CN103713059A - Qualification and quantification method for polyamide resin in polyamide engineering plastic - Google Patents
Qualification and quantification method for polyamide resin in polyamide engineering plastic Download PDFInfo
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- CN103713059A CN103713059A CN201310742378.4A CN201310742378A CN103713059A CN 103713059 A CN103713059 A CN 103713059A CN 201310742378 A CN201310742378 A CN 201310742378A CN 103713059 A CN103713059 A CN 103713059A
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- 239000004952 Polyamide Substances 0.000 title claims abstract description 75
- 229920002647 polyamide Polymers 0.000 title claims abstract description 75
- 229920006351 engineering plastic Polymers 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 7
- 229920006122 polyamide resin Polymers 0.000 title abstract 5
- 238000012797 qualification Methods 0.000 title abstract 3
- 238000011002 quantification Methods 0.000 title abstract 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 34
- 239000000945 filler Substances 0.000 claims description 19
- 239000008139 complexing agent Substances 0.000 claims description 17
- 238000009413 insulation Methods 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 13
- 238000004445 quantitative analysis Methods 0.000 claims description 13
- 239000000843 powder Substances 0.000 claims description 12
- 150000003863 ammonium salts Chemical class 0.000 claims description 11
- YNPNZTXNASCQKK-UHFFFAOYSA-N Phenanthrene Natural products C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 claims description 8
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- 238000004451 qualitative analysis Methods 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 238000011109 contamination Methods 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 239000000413 hydrolysate Substances 0.000 claims description 2
- 238000003808 methanol extraction Methods 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 2
- 239000012498 ultrapure water Substances 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims 2
- 238000001514 detection method Methods 0.000 abstract description 8
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 abstract description 6
- 230000000536 complexating effect Effects 0.000 abstract description 3
- 229910021645 metal ion Inorganic materials 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 81
- 239000000523 sample Substances 0.000 description 45
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 36
- SYECJBOWSGTPLU-UHFFFAOYSA-N hexane-1,1-diamine Chemical compound CCCCCC(N)N SYECJBOWSGTPLU-UHFFFAOYSA-N 0.000 description 27
- 239000012752 auxiliary agent Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 9
- QVYARBLCAHCSFJ-UHFFFAOYSA-N butane-1,1-diamine Chemical compound CCCC(N)N QVYARBLCAHCSFJ-UHFFFAOYSA-N 0.000 description 9
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 9
- 230000007062 hydrolysis Effects 0.000 description 8
- 238000006460 hydrolysis reaction Methods 0.000 description 8
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 229920000305 Nylon 6,10 Polymers 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 229910000019 calcium carbonate Inorganic materials 0.000 description 5
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 5
- 235000019796 monopotassium phosphate Nutrition 0.000 description 5
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 5
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 229910052918 calcium silicate Inorganic materials 0.000 description 3
- 239000000378 calcium silicate Substances 0.000 description 3
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- -1 plastifier Substances 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- VFKZTMPDYBFSTM-KVTDHHQDSA-N Mitobronitol Chemical compound BrC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CBr VFKZTMPDYBFSTM-KVTDHHQDSA-N 0.000 description 1
- 229920006152 PA1010 Polymers 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920006111 poly(hexamethylene terephthalamide) Polymers 0.000 description 1
- 229920006128 poly(nonamethylene terephthalamide) Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical compound [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polyamides (AREA)
- Investigating Or Analysing Materials By Optical Means (AREA)
Abstract
The invention discloses a qualification and quantification method for polyamide resin in polyamide engineering plastic, aiming at replacing polyamide resin in a complexing system formed by polyamide resin in polyamide engineering plastic and metal ions through a substance which is strong in complexing power, so as to realize accurate qualification and quantification of the polyamide resin in the polyamide engineering plastic through LC, LC-MS and other detection means.
Description
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Technical field
The present invention relates to the qualitative-and-quantitative method of major component in a kind of engineering plastics, specifically, is the qualitative-and-quantitative method of polyamide in a kind of Polyamide Engineering Plastic, the qualitative-and-quantitative method of polyamide in especially blend Polyamide Engineering Plastic.
Background technology
Polyamide (English: Polyamide, PA) is the macromolecule aggregating into by amido link by containing carboxyl and amino monomer.Polyamide Engineering Plastic is by polyamide, and adding the adjuvants such as plastifier, filler, lubricant, colorant is auxiliary element, and under uniform temperature, pressure, the plastic product that the type of making or crosslinking curing moulding obtain is moulded in processing.
In preparation Polyamide Engineering Plastic, often add the physical property that calcium carbonate, calcium silicate, metal oxide or metal powder improve plastics, reduce costs simultaneously.
To Polyamide Engineering Plastic, when the resinous principle in especially blend Polyamide Engineering Plastic carries out qualitative and quantitative analysis, only utilize instrument to detect and be difficult to accomplish accurate qualitative, quantitative, for example: utilize and infrared Polyamide Engineering Plastic is carried out when qualitative, because the interpolation auxiliary agent in plastics can cause the fingerprint region in infared spectrum not obvious, even do not go out peak, affected the accurately qualitative of Polyamide Engineering Plastic; Utilize the mass spectrum can only be by simple in structure, the functional group in the little non-blend Polyamide Engineering Plastic of molecular weight be qualitative, but because polyamide is of a great variety, complex structure is changeable, and for complex structure, molecular weight is large, the Polyamide Engineering Plastic of blend is difficult to accurately qualitative.Only by instrument means, be difficult to the Polyamide Engineering Plastic of various species all to carry out accurate qualitative, quantitative, therefore adopt the method for hydrolysis that Polyamide Engineering Plastic is decomposed into carboxylic acid and ammonium salt, the carboxylic acid kind generating by hydrolysis and ammonium salt kind can be carried out the polyamide of each type accurately qualitative, but the filler adding in Polyamide Engineering Plastic, calcium carbonate for example, can with carboxylic acid in hydroxyl, amino generation complex reaction in ammonium salt, this complex system Stability Analysis of Structures, and inconsistent with the relevant nature of the episome of carboxylic acid and ammonium salt, cause the quantitatively inaccurate of Polyamide Engineering Plastic.
For Polyamide Engineering Plastic, the qualitative inaccurate or quantitatively inaccurate problem of existence when the resinous principle in especially blend Polyamide Engineering Plastic carries out qualitative and quantitative analysis, the present invention is by hydrolytic process, add complexing agent and the filler that another complex performance is stronger and carry out complete complexing, carboxylic acid-filler and ammonium salt-filler complex system are decomposed, by discharging carboxylic acid and ammonium salt completely, utilize analytical instrument to carry out accurate qualitative, quantitative to the polyamide composition in Polyamide Engineering Plastic.
Summary of the invention
The qualitative-and-quantitative method that the object of this invention is to provide polyamide in a kind of Polyamide Engineering Plastic.
Carboxylic acid-filler that the present invention forms by strong complexing agent the carboxylic acid, ammonium salt and the filler that generate after Polyamide Engineering Plastic hydrolysis and carboxylic acid and the ammonium salt in ammonium salt-filler complex system cement out, form filler-strong complexing agent system, thereby realize with polyamide in the accurate qualitative, quantitative Polyamide Engineering Plastic of the multiple detection meanss such as LC, LC-MS, the polyamide in especially blend Polyamide Engineering Plastic.
To achieve these goals, the qualitative-and-quantitative method of polyamide in a kind of Polyamide Engineering Plastic, comprises the following steps:
A) Polyamide Engineering Plastic is dissolved in formic acid, until completely dissolved with methanol extraction filtration;
B) filter residue is at room temperature dried, make Silon powder sample;
C) in Polyamide Engineering Plastic sample, add concentrated hydrochloric acid, at 130 ℃, add hot reflux 30-50h;
D) hydrolysate is poured in beaker, hydrochloric acid is removed in evaporation;
E) in Silon powder sample, add strong complexing agent, regulate pH value to 5-8, be put in 80 ℃ of water baths, heating and thermal insulation is processed 5 hours;
F) in the sample after insulation is processed, add ultrapure water benefit and weigh, sample system, by carboxylic acid-filler and ammonium salt-filler complex system, is transformed into filler-strong complexing agent system;
G) free carboxylic acid and ammonium salt in the sample after processing carried out to qualitative and quantitative analysis, the contamination by carboxylic acid and ammonium salt carries out accurate qualitative, quantitative to the polyamide in Polyamide Engineering Plastic.
Can be used for Polyamide Engineering Plastic of the present invention and include but not limited to one or more in PA6, PA66, PAll, PAl2, PA46, PA610, PA612, PAl010, PA6T, PA9T.
Can be used for strong complexing agent of the present invention and include but not limited to one or more in DBM, oxine, Phen.
The described preferred oxine of strong complexing agent, one or both in Phen.
The filler that can be used for being added in Polyamide Engineering Plastic can be selected one or more in slaine, metal oxide, metal powder.
Described filler includes but not limited to one or more in calcium carbonate, calcium silicate, line borate, calcium hydroxide, barium sulphate, magnesium hydroxide, zinc paste, titanium dioxide.
One or more in the preferred calcium carbonate of described filler, calcium silicate, calcium hydroxide.
The features such as in a kind of Polyamide Engineering Plastic of the present invention, the qualitative-and-quantitative method of polyamide has accurately, quick, cost is low, simple to operate.
Embodiment
Below, in connection with principle and exemplary embodiment, describe the method for polyamide in the accurate qualitative, quantitative Polyamide Engineering Plastic of the present invention in detail.
PA66 related in following examples is general rank, the 80G33L type PA66 being produced by du pont company.
In following examples, related PA46 is general rank, the TW200F8 type PA46 being produced by Dutch DSM N. V..
Concentrated hydrochloric acid related in following examples, for analyzing pure rank, is produced by Chemical Reagent Co., Ltd., Sinopharm Group.
Strong complexing agent Phen related in following examples, for analyzing pure rank, is produced by Chemical Reagent Co., Ltd., Sinopharm Group.
Strong complexing agent oxine related in following examples is for analyzing pure rank, and by lark prestige, Science and Technology Ltd. produces.
The liquid chromatograph of the LC-20A type that in following examples, related LCWei Shimadzu company produces.
In following examples, related LC-MS is the LC-MS-2020 type liquid chromatograph-mass spectrometer that Shimadzu company produces.
Embodiment 1
Pre-service is to be hydrolyzed Polyamide Engineering Plastic:
Measure the Polyamide Engineering Plastic PA66 of 100g, after making polyamide powder sample, methyl alcohol processing adds concentrated hydrochloric acid 200ml, be put in 130 ℃ of oil bath casees, heating and thermal insulation is processed 40 hours, the product that evaporative removal hydrochloric acid obtains containing hexane diacid, hexane diamine and adds auxiliary agent.
Eliminate the impact of the rear filler of hydrolysis and hexane diacid and hexane diamine generation complex reaction:
In the product that contains hexane diacid, hexane diamine and interpolation auxiliary agent, drip strong complexing agent Phen 2g, regulate pH value to 5, be put in 80 ℃ of water baths, heating and thermal insulation is processed 5 hours, is then cooled to room temperature, obtains sample 1.
With LC, detect sample 1:
Prepared sample 1 directly uses LC as detection means, and the concentration content of wherein contained hexane diacid, hexane diamine is analyzed to mensuration.LC determination step carries out in the usual way, and wherein, Details as Follows for each parameter:
Chromatographic condition: chromatographic column is selected C18(250mm * 4.6mm * 5um) chromatographic column; Sample size 10 microlitres; Post case constant temperature is at 35 ℃; Potassium dihydrogen phosphate aqueous solution=5:95 of mobile phase: methyl alcohol: 15mmol; Flow velocity: 0.8mL/min; Detect wavelength: 204nm.
The testing result of sample 1: hexane diacid=48.33%, hexane diamine=47.24%.
Embodiment 2
Pre-service is to be hydrolyzed Polyamide Engineering Plastic:
Measure the Polyamide Engineering Plastic PA66 of 100g, after making polyamide powder sample, methyl alcohol processing adds concentrated hydrochloric acid 250ml, be put in 130 ℃ of oil bath casees, heating and thermal insulation is processed 40 hours, the product that evaporative removal hydrochloric acid obtains containing hexane diacid, hexane diamine and adds auxiliary agent.
Eliminate the impact of the rear filler of hydrolysis and hexane diacid and hexane diamine generation complex reaction:
In the product that contains hexane diacid, hexane diamine and interpolation auxiliary agent, drip strong complexing agent Phen 3g, regulate pH value to 5, be put in 80 ℃ of water baths, heating and thermal insulation is processed 5 hours, is then cooled to room temperature, obtains sample 2.
With LC, detect sample 2:
Prepared sample 2 directly uses LC as detection means, and the concentration content of wherein contained hexane diacid, hexane diamine is analyzed to mensuration.LC determination step carries out in the usual way, and wherein, Details as Follows for each parameter:
Chromatographic condition: chromatographic column is selected C18(250mm * 4.6mm * 5um) chromatographic column; Sample size 10 microlitres; Post case constant temperature is at 35 ℃; Potassium dihydrogen phosphate aqueous solution=5:95 of mobile phase: methyl alcohol: 15mmol; Flow velocity: 0.8mL/min; Detect wavelength: 204nm.
The testing result of sample 2: hexane diacid=47.84%, hexane diamine=48.51%.
Embodiment 3
Pre-service is to be hydrolyzed Polyamide Engineering Plastic:
Measure the PA46 of 60g and the PA66 of 40g fully mixes, after making polyamide powder sample, methyl alcohol processing adds concentrated hydrochloric acid 300ml, be put in 130 ℃ of oil bath casees, heating and thermal insulation is processed 40 hours, the product that evaporative removal hydrochloric acid obtains containing hexane diacid, butanediamine, hexane diamine and adds auxiliary agent.
Eliminate the impact of the rear filler of hydrolysis and hexane diacid, butanediamine and hexane diamine generation complex reaction:
In the product that contains hexane diacid, butanediamine, hexane diamine and interpolation auxiliary agent, drip strong complexing agent Phen 2g, regulate pH value to 5, be put in 80 ℃ of water baths, heating and thermal insulation is processed 5 hours, is then cooled to room temperature, obtains sample 3.
With LC, detect sample 3:
Prepared sample 3 directly uses LC as detection means, and the concentration content of wherein contained hexane diacid, butanediamine, hexane diamine is analyzed to mensuration.LC determination step carries out in the usual way, and wherein, Details as Follows for each parameter:
Chromatographic condition: chromatographic column is selected C18(250mm * 4.6mm * 5um) chromatographic column; Sample size 10 microlitres; Post case constant temperature is at 35 ℃; Potassium dihydrogen phosphate aqueous solution=5:95 of mobile phase: methyl alcohol: 15mmol; Flow velocity: 0.8mL/min; Detect wavelength: 204nm.
The testing result of sample 3: hexane diacid=47.52%, butanediamine=27.68%, hexane diamine=22.25%.
Embodiment 4
Pre-service is to be hydrolyzed Polyamide Engineering Plastic:
The PA1010 that measures the PA46 of 40g, the PA66 of 30g and 30g fully mixes, after making polyamide powder sample, methyl alcohol processing adds concentrated hydrochloric acid 300ml, be put in 130 ℃ of oil bath casees, heating and thermal insulation is processed 40 hours, the product that evaporative removal hydrochloric acid obtains containing hexane diacid, butanediamine, hexane diamine, decanedioic acid, decamethylene diamine and adds auxiliary agent.
Eliminate the impact of the rear filler of hydrolysis and polyamide generation complex reaction:
To the product that contains hexane diacid, butanediamine, hexane diamine, decanedioic acid, decamethylene diamine and interpolation auxiliary agent, drip strong complexing agent oxine 2g, regulate pH value to 5, be put in 80 ℃ of water baths, heating and thermal insulation is processed 2 hours, is then cooled to room temperature, obtains sample 4.
With LC, detect sample 4:
Prepared sample 4 directly uses LC as detection means, and the concentration content of wherein contained hexane diacid, butanediamine, hexane diamine, decanedioic acid and decamethylene diamine is analyzed to mensuration.LC determination step carries out in the usual way, and wherein, Details as Follows for each parameter:
Chromatographic condition: chromatographic column is selected C18(250mm * 4.6mm * 5um) chromatographic column; Sample size 10 microlitres; Post case constant temperature is at 35 ℃; Potassium dihydrogen phosphate aqueous solution=5:95 of mobile phase: methyl alcohol: 15mmol; Flow velocity: 0.8mL/min; Detect wavelength: 204nm.
The testing result of sample 4: hexane diacid=34.86%, butanediamine=13.56%, hexane diamine=18.78%, decanedioic acid=14.92%, decamethylene diamine=14.15%.
Embodiment 5
Pre-service is to be hydrolyzed Polyamide Engineering Plastic:
Measure the Polyamide Engineering Plastic PA66 of 100g, after making polyamide powder sample, methyl alcohol processing adds concentrated hydrochloric acid 200ml, be put in 130 ℃ of oil bath casees, heating and thermal insulation is processed 40 hours, the product that evaporative removal hydrochloric acid obtains containing hexane diacid, hexane diamine and adds auxiliary agent.
Eliminate the impact of the rear filler-calcium carbonate of hydrolysis and hexane diacid and hexane diamine generation complex reaction:
In the product that contains hexane diacid, hexane diamine and interpolation auxiliary agent, drip strong complexing agent Phen 2g, regulate pH value to 5, be put in 80 ℃ of water baths, heating and thermal insulation is processed 5 hours, is then cooled to room temperature, obtains sample 5.
With LC-MS, detect sample 5:
Prepared sample 5 directly uses LC-MS as detection means, and the concentration content of wherein contained hexane diacid, hexane diamine is analyzed to mensuration.LC-MS determination step carries out in the usual way, and wherein, Details as Follows for each parameter:
Chromatographic condition: chromatographic column is selected C18 (150mm * 2.1mm * 5um) chromatographic column; Sample size 10 microlitres; Post case constant temperature is at 35 ℃; Mobile phase: methyl alcohol: aqueous formic acid=5:95 of 0.1; Flow velocity: 0.2mL/min;
Mass spectrum condition: ionization source: electron spray (ESI); Ionization mode: negative ion mode; Interface parameters: atomizer: 40 psi; Dry gas: 10Lmin
-l; Dry gas temperature: 350 ℃; Capillary voltage: 3500 V; Detector voltage: 1.50kV; Ionization mode: ESI Positive nitrogen flow: 1.5L/min.
The testing result of sample 5: hexane diacid=49.12%, hexane diamine=49.75%.
Embodiment 6
Pre-service is to be hydrolyzed Polyamide Engineering Plastic:
Measure the Polyamide Engineering Plastic PA66 of 100g, after making polyamide powder sample, methyl alcohol processing adds concentrated hydrochloric acid 200ml, be put in 130 ℃ of oil bath casees, heating and thermal insulation is processed 40 hours, the product that evaporative removal hydrochloric acid obtains containing hexane diacid, hexane diamine and adds auxiliary agent.
With LC, detect sample 6:
Prepared sample 6 directly uses LC as detection means, and the concentration content of wherein contained hexane diacid, hexane diamine is analyzed to mensuration.LC determination step carries out in the usual way, and wherein, Details as Follows for each parameter:
Chromatographic condition: chromatographic column is selected C18(250mm * 4.6mm * 5um) chromatographic column; Sample size 10 microlitres; Post case constant temperature is at 35 ℃; Potassium dihydrogen phosphate aqueous solution=5:95 of mobile phase: methyl alcohol: 15mmol; Flow velocity: 0.8mL/min; Detect wavelength: 204nm.
The testing result of sample 6: hexane diacid=43.14%, hexane diamine=42.71%.
Embodiment 7
Relative standard deviation (RSD) test
To sample 1 and 2 respectively according to embodiment 1, embodiment 3 repeat 6 times independently pre-service to prepare solution to be detected, and analyze respectively mensuration, 6 measurement results are carried out to statistical treatment and according to relative standard deviation (RSD), assess precision of the present invention, the results are shown in following table:
As seen from the above table, RSD < 2%, it shows that precision of the present invention is good, and operation is succinct easily to be grasped, and the sample solution measurement result that repeatedly prepared by independent operation is consistent, and repeatability, repeatability are good.
Embodiment 8
The test that adds slaine impact
First sample 1 and 4 being carried out to pre-service according to embodiment 1, embodiment 4 prepares solution to be detected and analyzes mensuration, then metallic impurity of the artificial iron that adds 50mg/L, copper, nickel in its primary sample respectively, again according to embodiment 1, embodiment 4, carrying out pre-service again prepares solution to be detected and analyzes mensuration, the measurement result that relatively adds both sides, metallic impurity front and back, in order to verify the actual effect of this method elimination slaine impact, result sees table:
Unit: %
As seen from the above table, before and after metallic impurity add, the measurement result of sample is basically identical, indicates that the present invention can effectively eliminate the impact of slaine, has good reliability.
Although illustrated and described the present invention, the invention is not restricted to this in conjunction with the embodiments.In the situation that not departing from spirit of the present invention and instruction, can embodiment be made and being revised and distortion.Scope of the present invention is limited by claim and equivalent thereof.
Claims (2)
1. the qualitative-and-quantitative method of polyamide in Polyamide Engineering Plastic, is characterized in that, said method comprising the steps of:
A) Polyamide Engineering Plastic is dissolved in formic acid, until completely dissolved with methanol extraction filtration;
B) filter residue is at room temperature dried, make Silon powder sample;
C) in Polyamide Engineering Plastic sample, add concentrated hydrochloric acid, at 130 ℃, add hot reflux 30-50h;
D) hydrolysate is poured in beaker, hydrochloric acid is removed in evaporation;
E) in Silon powder sample, add the strong complexing agent of weight portion, regulate pH value to 5-8, be put in 80 ℃ of water baths, heating and thermal insulation is processed 5 hours;
F) in the sample after insulation is processed, add ultrapure water benefit and weigh, sample system, by carboxylic acid-filler and ammonium salt-filler complex system, is transformed into filler-strong complexing agent system;
G) free carboxylic acid and ammonium salt in the sample after processing carried out to qualitative and quantitative analysis, the contamination by carboxylic acid and ammonium salt carries out accurate qualitative, quantitative to the polyamide in Polyamide Engineering Plastic.
2. the qualitative-and-quantitative method of polyamide in Polyamide Engineering Plastic according to claim 1, is characterized in that, described strong complexing agent is selected from one or both in oxine, Phen.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105116077A (en) * | 2015-07-22 | 2015-12-02 | 乌鲁木齐谱尼测试科技有限公司 | Pretreatment method of polybrominated biphenyls and poly brominated diphenyl ethers in nylon resin and nylon resin products |
| CN106680275A (en) * | 2016-12-26 | 2017-05-17 | 上海微谱化工技术服务有限公司 | Method for analyzing polyurethane in polyvinyl chloride system |
| CN111537661A (en) * | 2020-04-02 | 2020-08-14 | 广东美塑塑料科技有限公司 | Method for identifying and quantitatively determining polyamide material by using GC/MS |
| US11549920B2 (en) | 2017-11-20 | 2023-01-10 | Lg Chem, Ltd. | Method for quantitative analysis of monomers in polyimide film |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1613962B1 (en) * | 2003-04-14 | 2008-10-29 | Caliper Life Sciences, Inc. | Reduction of migration shift assay interference |
| CN103134884A (en) * | 2011-12-01 | 2013-06-05 | 天津天士力之骄药业有限公司 | Method of detecting polyamide residues in Chinese medicine extractive |
-
2013
- 2013-12-30 CN CN201310742378.4A patent/CN103713059B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1613962B1 (en) * | 2003-04-14 | 2008-10-29 | Caliper Life Sciences, Inc. | Reduction of migration shift assay interference |
| CN103134884A (en) * | 2011-12-01 | 2013-06-05 | 天津天士力之骄药业有限公司 | Method of detecting polyamide residues in Chinese medicine extractive |
Non-Patent Citations (3)
| Title |
|---|
| 徐厚才 等: "树形聚酰胺胺与Cu2+的络合作用", 《分析测试学报》 * |
| 王建华 等: "高效液相色谱法测定尼龙6样品中的环状齐聚物", 《合成纤维工业》 * |
| 钟国秀 等: "氟盐置换-EDTA络合-铅盐滴定法测定硅铁中铝", 《理化试验-化学分册》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105116077A (en) * | 2015-07-22 | 2015-12-02 | 乌鲁木齐谱尼测试科技有限公司 | Pretreatment method of polybrominated biphenyls and poly brominated diphenyl ethers in nylon resin and nylon resin products |
| CN106680275A (en) * | 2016-12-26 | 2017-05-17 | 上海微谱化工技术服务有限公司 | Method for analyzing polyurethane in polyvinyl chloride system |
| CN106680275B (en) * | 2016-12-26 | 2019-12-17 | 上海微谱化工技术服务有限公司 | Method for analyzing polyurethane in polyvinyl chloride system |
| US11549920B2 (en) | 2017-11-20 | 2023-01-10 | Lg Chem, Ltd. | Method for quantitative analysis of monomers in polyimide film |
| CN111537661A (en) * | 2020-04-02 | 2020-08-14 | 广东美塑塑料科技有限公司 | Method for identifying and quantitatively determining polyamide material by using GC/MS |
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