274
GB9278
GB9286
GB9750
GB9754
GB9761
3 Technical requirements
Determination of appearance and transparency of varnish, clear oil and thinner General preparation method of paint film
Determination of drying time of paint film and putty film||t t||Determination of film thickness
Determination of abrasion resistance of paint film
Sampling of coating products
Determination of flash point of coating Rapid equilibrium method
Specifications and test methods of water for analytical laboratories Pencil method for determination of film hardness
Bending test of paint film (cylindrical axis)
Determination of volatile and non-volatile matters in paints and varnishes Paints and varnishes
Determination of resistance to liquid media
Temperature and humidity for condition adjustment and testing of coating specimens Cross-cut test of paint and varnish films
Packaging and marking of coating products
Paints and varnishes
Paints and varnishes
Determination of specular gloss at 20°, 60° and 85° of paint films without metallic pigments Visual colorimetry of paints
The products shall meet the technical requirements in the following table.
Appearance of original paint
Appearance of paint film
Non-volatile matter content, %
Not less than
Qualified products approved by the Ministry of Chemical Industry of the People's Republic of China on 1993-06-29
Light yellow to brownish yellow transparent liquid, free of mechanical impurities, smooth and level
Implemented on 1994-04-01
Component 2
Drying time, h
Drying ( 120±2℃)
Gloss, 60°
Cross-cut test, grade
Flexibility, mm
Water resistance (immersed in GB6682 grade 3 water, 23±2℃)Acid resistance (immersed in 50% ethanol)
Alcohol resistance (immersed in 5% sulfuric acid for 12h)
Abrasion resistance (750g/500r), g
Flash point, ℃
Free TDI monomer, %||tt| |4 Test method
4.1 General conditions of the test
HG2454-93
Not more than
Not less than
Not less than
First-class products
No blistering, wrinkling, or peeling for 72 hours. The paint film is allowed to turn white and recover within 2 hours
No blistering, wrinkling, or abnormal changes in the paint film within 5 hours
Qualified products
48 h No blistering, no wrinkling, no falling
, the paint film is allowed to turn white, and it will recover in 2h
No blistering, no wrinkling, no
abnormal changes in the paint film
No blistering, no wrinkling, no falling
No more than
No less than
No more than
4.1.1 The proportion of components shall be prepared according to the proportion of components in the product introduction and instructions of each manufacturer, and the plate making method shall be carried out in accordance with the provisions of GB1727.
4.1.2 The state adjustment of the test room shall be carried out in accordance with the provisions of GB9278. 4.1.3 The thickness of the paint film shall be measured in accordance with the provisions of GB1764, and the test dry film thickness shall be between 30±4um; unless otherwise specified, the test plate shall be made of tinplate.
4.1.4 After making the board, the physical properties of the paint film shall be tested. Except for the gloss, which shall be tested after drying for 48 hours under constant temperature and humidity conditions, the other properties shall be tested after baking for 1 hour under 120±2℃ and resting for 0.5~1 hour under constant temperature and humidity conditions. 4.2 Appearance of the original paint
According to the "Determination of Appearance" in GB1721. 4.3 Non-volatile content
According to GB6751.
4.4 Appearance of the paint film
According to GB9761.
Drying time
According to GB1728, among which surface drying shall be carried out according to method B and actual drying shall be carried out according to method A. 4.6 Gloss
According to GB9754.
4.7 Bending
According to GB6742.
4.8 Hardness
Perform according to GB6739.
4.9 Cross-cut test
HG2454-93
Perform according to GB9286, the number of cuts is 6×6, the spacing is 1mm, and no adhesive tape is used. 4.10 Water resistance
Prepare the water solution according to GB6682, and check the results according to 5.4 of GB9274. 4.11 Alcohol resistance
Perform according to the medium A method of GB9274. The test should be made on a glass plate with a specification of 90mm×120mm×(2~3)mm and sealed with paraffin.
4.12 Acid resistance
Perform according to the medium A method of GB9274. The test should be carried out on a steel plate with a specification of 50mmX120mm×(0.45~0.55)mm. 4.13 Abrasion resistance
According to GB1768.
4.14 Flash point
According to GB5208.
4.15 Free TDI monomer
Determine according to Appendix B.
5 Inspection rules
5.1 All items listed in the technical requirements of this standard are type inspection items. Among them, the state of the original paint in the container, the appearance of the paint film, the drying time, the gloss, the cross-cut test, the hardness, the bending, the outflow time, the water resistance, and the free TDI monomer are factory inspection items, and the remaining items are inspected every six months.
5.2 The inspection department of the manufacturer shall take samples of the products according to GB3186 and inspect them according to the items specified in this standard. The products shall have a certificate of conformity and, if necessary, instructions for use and precautions. 5.3 The receiving department has the right to inspect the product according to the provisions of this standard. If the quality is found not to meet the requirements of the indicators of this standard, the supply and demand parties shall jointly resample and re-test according to GB3186. If it still does not meet the technical requirements of this standard, the product is considered unqualified and the receiving department has the right to return it.
5.4 The supply and demand parties shall check and verify the product packaging, quantity and marking. If the packaging is damaged or leaking, the quantity is inconsistent, or the marking does not meet the requirements, it is considered unqualified.
5.5 If there is a dispute between the supply and demand parties over the quality of the product, the product quality supervision and inspection agency shall perform arbitration inspection. 6 Packaging, marking, purchase, storage and transportation
6.1 The product should be stored in a clean, dry and sealed container, and the outer marking of the container shall be carried out in accordance with the provisions of GB9750. 6.2 The product should be kept ventilated and dry during storage, and should be protected from direct sunlight, isolated from fire and away from heat sources. In summer, when the temperature is too high, it should be cooled down.
6.3 Products should be protected from rain and sunlight during transportation and should comply with the relevant regulations of the transportation department. 6.4 Products should comply with 6.1 and 6.2. Under the storage and transportation conditions, the effective storage period is one year from the date of production. 7. Safety, health and environmental protection regulations
The paint contains organic solvents such as cyclohexanone and xylene, which are flammable liquids, and contains a small amount of free TDI monomer, which is toxic to a certain extent. Therefore, the construction site should comply with the coating operation and safety operation procedures, and take measures such as fire prevention, dust prevention, anti-static and anti-toxic. 3
HG2454-93
Appendix A
Construction reference
(reference)
A1 Brushing, spraying and dipping are all possible, and the viscosity can be adjusted by diluting with polyurethane paint thinner. A2 Before use, the two components are used in accordance with the ratio specified on the manufacturer's packaging or instruction manual, and the amount is used. The prepared paint liquid is best used up within 4 hours (23±2℃). A3 The paint is dried at room temperature, and can also be baked for 1 hour at 120±2℃. The paint component must be properly stored, and the container must be tightly sealed to prevent water seepage and air leakage from causing the paint liquid to gel and deteriorate. A4
Appendix B
Determination of free toluene diisocyanate in polyurethane coatings by gas chromatography
(Supplement)
B1 Scope of application
This appendix applies to the determination of free toluene diisocyanate (TDI) in polyurethane coatings. B2
Principle of the method
The sample is gasified and passed through the chromatographic column to separate the free toluene diisocyanate to be measured from other components, and then detected by a hydrogen flame ionization detector and quantified by the internal standard method.
B3 Materials
B3.1 Carrier gas: nitrogen, purity 99.8%
B3.2 Fuel gas: hydrogen, purity ≥99.8%
B3.3 Fuel-supporting gas: air.
B4 Reagents
B4.1 Ethyl acetate: analytical grade, dehydrated with 5A molecular sieves B4.2 Tetradecane: chromatographic grade;
B4.3 Toluene diisocyanate: analytical grade (mixture of 80% 2.4-toluene diisocyanate and 20% 2.6-toluene diisocyanate). B5 Instruments
B5.1 Gas chromatograph: any type of chromatograph that can meet the requirements of analytical conditions, equipped with a hydrogen flame ionization detector, and the detection limit of benzene D<1×10-g/s. The inner lining of the vaporizer can be replaced with a glass tube or a section of empty column in front of the column, and it should be cleaned regularly. B5.2 Chromatographic column: stainless steel column with an inner diameter of 2mm and a length of 1m. Column packing:
Fixed liquid: 7% dimethyl silicone oil SE-30.
b. Carrier: 102 silanized white carrier, 80100 mesh. B5.3 Injector: micro syringe, 1uL. 4
B6 chromatographic operating conditions
Internal standard: tetradecane;
Column temperature: 150℃,
Detector temperature: 200℃;
Vaporization chamber temperature: 150℃;
Carrier gas flow rate: nitrogen, 30mL/min;
Injection volume: 0.2uL.
B7 Preparation
B7.1 Preparation of stationary phase
HG2454—93
According to the liquid-carrier ratio, accurately weigh a certain amount of stationary liquid dimethyl silicone oil, measure 1.2 times the volume of the carrier solvent chloroform, add it to a ground-mouth round-bottom flask, connect a ground-mouth condenser, heat and reflux for half an hour, after the stationary liquid is completely dissolved, pour the carrier in, continue to reflux for 1.5 to 2 hours, then cut off the power supply and remove the condenser, heat to about 50℃ in a fume hood with an infrared lamp, slowly evaporate the solvent until dry, heat to 60℃, dry for half an hour, sieve and set aside. B7.2 Filling and aging of chromatographic column
Plug one end of the washed and dried column with a copper wire mesh, connect it to a vacuum pump to evacuate, connect the other end to a funnel, slowly add the prepared stationary phase, and gently tap the chromatographic column until the stationary phase no longer enters, plug both ends with glass wool. Then connect the column to the chromatograph (without the detector) and pass nitrogen for segmented aging. Aging at 80℃, 120℃, and 160℃ for 2h respectively, and then aging at 185℃ until the baseline is straight. B7.3 Determination of correction factor
B7.3.1 Preparation of internal standard solution: weigh 1.0g (accurate to 0.0002g) of tetradecane, put it into a dry volumetric flask, and dilute it to 100mL with anhydrous ethyl acetate.
B7.3.2 Preparation of toluene diisocyanate solution: weigh 1.0g (accurate to 0.0002g) of toluene diisocyanate monomer, put it into a dry volumetric flask, and dilute it to 100mL with anhydrous ethyl acetate. The shelf life of this solution is two days. B7.3.3 Prepare standard samples: Use a pipette to accurately draw 5 mL of internal standard solution and 5 mL of toluene diisocyanate solution, inject into the sample bottle, mix, and shake well. B7.3.4 According to the chromatographic operating conditions, after the instrument is stabilized, inject the standard sample into the chromatograph and record the chromatogram. B7.3.5 Calculate the relative correction factor of toluene diisocyanate according to formula (B1): mTDIAcL4
mcI4·ATDI
Relative correction factor of toluene diisocyanate In the formula -
The mass of toluene diisocyanate in the standard sample; mc14——The mass of tetradecane in the standard sample, gATD1——The peak area of toluene diisocyanate; Ac14——The peak area of tetradecane.
The relative correction factor measured by the above test steps can be used only if the difference between the two measurement results is less than 10%. B7.4 Determination of relative retention time
B7.4.1 According to the chromatographic operating conditions, after the instrument is stable, inject the standard sample into the chromatograph and record the retention time of each component. Take tetradecane as the benchmark, calculate the relative retention time of each component, and use this relative retention time for qualitative analysis. B7.4.2 The retention time of each component is in the following order: ethyl acetate;
toluene diisocyanate;
tetradecane.
HG2454-93
Attached is a typical chromatogram of free toluene diisocyanate monomer in polyurethane coating. 241
B8 Determination steps
Typical chromatogram of free toluene diisocyanate monomer in polyurethane coating 1-ethyl acetate; 2-solvent in coating
B8.1 Determination of sample weight: The sample weight is determined based on the content of free toluene diisocyanate. See Table B1: Table B1
Percentage of free toluene diisocyanate
Weighing amount
B8.2 Inject the sample into the sample bottle according to the above table, weigh the mass of the sample by the incremental method (accurate to 0.0002g), then add 5mL of internal standard solution with a pipette, add 5mL of anhydrous ethyl acetate with a 10mL measuring cylinder, and mix and shake well. B8.3 According to the chromatographic operating conditions, after the instrument is stable, inject 0.2mL of the sample prepared according to the above requirements into the chromatograph, and record the chromatogram. B8.4 Qualitatively analyze each component according to the relative retention time. B8.5 Measure the peak area of free toluene diisocyanate and tetradecane (internal standard). When measuring manually, measure the peak height and half-peak width. The peak area is obtained by multiplying the peak height by the half-peak width. If a data processor is used, the analysis and calculation program can be pre-programmed for automatic calculation. 6
B9 Calculation
HG2454—93
Calculate the percentage of free toluene diisocyanate according to formula (B2). Calculate to 0.01%. Xrm%_meuy · Arnr f
m·Acl4
-The mass percentage of free toluene diisocyanate in the sample; where: Xor
-The mass of the sample,;
-The mass of the added internal standard tetradecane, g; Armr——The peak area of free toluene diisocyanate, cmAcu——The peak area of the internal standard tetradecane, cm\-Relative correction factor for toluene diisocyanate. Precision
Use the following values to judge the reliability of the results. B10.1 Repeatability: The absolute value of the difference between two repeated measurements by the same operator should not be greater than 0.10%. 2 Reproducibility: The absolute value of the difference between the results of the same sample measured by two laboratories should not be greater than 0.20%. B10.2
B11 Report
Take the arithmetic mean of the results of two parallel determinations as the determination result of free toluene diisocyanate in the sample, and report the result to 0.01%.
Additional Notes:
This standard is proposed by the Science and Technology Department of the Ministry of Chemical Industry of the People's Republic of China. This standard is under the jurisdiction of the Coatings Product Technical Committee. This standard was drafted by Wuhan Shuanghu Coatings Industry Company and the Coatings Industry Research Institute of the Ministry of Chemical Industry. The main drafters of this standard are Liu Xingping, Wang Yihong and Liu Jiyuan. This standard refers to the Canadian Government Specification Bureau 1-GP-180M general-purpose two-pack polyurethane coating standard. From the date of implementation of this standard, the original professional standard ZBG51107-88 (S01-3 Polyurethane varnish (repackaging) of the People's Republic of China will be invalid.01%.
Additional Notes:
This standard was proposed by the Science and Technology Department of the Ministry of Chemical Industry of the People's Republic of China. This standard is under the jurisdiction of the Coatings Product Technical Committee. This standard was drafted by Wuhan Shuanghu Coatings Industry Company and the Coatings Industry Research Institute of the Ministry of Chemical Industry. The main drafters of this standard are Liu Xingping, Wang Yihong and Liu Jiyuan. This standard refers to the Canadian Government Specification Bureau 1-GP-180M general-purpose two-pack polyurethane coating standard. From the date of implementation of this standard, the original professional standard ZBG51107-88 (S01-3 Polyurethane varnish (repackaging) of the People's Republic of China will be invalid.01%.
Additional Notes:
This standard was proposed by the Science and Technology Department of the Ministry of Chemical Industry of the People's Republic of China. This standard is under the jurisdiction of the Coatings Product Technical Committee. This standard was drafted by Wuhan Shuanghu Coatings Industry Company and the Coatings Industry Research Institute of the Ministry of Chemical Industry. The main drafters of this standard are Liu Xingping, Wang Yihong and Liu Jiyuan. This standard refers to the Canadian Government Specification Bureau 1-GP-180M general-purpose two-pack polyurethane coating standard. From the date of implementation of this standard, the original professional standard ZBG51107-88 (S01-3 Polyurethane varnish (repackaging) of the People's Republic of China will be invalid.01%.
Additional Notes:
This standard was proposed by the Science and Technology Department of the Ministry of Chemical Industry of the People's Republic of China. This standard is under the jurisdiction of the Coatings Product Technical Committee. This standard was drafted by Wuhan Shuanghu Coatings Industry Company and the Coatings Industry Research Institute of the Ministry of Chemical Industry. The main drafters of this standard are Liu Xingping, Wang Yihong and Liu Jiyuan. This standard refers to the Canadian Government Specification Bureau 1-GP-180M general-purpose two-pack polyurethane coating standard. From the date of implementation of this standard, the original professional standard ZBG51107-88 (S01-3 Polyurethane varnish (repackaging) of the People's Republic of China will be invalid.01%.
Additional Notes:
This standard was proposed by the Science and Technology Department of the Ministry of Chemical Industry of the People's Republic of China. This standard is under the jurisdiction of the Coatings Product Technical Committee. This standard was drafted by Wuhan Shuanghu Coatings Industry Company and the Coatings Industry Research Institute of the Ministry of Chemical Industry. The main drafters of this standard are Liu Xingping, Wang Yihong and Liu Jiyuan. This standard refers to the Canadian Government Specification Bureau 1-GP-180M general-purpose two-pack polyurethane coating standard. From the date of implementation of this standard, the original professional standard ZBG51107-88 (S01-3 Polyurethane varnish (repackaging) of the People's Republic of China will be invalid.1Carrier gas: nitrogen, purity 99.8%
B3.2Fuel gas: hydrogen, purity ≥99.8%
B3.3Combustion-supporting gas: air.
B4Reagents
B4.1Ethyl acetate: analytical grade, dehydrated with 5A molecular sieveB4.2Tetradecane: chromatographic grade;
B4.3Toluene diisocyanate: analytical grade (mixture of 80% 2.4-toluene diisocyanate and 20% 2.6-toluene diisocyanate). B5Instrument
B5.1Gas chromatograph: any type of chromatograph that can meet the requirements of analytical conditions, equipped with a hydrogen flame ionization detector, and the detection limit of benzene D<1×10-g/s. The inner lining of the vaporizer can be replaced with a glass tube or a section of empty column in front of the column, and it should be cleaned regularly. B5.2Chromatographic column: 2mm inner diameter, 1m long stainless steel column. Column packing:
Fixed liquid: 7% dimethyl silicone oil SE-30.
b. Carrier: 102 silanized white carrier, 80100 mesh. B5.3 Injector: micro syringe, 1uL. 4
B6 Chromatographic operating conditions
Internal standard: tetradecane;
Column temperature: 150℃,
Detector temperature: 200℃;
Vaporization chamber temperature: 150℃;
Carrier gas flow rate: nitrogen, 30mL/min;
Injection volume: 0.2uL.
B7 Preparation
B7.1 Preparation of stationary phase
HG2454—93
According to the liquid-carrier ratio, accurately weigh a certain amount of stationary liquid dimethyl silicone oil, measure 1.2 times the volume of the carrier solvent chloroform, add it to a ground-mouth round-bottom flask, connect a ground-mouth condenser, heat and reflux for half an hour, after the stationary liquid is completely dissolved, pour the carrier in, continue to reflux for 1.5 to 2 hours, then cut off the power supply and remove the condenser, heat to about 50℃ in a fume hood with an infrared lamp, slowly evaporate the solvent until dry, heat to 60℃, dry for half an hour, sieve and set aside. B7.2 Filling and aging of chromatographic column
Plug one end of the washed and dried column with a copper wire mesh, connect it to a vacuum pump to evacuate, connect the other end to a funnel, slowly add the prepared stationary phase, and gently tap the chromatographic column until the stationary phase no longer enters, plug both ends with glass wool. Then connect the column to the chromatograph (without the detector) and pass nitrogen for segmented aging. Aging at 80℃, 120℃, and 160℃ for 2h respectively, and then aging at 185℃ until the baseline is straight. B7.3 Determination of correction factor
B7.3.1 Preparation of internal standard solution: weigh 1.0g (accurate to 0.0002g) of tetradecane, put it into a dry volumetric flask, and dilute it to 100mL with anhydrous ethyl acetate.
B7.3.2 Preparation of toluene diisocyanate solution: weigh 1.0g (accurate to 0.0002g) of toluene diisocyanate monomer, put it into a dry volumetric flask, and dilute it to 100mL with anhydrous ethyl acetate. The shelf life of this solution is two days. B7.3.3 Prepare standard samples: Use a pipette to accurately draw 5 mL of internal standard solution and 5 mL of toluene diisocyanate solution, inject into the sample bottle, mix, and shake well. B7.3.4 According to the chromatographic operating conditions, after the instrument is stabilized, inject the standard sample into the chromatograph and record the chromatogram. B7.3.5 Calculate the relative correction factor of toluene diisocyanate according to formula (B1): mTDIAcL4
mcI4·ATDI
Relative correction factor of toluene diisocyanate In the formula -
The mass of toluene diisocyanate in the standard sample; mc14——The mass of tetradecane in the standard sample, gATD1——The peak area of toluene diisocyanate; Ac14——The peak area of tetradecane. wwW.bzxz.Net
The relative correction factor measured by the above test steps can be used only if the difference between the two measurement results is less than 10%. B7.4 Determination of relative retention time
B7.4.1 According to the chromatographic operating conditions, after the instrument is stable, inject the standard sample into the chromatograph and record the retention time of each component. Take tetradecane as the benchmark, calculate the relative retention time of each component, and use this relative retention time for qualitative analysis. B7.4.2 The retention time of each component is in the following order: ethyl acetate;
toluene diisocyanate;
tetradecane.
HG2454-93
Attached is a typical chromatogram of free toluene diisocyanate monomer in polyurethane coating. 241
B8 Determination steps
Typical chromatogram of free toluene diisocyanate monomer in polyurethane coating 1-ethyl acetate; 2-solvent in coating
B8.1 Determination of sample weight: The sample weight is determined based on the content of free toluene diisocyanate. See Table B1: Table B1
Percentage of free toluene diisocyanate
Weighing amount
B8.2 Inject the sample into the sample bottle according to the above table, weigh the mass of the sample by the incremental method (accurate to 0.0002g), then add 5mL of internal standard solution with a pipette, add 5mL of anhydrous ethyl acetate with a 10mL measuring cylinder, and mix and shake well. B8.3 According to the chromatographic operating conditions, after the instrument is stable, inject 0.2mL of the sample prepared according to the above requirements into the chromatograph, and record the chromatogram. B8.4 Qualitatively analyze each component according to the relative retention time. B8.5 Measure the peak area of free toluene diisocyanate and tetradecane (internal standard). When measuring manually, measure the peak height and half-peak width. The peak area is obtained by multiplying the peak height by the half-peak width. If a data processor is used, the analysis and calculation program can be pre-programmed for automatic calculation. 6
B9 Calculation
HG2454—93
Calculate the percentage of free toluene diisocyanate according to formula (B2). Calculate to 0.01%. Xrm%_meuy · Arnr f
m·Acl4
-The mass percentage of free toluene diisocyanate in the sample; where: Xor
-The mass of the sample,;
-The mass of the added internal standard tetradecane, g; Armr——The peak area of free toluene diisocyanate, cmAcu——The peak area of the internal standard tetradecane, cm\-Relative correction factor for toluene diisocyanate. Precision
Use the following values to judge the reliability of the results. B10.1 Repeatability: The absolute value of the difference between two repeated measurements by the same operator should not be greater than 0.10%. 2 Reproducibility: The absolute value of the difference between the results of the same sample measured by two laboratories should not be greater than 0.20%. B10.2
B11 Report
Take the arithmetic mean of the results of two parallel determinations as the determination result of free toluene diisocyanate in the sample, and report the result to 0.01%.
Additional Notes:
This standard is proposed by the Science and Technology Department of the Ministry of Chemical Industry of the People's Republic of China. This standard is under the jurisdiction of the Coatings Product Technical Committee. This standard was drafted by Wuhan Shuanghu Coatings Industry Company and the Coatings Industry Research Institute of the Ministry of Chemical Industry. The main drafters of this standard are Liu Xingping, Wang Yihong and Liu Jiyuan. This standard refers to the Canadian Government Specification Bureau 1-GP-180M general-purpose two-pack polyurethane coating standard. From the date of implementation of this standard, the original professional standard ZBG51107-88 (S01-3 Polyurethane varnish (repackaging) of the People's Republic of China will be invalid.1Carrier gas: nitrogen, purity 99.8%
B3.2Fuel gas: hydrogen, purity ≥99.8%
B3.3Combustion-supporting gas: air.
B4Reagents
B4.1Ethyl acetate: analytical grade, dehydrated with 5A molecular sieveB4.2Tetradecane: chromatographic grade;
B4.3Toluene diisocyanate: analytical grade (mixture of 80% 2.4-toluene diisocyanate and 20% 2.6-toluene diisocyanate). B5Instrument
B5.1Gas chromatograph: any type of chromatograph that can meet the requirements of analytical conditions, equipped with a hydrogen flame ionization detector, and the detection limit of benzene D<1×10-g/s. The inner lining of the vaporizer can be replaced with a glass tube or a section of empty column in front of the column, which should be cleaned regularly. B5.2Chromatographic column: 2mm inner diameter, 1m long stainless steel column. Column packing:
Fixed liquid: 7% dimethyl silicone oil SE-30.
b. Carrier: 102 silanized white carrier, 80100 mesh. B5.3 Injector: micro syringe, 1uL. 4
B6 Chromatographic operating conditions
Internal standard: tetradecane;
Column temperature: 150℃,
Detector temperature: 200℃;
Vaporization chamber temperature: 150℃;
Carrier gas flow rate: nitrogen, 30mL/min;
Injection volume: 0.2uL.
B7 Preparation
B7.1 Preparation of stationary phase
HG2454—93
According to the liquid-carrier ratio, accurately weigh a certain amount of stationary liquid dimethyl silicone oil, measure 1.2 times the volume of the carrier solvent chloroform, add it to a ground-mouth round-bottom flask, connect a ground-mouth condenser, heat and reflux for half an hour, after the stationary liquid is completely dissolved, pour the carrier in, continue to reflux for 1.5 to 2 hours, then cut off the power supply and remove the condenser, heat to about 50℃ in a fume hood with an infrared lamp, slowly evaporate the solvent until dry, heat to 60℃, dry for half an hour, sieve and set aside. B7.2 Filling and aging of chromatographic column
Plug one end of the washed and dried column with a copper wire mesh, connect it to a vacuum pump to evacuate, connect the other end to a funnel, slowly add the prepared stationary phase, and gently tap the chromatographic column until the stationary phase no longer enters, plug both ends with glass wool. Then connect the column to the chromatograph (without the detector) and pass nitrogen for segmented aging. Aging at 80℃, 120℃, and 160℃ for 2h respectively, and then aging at 185℃ until the baseline is straight. B7.3 Determination of correction factor
B7.3.1 Preparation of internal standard solution: weigh 1.0g (accurate to 0.0002g) of tetradecane, put it into a dry volumetric flask, and dilute it to 100mL with anhydrous ethyl acetate.
B7.3.2 Preparation of toluene diisocyanate solution: weigh 1.0g (accurate to 0.0002g) of toluene diisocyanate monomer, put it into a dry volumetric flask, and dilute it to 100mL with anhydrous ethyl acetate. The shelf life of this solution is two days. B7.3.3 Prepare standard samples: Use a pipette to accurately draw 5 mL of internal standard solution and 5 mL of toluene diisocyanate solution, inject into the sample bottle, mix, and shake well. B7.3.4 According to the chromatographic operating conditions, after the instrument is stabilized, inject the standard sample into the chromatograph and record the chromatogram. B7.3.5 Calculate the relative correction factor of toluene diisocyanate according to formula (B1): mTDIAcL4
mcI4·ATDI
Relative correction factor of toluene diisocyanate In the formula -
The mass of toluene diisocyanate in the standard sample; mc14——The mass of tetradecane in the standard sample, gATD1——The peak area of toluene diisocyanate; Ac14——The peak area of tetradecane.
The relative correction factor measured by the above test steps can only be used if the difference between the two measurement results is less than 10%. B7.4 Determination of relative retention time
B7.4.1 According to the chromatographic operating conditions, after the instrument is stable, inject the standard sample into the chromatograph and record the retention time of each component. Take tetradecane as the benchmark, calculate the relative retention time of each component, and use this relative retention time for qualitative analysis. B7.4.2 The retention time of each component is in the following order: ethyl acetate;
toluene diisocyanate;
tetradecane.
HG2454-93
Attached is a typical chromatogram of free toluene diisocyanate monomer in polyurethane coating. 241
B8 Determination steps
Typical chromatogram of free toluene diisocyanate monomer in polyurethane coating 1-ethyl acetate; 2-solvent in coating
B8.1 Determination of sample weight: The sample weight is determined based on the content of free toluene diisocyanate. See Table B1: Table B1
Percentage of free toluene diisocyanate
Weighing amount
B8.2 Inject the sample into the sample bottle according to the above table, weigh the mass of the sample by the incremental method (accurate to 0.0002g), then add 5mL of internal standard solution with a pipette, add 5mL of anhydrous ethyl acetate with a 10mL measuring cylinder, and mix and shake well. B8.3 According to the chromatographic operating conditions, after the instrument is stable, inject 0.2mL of the sample prepared according to the above requirements into the chromatograph, and record the chromatogram. B8.4 Qualitatively analyze each component according to the relative retention time. B8.5 Measure the peak area of free toluene diisocyanate and tetradecane (internal standard). When measuring manually, measure the peak height and half-peak width. The peak area is obtained by multiplying the peak height by the half-peak width. If a data processor is used, the analysis and calculation program can be pre-programmed for automatic calculation. 6
B9 Calculation
HG2454—93
Calculate the percentage of free toluene diisocyanate according to formula (B2). Calculate to 0.01%. Xrm%_meuy · Arnr f
m·Acl4
-The mass percentage of free toluene diisocyanate in the sample; where: Xor
-The mass of the sample,;
-The mass of the added internal standard tetradecane, g; Armr——The peak area of free toluene diisocyanate, cmAcu——The peak area of the internal standard tetradecane, cm\-Relative correction factor for toluene diisocyanate. Precision
Use the following values to judge the reliability of the results. B10.1 Repeatability: The absolute value of the difference between two repeated measurements by the same operator should not be greater than 0.10%. 2 Reproducibility: The absolute value of the difference between the results of the same sample measured by two laboratories should not be greater than 0.20%. B10.2
B11 Report
Take the arithmetic mean of the results of two parallel determinations as the determination result of free toluene diisocyanate in the sample, and report the result to 0.01%.
Additional Notes:
This standard is proposed by the Science and Technology Department of the Ministry of Chemical Industry of the People's Republic of China. This standard is under the jurisdiction of the Coatings Product Technical Committee. This standard was drafted by Wuhan Shuanghu Coatings Industry Company and the Coatings Industry Research Institute of the Ministry of Chemical Industry. The main drafters of this standard are Liu Xingping, Wang Yihong and Liu Jiyuan. This standard refers to the Canadian Government Specification Bureau 1-GP-180M general-purpose two-pack polyurethane coating standard. From the date of implementation of this standard, the original professional standard ZBG51107-88 (S01-3 Polyurethane varnish (repackaging) of the People's Republic of China will be invalid.Add 2 times the solvent chloroform into a ground-mouth round-bottom flask, connect a ground-mouth condenser, heat and reflux for half an hour, and after the stationary liquid is completely dissolved, pour the carrier in, continue to reflux for 1.5 to 2 hours, then cut off the power supply and remove the condenser, heat to about 50°C with an infrared lamp in a fume hood, slowly evaporate the solvent until dry, heat to 60°C, dry for half an hour, sieve and set aside. B7.2 Filling and aging of chromatographic columns
Plug one end of the washed and dried column with a copper wire mesh, and connect it to a vacuum pump for air extraction, connect the other end to a funnel, slowly add the prepared stationary phase, and gently tap the chromatographic column until the stationary phase no longer enters, and plug both ends with glass wool. Then connect the column to a chromatograph (without a detector) and pass nitrogen for segmented aging, aging at 80°C, 120°C, and 160°C for 2 hours respectively, and then raise it to 185°C for aging until the baseline is straight. B7.3 Determination of correction factor
B7.3.1 Preparation of internal standard solution: Weigh 1.0g (accurate to 0.0002g) of tetradecane, put it into a dry volumetric flask, and dilute it to 100mL with anhydrous ethyl acetate.
B7.3.2 Preparation of toluene diisocyanate solution: Weigh 1.0g (accurate to 0.0002g) of toluene diisocyanate monomer, put it into a dry volumetric flask, and dilute it to 100mL with anhydrous ethyl acetate. The shelf life of this solution is two days. B7.3.3 Preparation of standard sample: Use a pipette to accurately draw 5mL of internal standard solution and 5mL of toluene diisocyanate solution, inject them into the sample bottle, mix them, and shake them well
B7.3.4 According to the chromatographic operating conditions, after the instrument is stabilized, inject the standard sample into the chromatograph and record the chromatogram. B7.3.5 Calculate the relative correction factor of toluene diisocyanate according to formula (B1): mTDIAcL4
mcI4·ATDI
Relative correction factor of toluene diisocyanate Where -
mass of toluene diisocyanate in the standard sample; mc14——mass of tetradecane in the standard sample, gATD1——peak area of toluene diisocyanate; Ac14——peak area of tetradecane.
The relative correction factor measured by the above test steps can only be used if the difference between the two measurement results is less than 10%. B7.4 Determination of relative retention time
B7.4.1 According to the chromatographic operating conditions, after the instrument is stable, inject the standard sample into the chromatograph and record the retention time of each component. Take tetradecane as the benchmark, calculate the relative retention time of each component, and use this relative retention time for qualitative analysis. B7.4.2 The retention time sequence of each component is as follows: ethyl acetate;
toluene diisocyanate;
tetradecane.
HG2454-93
Attached is a typical chromatogram of free toluene diisocyanate monomer in polyurethane coating. 241
B8 Determination steps
Typical chromatogram of free toluene diisocyanate monomer in polyurethane coating 1-ethyl acetate; 2-solvent in coating
B8.1 Determination of sample weight: The sample weight is determined based on the content of free toluene diisocyanate. See Table B1: Table B1
Percentage of free toluene diisocyanate
Weighing amount
B8.2 Inject the sample into the sample bottle according to the above table, weigh the mass of the sample by the incremental method (accurate to 0.0002g), then add 5mL of internal standard solution with a pipette, add 5mL of anhydrous ethyl acetate with a 10mL measuring cylinder, and mix and shake well. B8.3 According to the chromatographic operating conditions, after the instrument is stable, inject 0.2mL of the sample prepared according to the above requirements into the chromatograph, and record the chromatogram. B8.4 Qualitatively analyze each component according to the relative retention time. B8.5 Measure the peak area of free toluene diisocyanate and tetradecane (internal standard). When measuring manually, measure the peak height and half-peak width. The peak area is obtained by multiplying the peak height by the half-peak width. If a data processor is used, the analysis and calculation program can be pre-programmed for automatic calculation. 6
B9 Calculation
HG2454—93
Calculate the percentage of free toluene diisocyanate according to formula (B2). Calculate to 0.01%. Xrm%_meuy · Arnr f
m·Acl4
-The mass percentage of free toluene diisocyanate in the sample; where: Xor
-The mass of the sample,;
-The mass of the added internal standard tetradecane, g; Armr——The peak area of free toluene diisocyanate, cmAcu——The peak area of the internal standard tetradecane, cm\-Relative correction factor for toluene diisocyanate. Precision
Use the following values to judge the reliability of the results. B10.1 Repeatability: The absolute value of the difference between two repeated measurements by the same operator should not be greater than 0.10%. 2 Reproducibility: The absolute value of the difference between the results of the same sample measured by two laboratories should not be greater than 0.20%. B10.2
B11 Report
Take the arithmetic mean of the results of two parallel determinations as the determination result of free toluene diisocyanate in the sample, and report the result to 0.01%.
Additional Notes:
This standard is proposed by the Science and Technology Department of the Ministry of Chemical Industry of the People's Republic of China. This standard is under the jurisdiction of the Coatings Product Technical Committee. This standard was drafted by Wuhan Shuanghu Coatings Industry Company and the Coatings Industry Research Institute of the Ministry of Chemical Industry. The main drafters of this standard are Liu Xingping, Wang Yihong and Liu Jiyuan. This standard refers to the Canadian Government Specification Bureau 1-GP-180M general-purpose two-pack polyurethane coating standard. From the date of implementation of this standard, the original professional standard ZBG51107-88 (S01-3 Polyurethane varnish (repackaging) of the People's Republic of China will be invalid.Add 2 times the solvent chloroform into a ground-mouth round-bottom flask, connect a ground-mouth condenser, heat and reflux for half an hour, and after the stationary liquid is completely dissolved, pour the carrier in, continue to reflux for 1.5 to 2 hours, then cut off the power supply and remove the condenser, heat to about 50°C with an infrared lamp in a fume hood, slowly evaporate the solvent until dry, heat to 60°C, dry for half an hour, sieve and set aside. B7.2 Filling and aging of chromatographic columns
Plug one end of the washed and dried column with a copper wire mesh, and connect it to a vacuum pump for air extraction, connect the other end to a funnel, slowly add the prepared stationary phase, and gently tap the chromatographic column until the stationary phase no longer enters, and plug both ends with glass wool. Then connect the column to a chromatograph (without a detector) and pass nitrogen for segmented aging, aging at 80°C, 120°C, and 160°C for 2 hours respectively, and then raise it to 185°C for aging until the baseline is straight. B7.3 Determination of correction factor
B7.3.1 Preparation of internal standard solution: Weigh 1.0g (accurate to 0.0002g) of tetradecane, put it into a dry volumetric flask, and dilute it to 100mL with anhydrous ethyl acetate.
B7.3.2 Preparation of toluene diisocyanate solution: Weigh 1.0g (accurate to 0.0002g) of toluene diisocyanate monomer, put it into a dry volumetric flask, and dilute it to 100mL with anhydrous ethyl acetate. The shelf life of this solution is two days. B7.3.3 Preparation of standard sample: Use a pipette to accurately draw 5mL of internal standard solution and 5mL of toluene diisocyanate solution, inject them into the sample bottle, mix them, and shake them well
B7.3.4 According to the chromatographic operating conditions, after the instrument is stabilized, inject the standard sample into the chromatograph and record the chromatogram. B7.3.5 Calculate the relative correction factor of toluene diisocyanate according to formula (B1): mTDIAcL4
mcI4·ATDI
Relative correction factor of toluene diisocyanate Where -
mass of toluene diisocyanate in the standard sample; mc14——mass of tetradecane in the standard sample, gATD1——peak area of toluene diisocyanate; Ac14——peak area of tetradecane.
The relative correction factor measured by the above test steps can only be used if the difference between the two measurement results is less than 10%. B7.4 Determination of relative retention time
B7.4.1 According to the chromatographic operating conditions, after the instrument is stable, inject the standard sample into the chromatograph and record the retention time of each component. Take tetradecane as the benchmark, calculate the relative retention time of each component, and use this relative retention time for qualitative analysis. B7.4.2 The retention time sequence of each component is as follows: ethyl acetate;
toluene diisocyanate;
tetradecane.
HG2454-93
Attached is a typical chromatogram of free toluene diisocyanate monomer in polyurethane coating. 241
B8 Determination steps
Typical chromatogram of free toluene diisocyanate monomer in polyurethane coating 1-ethyl acetate; 2-solvent in coating
B8.1 Determination of sample weight: The sample weight is determined based on the content of free toluene diisocyanate. See Table B1: Table B1
Percentage of free toluene diisocyanate
Weighing amount
B8.2 Inject the sample into the sample bottle according to the above table, weigh the mass of the sample by the incremental method (accurate to 0.0002g), then add 5mL of internal standard solution with a pipette, add 5mL of anhydrous ethyl acetate with a 10mL measuring cylinder, and mix and shake well. B8.3 According to the chromatographic operating conditions, after the instrument is stable, inject 0.2mL of the sample prepared according to the above requirements into the chromatograph, and record the chromatogram. B8.4 Qualitatively analyze each component according to the relative retention time. B8.5 Measure the peak area of free toluene diisocyanate and tetradecane (internal standard). When measuring manually, measure the peak height and half-peak width. The peak area is obtained by multiplying the peak height by the half-peak width. If a data processor is used, the analysis and calculation program can be pre-programmed for automatic calculation. 6
B9 Calculation
HG2454—93
Calculate the percentage of free toluene diisocyanate according to formula (B2). Calculate to 0.01%. Xrm%_meuy · Arnr f
m·Acl4
-The mass percentage of free toluene diisocyanate in the sample; where: Xor
-The mass of the sample,;
-The mass of the added internal standard tetradecane, g; Armr——The peak area of free toluene diisocyanate, cmAcu——The peak area of the internal standard tetradecane, cm\-Relative correction factor for toluene diisocyanate. Precision
Use the following values to judge the reliability of the results. B10.1 Repeatability: The absolute value of the difference between two repeated measurements by the same operator should not be greater than 0.10%. 2 Reproducibility: The absolute value of the difference between the results of the same sample measured by two laboratories should not be greater than 0.20%. B10.2
B11 Report
Take the arithmetic mean of the results of two parallel determinations as the determination result of free toluene diisocyanate in the sample, and report the result to 0.01%.
Additional Notes:
This standard is proposed by the Science and Technology Department of the Ministry of Chemical Industry of the People's Republic of China. This standard is under the jurisdiction of the Coatings Product Technical Committee. This standard was drafted by Wuhan Shuanghu Coatings Industry Company and the Coatings Industry Research Institute of the Ministry of Chemical Industry. The main drafters of this standard are Liu Xingping, Wang Yihong and Liu Jiyuan. This standard refers to the Canadian Government Specification Bureau 1-GP-180M general-purpose two-pack polyurethane coating standard. From the date of implementation of this standard, the original professional standard ZBG51107-88 (S01-3 Polyurethane varnish (repackaging) of the People's Republic of China will be invalid.0002g), then add 5mL of internal standard solution with a pipette, add 5mL of anhydrous ethyl acetate with a 10mL measuring cylinder, mix and shake. B8.3 According to the chromatographic operating conditions, after the instrument is stable, inject 0.2mL of the sample prepared according to the above requirements into the chromatograph and record the chromatogram. B8.4 Qualitatively characterize each component according to the relative retention time. B8.5 Measure the peak area of free toluene diisocyanate and tetradecane (internal standard). When measuring manually, measure the peak height and half-peak width. The peak area is obtained by multiplying the peak height by the half-peak width. If a data processor is used, the analysis and calculation program can be pre-programmed for automatic calculation. 6
B9 Calculation
HG2454—93
Calculate the percentage of free toluene diisocyanate according to formula (B2). Calculate to 0.01%. Xrm%_meuy · Arnr f
m·Acl4
-The mass percentage of free toluene diisocyanate in the sample; where: Xor
-The mass of the sample, g;
-The mass of the added internal standard tetradecane, g; Armr-The peak area of free toluene diisocyanate, cmAcu-The peak area of the internal standard tetradecane, cm\-Relative correction factor for toluene diisocyanate. Precision
The following values are used to judge the reliability of the results. B10.1 Repeatability: The absolute value of the difference between the results of two repeated measurements by the same operator should not be greater than 0.10%. 2 Reproducibility: The absolute value of the difference between the results of the same sample measured by two laboratories should not be greater than 0.20%. B10.2
B11 Report
Take the arithmetic mean of the results of two parallel measurements as the determination result of free toluene diisocyanate in the sample, and report the result to 0.01%.
Additional Notes:
This standard was proposed by the Science and Technology Department of the Ministry of Chemical Industry of the People's Republic of China. This standard is under the jurisdiction of the Coatings Product Technical Committee. This standard was drafted by Wuhan Shuanghu Coatings Industry Company and the Coatings Industry Research Institute of the Ministry of Chemical Industry. The main drafters of this standard are Liu Xingping, Wang Yihong and Liu Jiyuan. This standard refers to the Canadian Government Specification Bureau 1-GP-180M general-purpose two-pack polyurethane coating standard. From the date of implementation of this standard, the original professional standard ZBG51107-88 (S01-3 Polyurethane varnish (repackaging) of the People's Republic of China will be invalid.0002g), then add 5mL of internal standard solution with a pipette, add 5mL of anhydrous ethyl acetate with a 10mL measuring cylinder, and mix and shake. B8.3 According to the chromatographic operating conditions, after the instrument is stable, inject 0.2mL of the sample prepared according to the above requirements into the chromatograph, and record the chromatogram. B8.4 Qualitatively characterize each component according to the relative retention time. B8.5 Measure the peak area of free toluene diisocyanate and tetradecane (internal standard). When measuring manually, measure the peak height and half-peak width. The peak area is obtained by multiplying the peak height by the half-peak width. If a data processor is used, the analysis and calculation program can be pre-programmed for automatic calculation. 6
B9 Calculation
HG2454—93
Calculate the percentage of free toluene diisocyanate according to formula (B2). Calculate to 0.01%. Xrm%_meuy · Arnr f
m·Acl4
-The mass percentage of free toluene diisocyanate in the sample; where: Xor
-The mass of the sample,;
-The mass of the added internal standard tetradecane, g; Armr-The peak area of free toluene diisocyanate, cmAcu-The peak area of the internal standard tetradecane, cm\-Relative correction factor for toluene diisocyanate. Precision
The following values are used to judge the reliability of the results. B10.1 Repeatability: The absolute value of the difference between the results of two repeated measurements by the same operator should not be greater than 0.10%. 2 Reproducibility: The absolute value of the difference between the results of the same sample measured by two laboratories should not be greater than 0.20%. B10.2
B11 Report
Take the arithmetic mean of the results of two parallel measurements as the determination result of free toluene diisocyanate in the sample, and report the result to 0.01%.
Additional Notes:
This standard was proposed by the Science and Technology Department of the Ministry of Chemical Industry of the People's Republic of China. This standard is under the jurisdiction of the Coatings Product Technical Committee. This standard was drafted by Wuhan Shuanghu Coatings Industry Company and the Coatings Industry Research Institute of the Ministry of Chemical Industry. The main drafters of this standard are Liu Xingping, Wang Yihong and Liu Jiyuan. This standard refers to the Canadian Government Specification Bureau 1-GP-180M general-purpose two-pack polyurethane coating standard. From the date of implementation of this standard, the original professional standard ZBG51107-88 (S01-3 Polyurethane varnish (repackaging) of the People's Republic of China will be invalid.
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