CN115629142B - Detection method and application of free maleic anhydride in PP-g-MAH - Google Patents
Detection method and application of free maleic anhydride in PP-g-MAH Download PDFInfo
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- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 238000001514 detection method Methods 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 40
- 238000001819 mass spectrum Methods 0.000 claims abstract description 19
- 230000004044 response Effects 0.000 claims abstract description 19
- 239000012086 standard solution Substances 0.000 claims abstract description 18
- 238000012360 testing method Methods 0.000 claims abstract description 18
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 238000002347 injection Methods 0.000 claims description 7
- 239000007924 injection Substances 0.000 claims description 7
- 208000033962 Fontaine progeroid syndrome Diseases 0.000 claims description 6
- 238000003795 desorption Methods 0.000 claims description 6
- 238000004949 mass spectrometry Methods 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 238000002076 thermal analysis method Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 238000004458 analytical method Methods 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 5
- 231100000331 toxic Toxicity 0.000 abstract description 5
- 230000002588 toxic effect Effects 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000004743 Polypropylene Substances 0.000 description 11
- 239000000178 monomer Substances 0.000 description 8
- -1 polypropylene Polymers 0.000 description 8
- 229920001155 polypropylene Polymers 0.000 description 7
- 238000004448 titration Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000004566 IR spectroscopy Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000000859 sublimation Methods 0.000 description 3
- 230000008022 sublimation Effects 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 238000002479 acid--base titration Methods 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000004227 thermal cracking Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- WVRNUXJQQFPNMN-VAWYXSNFSA-N 3-[(e)-dodec-1-enyl]oxolane-2,5-dione Chemical compound CCCCCCCCCC\C=C\C1CC(=O)OC1=O WVRNUXJQQFPNMN-VAWYXSNFSA-N 0.000 description 1
- 239000004831 Hot glue Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000002372 labelling Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229920001911 maleic anhydride grafted polypropylene Polymers 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000013094 purity test Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
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- G—PHYSICS
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N30/12—Preparation by evaporation
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
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- G01N30/8675—Evaluation, i.e. decoding of the signal into analytical information
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Abstract
The invention provides a detection method and application of free maleic anhydride in PP-g-MAH, and particularly relates to the technical field of maleic anhydride detection. The detection method comprises the steps of preparing maleic anhydride standard substances into 4-6 standard solutions with different concentrations, and testing MAH mass spectrum response areas in the standard solutions in a thermal cracking-gas chromatography-mass spectrometry combined instrument; drawing a standard curve according to MAH mass spectrum response area and concentration; and finally, placing the PP-g-MAH sample in a thermal cracking-gas chromatograph-mass spectrometer, and substituting the mass spectrum response area of the free maleic anhydride obtained by testing into a standard curve to obtain the content of the free maleic anhydride. The detection method is environment-friendly, and toxic reagents are not used; the method is quick and efficient, the standard curve is simple to manufacture, and the test time of a single sample is less than 15 minutes; the result is accurate, the detection limit is low (RL=0.025 wt%) and the detection efficiency is improved, which is beneficial to industrial production.
Description
Technical Field
The invention relates to the technical field of maleic anhydride detection, in particular to a detection method and application of free maleic anhydride in PP-g-MAH.
Background
The maleic anhydride grafted polypropylene (PP-g-MAH) is prepared by introducing active monomer Maleic Anhydride (MAH) on a non-polar macromolecular polypropylene PP chain segment, is mainly applied to products such as engineering plastics, adhesives and the like, and is widely applied to industries such as automobiles, solar energy, packaging, furniture and the like, wherein the PP-g-MAH serves as a compatilizer and hot melt adhesive.
The preparation method of the PP-g-MAH mainly comprises a solution grafting method, a melt grafting method and the like. The solution grafting method can cause free MAH monomer residues after sample preparation, the melt grafting method can have a higher proportion of free MAH monomers which are not grafted successfully, the residual free MAH monomers have strong volatility, the material has obvious smell, and polypropylene chains are thermally oxidized in the extrusion processing process, so that the basic performance of the material is affected.
The grafting rate of PP-g-MAH, namely the content of MAH grafted on the PP chain segment, can have a great influence on the interfacial properties of the polymer, and the method for measuring the grafting rate of PP-g-MAH mainly comprises an acid-base titration method and an infrared spectrophotometry at present, so that the accurate measurement of free MAH residual monomers can obtain more accurate MAH grafting rate. The main method for testing MAH at present is to test the eluent by chemical titration after dissolution and elution of solvent (such as dimethylbenzene), and the method needs a large amount of samples and toxic reagents, is time-consuming and tedious in operation, has a relatively fuzzy titration end point and has a certain error due to a large residual MAH range (0.1-20wt%).
In view of this, the present invention has been made.
Disclosure of Invention
The invention aims to provide a method for detecting free maleic anhydride in PP-g-MAH, so as to solve the technical problems that a large amount of samples and toxic reagents are needed in the titration method in the prior art, and the operation is time-consuming, tedious and poor in accuracy.
In order to solve the technical problems, the invention adopts the following technical scheme:
the first aspect of the invention provides a method for detecting free maleic anhydride in PP-g-MAH, which comprises the following steps:
step A: preparing maleic anhydride standard substances into 4-6 standard solutions with different concentrations, and testing MAH mass spectrum response areas in the standard solutions in a thermal cracking-gas chromatography-mass spectrometry combined instrument (Py-GCMS);
and (B) step (B): drawing a standard curve according to MAH mass spectrum response area and concentration;
step C: and placing the PP-g-MAH sample in a thermal cracking-gas chromatograph-mass spectrometer, testing to obtain the mass spectrum response area of the free maleic anhydride, and substituting the mass spectrum response area of the free maleic anhydride into a standard curve to obtain the concentration of the free maleic anhydride.
Optionally, the purity of the maleic anhydride standard is more than or equal to 99.0%.
Optionally, in step a, the solvent used for the standard solution includes at least one of methanol, acetonitrile, acetone and ethyl acetate.
Optionally, the linear correlation coefficient of the standard curve obtained in the step B is more than or equal to 0.999.
Optionally, in the thermal cracking process, the thermal desorption temperature is set to 170-200 ℃ and the desorption time is 10-15 min.
Alternatively, the chromatography column model is HP-5MS;
the temperature-raising program is that the temperature is kept at 40 ℃ for 2min, then the temperature is raised to 200 ℃ at 20 ℃/min, and finally the temperature is kept at 200 ℃ for 2min;
the sample injection mode is split sample injection, and the split ratio is 50-100:1;
the sample injection amount is 5-10 mu L.
Alternatively, the MAH-feature mass spectrometry ions comprise m/z:54, 98.
Optionally, the interface temperature is 250-300 ℃, and the front sample inlet temperature is 250-300 ℃.
Optionally, the model of the thermal cracking-gas chromatograph-mass spectrometer comprises front Py-3030D/Agilent 7890B-5977A.
The second aspect of the invention provides the use of the detection method for detecting free maleic anhydride in PP-g-MAH.
Compared with the prior art, the invention has at least the following beneficial effects:
according to the method for detecting the free maleic anhydride in the PP-g-MAH, the energy required by breaking the C-C bond of the maleic anhydride successfully grafted and the polypropylene is high, so that the cracking temperature of the grafted maleic anhydride which is separated from a polypropylene polymer system is higher than 450 ℃, the free maleic anhydride remains in the PP-g-MAH system in a monomer form, sublimation starts at 50 ℃, the free maleic anhydride in the system can be effectively and fully separated by using a thermal cracking-gas chromatography and mass spectrometry combined instrument, the polypropylene is not thermally oxidized, the maleic anhydride successfully grafted by the system is not separated, the free maleic anhydride is accurately captured, and the better accuracy is obtained by measuring. Compared with titration and infrared spectrometry, the relative deviation is smaller than 10%. The detection method is environment-friendly, and toxic reagents are not used; the method is quick and efficient, the standard curve is simple to manufacture, and the test time of a single sample is less than 15 minutes; the result is accurate, the detection limit is low (RL=0.025 wt%) and the detection efficiency is improved, which is beneficial to industrial production.
The application of the invention provides a more accurate detection method for detecting the free maleic anhydride in the PP-g-MAH, and is suitable for large-scale popularization and use.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is a thermogravimetric plot (TGA) of MAH;
FIG. 2 is a graph of purity of MAH after recrystallization in example 1;
FIG. 3 is a MAH standard curve plotted in example 1;
FIG. 4 is a graph of total TIC and m/z54 for standard solution VI;
FIG. 5 is a graph of total TIC and m/z54 for PP-g-MAH samples.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. The components of embodiments of the present invention may be arranged and designed in a wide variety of different configurations.
It is noted that relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
In the present invention, the temperature is not specifically defined, that is, at room temperature or at room temperature, that is, the temperature influence is not particularly considered in the related operation, and heating or refrigerating treatment is not required.
According to the first aspect of the invention, the method for detecting the free maleic anhydride in the PP-g-MAH comprises the following steps:
step A: preparing maleic anhydride standard substances into 4-6 standard solutions with different concentrations, and testing MAH mass spectrum response areas in the standard solutions in a thermal cracking-gas chromatography-mass spectrometry combined instrument;
and (B) step (B): drawing a standard curve according to MAH mass spectrum response area and concentration;
step C: and placing the PP-g-MAH sample in a thermal cracking-gas chromatograph-mass spectrometer, testing to obtain the mass spectrum response area of the free maleic anhydride, and substituting the mass spectrum response area of the free maleic anhydride into a standard curve to obtain the concentration of the free maleic anhydride.
According to the method for detecting the free maleic anhydride in the PP-g-MAH, the energy required by breaking the C-C bond of the maleic anhydride successfully grafted and the polypropylene is high, so that the cracking temperature of the grafted maleic anhydride which is separated from a polypropylene polymer system is higher than 450 ℃, the free maleic anhydride remains in the PP-g-MAH system in a monomer form, sublimation starts at 50 ℃, the free maleic anhydride in the system can be effectively and fully separated by using a thermal cracking-gas chromatography and mass spectrometry combined instrument, the polypropylene is not thermally oxidized, the maleic anhydride successfully grafted by the system is not separated, the free maleic anhydride is accurately captured, and the better accuracy is obtained by measuring. Compared with titration and infrared spectrometry, the relative deviation is smaller than 10%. The detection method is environment-friendly, and toxic reagents are not used; the method is quick and efficient, the standard curve is simple to manufacture, and the test time of a single sample is less than 15 minutes; the result is accurate, the detection limit is low (RL=0.025 wt%) and the detection efficiency is improved, which is beneficial to industrial production.
Optionally, the purity of the maleic anhydride standard is more than or equal to 99.0%.
In some embodiments of the invention, to meet purity requirements, commercially available maleic anhydride is recrystallized and the recrystallized MAH is then tested for purity using a differential scanning calorimeter.
Preferably, the purity of the maleic anhydride standard is more than or equal to 99.5%.
Optionally, in step a, the solvent used for the standard solution includes at least one of methanol, acetonitrile, acetone and ethyl acetate.
Optionally, the linear correlation coefficient of the standard curve obtained in the step B is more than or equal to 0.999.
The linear correlation coefficient represents a statistics or parameters of the direction and degree of linear correlation of two variables.
When the linear correlation coefficient of the standard curve is more than or equal to 0.999, the better the fitting degree of the regression line in the standard curve to the observed value is, the higher the reliability of the result for calculating the concentration of the free maleic anhydride in the sample is.
Optionally, in the thermal cracking process, the thermal desorption temperature is set to 170-200 ℃ and the desorption time is 10-15 min.
The free maleic anhydride remained in the form of monomer in the PP-g-MAH system, and started to sublimate at 50 ℃, and when the content was less than 3mg as shown in FIG. 1, it was completely changed into gaseous MAH at 120 ℃, and the sublimation was completed. The thermal desorption temperature of 170-200 ℃ is selected, so that free MAH is rapidly separated from a PP-g-MAH system, the PP is not thermally oxidized, maleic anhydride grafted successfully by the system is not separated, free maleic anhydride is accurately captured, and better accuracy is obtained by measurement.
Alternatively, the chromatography column model is HP-5MS;
the temperature-raising program is that the temperature is kept at 40 ℃ for 2min, then the temperature is raised to 200 ℃ at 20 ℃/min, and finally the temperature is kept at 200 ℃ for 2min;
the sample injection mode is split sample injection, and the split ratio is 50-100:1;
the sample injection amount is 5-10 mu L.
Alternatively, the MAH-feature mass spectrometry ions comprise m/z:54, 98.
The characteristic mass spectrum ions are used to identify MAH and calculate the content of MAH.
Optionally, the interface temperature is 250-300 ℃, and the front sample inlet temperature is 250-300 ℃.
Optionally, the model of the thermal cracking-gas chromatograph-mass spectrometer comprises front Py-3030D/Agilent 7890B-5977A.
The second aspect of the invention provides the use of the detection method for detecting free maleic anhydride in PP-g-MAH.
The application of the invention provides a more accurate detection method for detecting the free maleic anhydride in the PP-g-MAH, and is suitable for large-scale popularization and use.
Some embodiments of the present invention will be described in detail below with reference to examples. The following embodiments and features of the embodiments may be combined with each other without conflict.
Example 1
In this example, the amount of free maleic anhydride in PP-g-MAH, which is a laboratory synthetic sample PP-L1, was measured as follows:
1. the commercially available MAH (Tianjin metallocene, analytical grade) was recrystallized by heating and condensing, and the recrystallized MAH was subjected to purity test by using a differential scanning calorimeter (TA, Q2000), and the obtained differential scanning calorimeter is shown in FIG. 2, and the purity of the recrystallized MAH was 99.8%.
2. 1mg of recrystallized MAH was weighed using a ten-thousandth balance, and a MAH solution I was prepared using ethyl acetate. The solution I was diluted to prepare standard solutions II, III, IV, V, VI, VII having concentrations of 25mg/L, 50mg/L, 100mg/L, 150mg/L, 200mg/L and 250mg/L, respectively.
3. Setting Py-GCMS (front Py-3030D/Agilent 7890B-5977A), setting the thermal analysis temperature to 170 ℃ and the analysis time to 10 minutes; the sample loading of the solution was 10. Mu.L. The chromatographic column model is HP-5MS, the temperature programming is that the temperature is kept for 2min at 40 ℃, the temperature is raised to 200 ℃ at 20 ℃/min, then the chromatographic column model is kept for 2min at 200 ℃, and the split ratio is 100:1. The interface temperature is 300 ℃, the front sample inlet temperature is 300 ℃, and the Py-GCMS draws a standard curve by self-contained software, as shown in figure 3. FIG. 4 is a graph of total TIC and m/z54 for standard solution VI.
4. Accurately weighing PP-g-MAH of 1.00mg, which is a laboratory synthesized sample PP-L1, and directly placing the sample in a thermal analysis crucible. The procedure of Py-GCMS was followed to obtain the mass spectrometry response area of free MAH according to step 3, wherein FIG. 5 is a plot of total TIC and m/z54 of PP-g-MAH samples.
5. Substituting the mass spectrum response area obtained in the step 4 into the standard curve of the step 3, and calculating to obtain the concentration of the free maleic anhydride in the PP-g-MAH to be 0.14%.
Example 2
In this example, the amount of free maleic anhydride in PP-g-MAH was measured, and the method and procedure were the same as in example 1 except that PP-g-MAH in the test sample was PP-L2 in the laboratory synthesis sample.
The concentrations of the standard solutions II, III, IV, V, VI, VII in the step 2 were 50mg/L, 100mg/L, 200mg/L, 500mg/L, 1000mg/L and 2000mg/L, respectively.
The standard curve obtained in step 3 is y= 70498x-2011, r 2 ＝0.9993；
The mass spectrum response area of the free MAH obtained in the step 4 is 953459;
the free maleic anhydride concentration in the PP-g-MAH was calculated in step 5 to be 1.37%.
Example 3
In this example, the amount of free maleic anhydride in PP-g-MAH was measured, and the method and procedure were the same as in example 1 except that PP-g-MAH in the test sample was PP-L3, which was not repeated.
The concentrations of the standard solutions II, III, IV, V, VI, VII in the step 2 were 50mg/L, 100mg/L, 200mg/L, 500mg/L, 1000mg/L and 2000mg/L, respectively.
The standard curve obtained in step 3 is y= 70498x-2011, r 2 ＝0.9993；
The mass spectrum response area of the free MAH obtained in the step 4 is 1207805;
the free maleic anhydride concentration in the PP-g-MAH was calculated in step 5 to be 1.72%.
Comparative example 1
The content of free maleic anhydride in PP-g-MAH was determined by titration in this comparative example, as follows: 1g of PP-L1, PP-L2 and PP-L3 are respectively taken and sheared into small particles as far as possible, 200mL of water is added for condensing, refluxing and extracting for 24 hours, insoluble substances are filtered out, 100mL of deionized water is used for cleaning the insoluble substances for 2-3 times, and then the extracting solution and the cleaning solution are combined. Acid-base titration was directly performed with 0.02mol/L aqueous potassium hydroxide. A1% phenolphthalein solution was used as an indicator.
The free maleic anhydride content in the PP-L1, the PP-L2 and the PP-L3 is calculated to be 0.13%, 1.24% and 1.62% respectively; the deviations of the two methods are-6.4%, 4.8% and 4.93%, respectively.
Comparative example 2
The content of free maleic anhydride in PP-g-MAH was determined by infrared spectroscopy in this comparative example, and the specific steps were as follows: accurately weighing 50g of PP raw material, respectively adding 0.253g, 0.489g, 0.979g, 1.480g and 2.991g of dodecenyl succinic anhydride, and banburying at 180 ℃ for 6min; taking 70mg of each banburying standard sample, and performing infrared spectrum test after film pressing by a flat vulcanizing machine at 190 ℃; and (3) performing standard curve straight line fitting by taking A1791/A1110 as x and the grafting rate of succinic anhydride as y, wherein the curve equation is y=0.2401x+0.0034. After the actual sample is pressed into a film, the value of A1791/A1110 is tested, and then the value of A1791/A1110 is tested again after baking at 120 ℃ for 3 hours, and the free MAH content is calculated by a difference method.
The free maleic anhydride content in the PP-L1, the PP-L2 and the PP-L3 is calculated to be 0.13%, 1.26% and 1.58% respectively; the deviation of the two methods is-4.0%, 5.98% and 2.20% respectively.
Verification example
Preparing a standard solution: 25mg/L, 50mg/L, 100mg/L, 150mg/L, 200mg/L and 250mg/L of standard solution II, III, IV, V, VI, VII were prepared according to the method of step 2 of example 1.
1. Detection limit
Samples were taken in parallel 6 times at 25mg/L and 10. Mu.L were added to a pyrolyzer crucible, the pyrolyzer conditions were set at 170℃for 10min, and after the completion of the test, the samples were calculated by substituting the standard curve, and the results were 0.233. Mu.g, 0.224. Mu.g, 0.241. Mu.g, 0.266. Mu.g, 0.258. Mu.g and 0.240. Mu.g, respectively, with an accuracy of-2.53% and a repeatability error of 6.42%. It is demonstrated that the method can accurately quantify a sample having a free maleic anhydride content of 0.025%.
2. Recovery rate
The samples were verified to be PP-L1, PP-L2, PP-L3 used in the examples and comparative examples, and the labeling results are shown in Table 1.
TABLE 1 actual sample Py-GCMS method for testing MAH content and adding standard recovery rate
As can be seen from Table 1, the detection method provided by the invention has the advantages that the standard adding recovery rate is more than 95%, and the method has excellent accuracy.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (6)
1. The method for detecting the free maleic anhydride in the PP-g-MAH is characterized by comprising the following steps of:
step A: preparing maleic anhydride standard substances into 4-6 standard solutions with different concentrations, and testing MAH mass spectrum response areas in the standard solutions in a thermal cracking-gas chromatography-mass spectrometry combined instrument;
and (B) step (B): drawing a standard curve according to MAH mass spectrum response area and concentration;
step C: setting Py-GCMS in the model of front Py-3030D/Agilent 7890B-5977A, setting the thermal analysis temperature to 170 ℃ and the analysis time to 10 minutes; the sample injection amount of the solution is 10 mu L;
the chromatographic column model is HP-5MS, the temperature programming is that the temperature is kept for 2min at 40 ℃, the temperature is raised to 200 ℃ at 20 ℃/min, then the chromatographic column model is kept for 2min at 200 ℃, and the split ratio is 100:1; the temperature of the interface is 300 ℃, and the temperature of the front sample inlet is 300 ℃;
accurately weighing PP-g-MAH of 1.00mg, taking a laboratory synthesized sample as the sample, directly placing the sample in a thermal desorption crucible, placing the PP-g-MAH sample in a thermal cracking-gas chromatograph-mass spectrometer, testing to obtain the mass spectrum response area of free maleic anhydride, and substituting the mass spectrum response area of the free maleic anhydride into a standard curve to obtain the content of the free maleic anhydride.
2. The method according to claim 1, wherein the maleic anhydride standard has a purity of 99.0% or more.
3. The method according to claim 1, wherein in the step a, the solvent used for the standard solution includes at least one of methanol, acetonitrile, acetone and ethyl acetate.
4. The method according to claim 1, wherein the linear correlation coefficient of the standard curve obtained in the step B is not less than 0.999.
5. The method of claim 1, wherein MAH-feature mass spectrometry ions comprise m/z:54, 98.
6. Use of the detection method according to any one of claims 1-5 for detecting free maleic anhydride in PP-g-MAH.
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| Title |
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| GC/MS法测定苯酐中的马来酸酐;关剑锋;李丹;周明辉;刘莹峰;郑建国;翟翠萍;;现代测量与实验室管理(第06期);全文 * |
| Synthesis and Characterization of Solid-Phase Graft Copolymer of Polypropylene with Styrene and Maleic Anhydride;DEMIN JIA et al.;《Journal of Applied Polymer Science》;第78卷;第2483页右栏至第2484页左栏，第2486页右栏至第2487页左栏 * |
| 气相色谱法测定四氢苯酐中杂质马来酸酐;郝成婷 等;《分析试验室》;第32卷(第4期);第122页右栏，第123页"2. 3 工作曲线和检出限" * |
| 气相色谱法测定苯酐中杂质马来酸酐;郝成婷;王红松;吴珂;孙文文;汤礼军;王文辉;韩品新;;检验检疫学刊(第02期);全文 * |
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