CN106442780A - Purity detection method of quinacridone pigment intermediates - Google Patents
Purity detection method of quinacridone pigment intermediates Download PDFInfo
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- CN106442780A CN106442780A CN201610831178.XA CN201610831178A CN106442780A CN 106442780 A CN106442780 A CN 106442780A CN 201610831178 A CN201610831178 A CN 201610831178A CN 106442780 A CN106442780 A CN 106442780A
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- phosphoric acid
- quinacridone
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- aqueous solution
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- 239000000049 pigment Substances 0.000 title claims abstract description 53
- 238000001514 detection method Methods 0.000 title claims abstract description 49
- 239000000543 intermediate Substances 0.000 title abstract description 58
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 title abstract description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 134
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 67
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000004007 reversed phase HPLC Methods 0.000 claims abstract description 11
- 239000007864 aqueous solution Substances 0.000 claims description 40
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 39
- -1 anionic ion Chemical class 0.000 claims description 39
- 239000003153 chemical reaction reagent Substances 0.000 claims description 32
- 238000012360 testing method Methods 0.000 claims description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 19
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 9
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 8
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- YFSUTJLHUFNCNZ-UHFFFAOYSA-M 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluorooctane-1-sulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YFSUTJLHUFNCNZ-UHFFFAOYSA-M 0.000 claims description 3
- KVGOXGQSTGQXDD-UHFFFAOYSA-N 1-decane-sulfonic-acid Chemical compound CCCCCCCCCCS(O)(=O)=O KVGOXGQSTGQXDD-UHFFFAOYSA-N 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- REFMEZARFCPESH-UHFFFAOYSA-M sodium;heptane-1-sulfonate Chemical compound [Na+].CCCCCCCS([O-])(=O)=O REFMEZARFCPESH-UHFFFAOYSA-M 0.000 claims description 3
- ROBLTDOHDSGGDT-UHFFFAOYSA-M sodium;pentane-1-sulfonate Chemical compound [Na+].CCCCCS([O-])(=O)=O ROBLTDOHDSGGDT-UHFFFAOYSA-M 0.000 claims description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 3
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- QWSZRRAAFHGKCH-UHFFFAOYSA-M sodium;hexane-1-sulfonate Chemical compound [Na+].CCCCCCS([O-])(=O)=O QWSZRRAAFHGKCH-UHFFFAOYSA-M 0.000 claims description 2
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 claims 1
- 125000003368 amide group Chemical group 0.000 claims 1
- 125000000129 anionic group Chemical group 0.000 claims 1
- 239000012535 impurity Substances 0.000 abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- 239000012158 anionic ion-pair reagent Substances 0.000 abstract 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 28
- 229910052938 sodium sulfate Inorganic materials 0.000 description 28
- 235000011152 sodium sulphate Nutrition 0.000 description 28
- 238000004587 chromatography analysis Methods 0.000 description 12
- 238000000926 separation method Methods 0.000 description 12
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 8
- 239000012086 standard solution Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 238000002479 acid--base titration Methods 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 3
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- XORXDJBDZJBCOC-UHFFFAOYSA-N azanium;acetonitrile;acetate Chemical compound [NH4+].CC#N.CC([O-])=O XORXDJBDZJBCOC-UHFFFAOYSA-N 0.000 description 1
- 238000013375 chromatographic separation Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000012417 linear regression Methods 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N o-dicarboxybenzene Natural products OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000004366 reverse phase liquid chromatography Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
Classifications
-
- 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
Landscapes
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
Abstract
The invention provides a purity detection method of quinacridone pigment intermediates. Samples to be detected of the quinacridone pigment intermediates are detected through reversed-phase high-performance liquid chromatography to obtain the purity of the quinacridone pigment intermediates, wherein the detected flow phase is acetonitrile and water solution containing phosphoric acid and anionic ion pair reagents; in addition, in the water solution containing phosphoric acid and anionic ion pair reagents, the concentration of the phosphoric acid is 0.02 to 0.06 weight percent; the concentration of the anionic ion pair reagents is 1 to 5 mmol/L. Further, the retaining capability of impurities and intermediates on the chromatographic column can be greatly improved during the detection; the impurities and the intermediates are enabled to be completely separated, so that the interference of the impurities on the intermediate detection can be completely avoided; the detection accuracy is ensured.
Description
Technical field
The present invention relates to analysis field, more particularly to a kind of detection method of quinacridone-type pigments intermediate purity.
Background technology
Quinacridone-type pigments are a kind of top grade organic pigments, with excellent fastness to light, fastness to heat, in various modelings
Do not migrate in material, be widely used in high-grade paint, engineering plastics, resin, pigment printing, ink, the coloring of rubber and synthesis fine
The fields such as the coloring of dimension oleo stock.Global Ge great pigment company has all carried out more deep grinding to the synthesis of quinacridone-type pigments
Study carefully.For the synthesis of quinacridone-type pigments, China has abundant raw material resources, and product has very big application market again,
But at present the quinacridone-type pigments of domestic product but can only be in some, the using as pigment of low grade products.Which is main
Reason is to lack the effective control to product and its middle weight in process of production, and the synthetic route of quinacridone pigment
Longer, so the control to each middle weight seems increasingly important, only control obtains the key intermediate ability of high-quality
Ensure the high-quality of final products, and the preparation of high-quality key intermediate not only needs suitable preparation technology, which obtains
The management and control of the purity of intermediate is also critically important.
The detection method of quinacridone-type pigments intermediate purity is main three kinds at present：Ultraviolet visible spectrophotometry, general
Logical reversed-phase high-performance liquid chromatography (RP-HPLC) method, acid-base titrations.Ultraviolet visible spectrophotometry is mainly used in quinacridone
The measure of class Pigment Intermediates 2,5- diaryl-amine base-p-phthalic acid purity, in the measure of the method, as impurity is determining ripple
Strong point also has light absorbs, i.e., cannot differentiate the interference of impurity in intermediate sample, thus have a strong impact on the standard of middle body measurement
Exactness.Common reversed phase high-performance liquid chromatography selects C18 reverse phase separation post, and acetonitrile-ammonium acetate is that mobile phase, which is used for quinacridine
Measure of ketone Pigment Intermediates 2, the 5- bis- to chloroanilino-Isosorbide-5-Nitrae-phthalic acid purity, but from the " anti-of the reports such as Chu Chaoxia
Phase high effective liquid chromatography for measuring quinacridone pigment series intermediate 2,5- bis- is to the pure of chloroanilino -1,4- phthalic acid
The chromatogram for being given in degree " article sees, its appearance time is short, and then which cannot be effectively separated with its impurity, impact
The accuracy of its test；Acid-base titrations are widely used in quinacridone-type pigments intermediate 2,5- hexichol amido during industry is generated
The detection of p-phthalic acid methyl ester (structural formula is shown in formula (1)), as such intermediate makes phosphate preservation mostly, thus determines
When be initially charged excess base, then with the content of intermediate in hydrochloric acid standard solution back titration determination sample.In formula (1) R be can
Become substituent group：During R=H, full name 2,5- hexichol amido p-phthalic acid methyl ester (abbreviation DATADE)；During R=Cl, full name 2,5- bis-
(parachloroanilinum base) p-phthalic acid methyl ester (DpCTADE)；During R=CH3, bis- para-totuidine base-Isosorbide-5-Nitrae-benzene diformazan of full name 2,5-
Sour methyl ester (referred to as DpTTADE).Three kinds of intermediate are referred to as DXTADE.In the method for testing, as impurity may be also have
Machine aminated compoundss, can also consume soda acid, and then affect the accuracy of test.
Therefore it provides a kind of detection method for being capable of Accurate Determining quinacridone-type pigments intermediate purity have important
Meaning.
Content of the invention
In view of this, the technical problem to be solved is to provide the inspection of quinacridone-type pigments intermediate purity
Survey method, the method accuracy height of the detection quinacridone-type pigments intermediate purity that the present invention is provided.
The invention provides a kind of detection method of quinacridone-type pigments intermediate purity, including：
Quinacridone-type pigments intermediate is treated that test sample is detected by reversed-phase high-performance liquid chromatography, obtains quinacridone
The purity of class Pigment Intermediates；
Wherein, the mobile phase of the detection is phosphoric acid and anionic ion aqueous solution and acetonitrile to reagent；
The phosphoric acid and anionic ion in the aqueous solution of reagent, the concentration of the phosphoric acid is 0.02～
0.06wt%；The anionic ion is 1～5mmol/L to the concentration of reagent.
Preferably, the acetonitrile and the phosphoric acid and anionic ion to the volume ratio of the aqueous solution of reagent for (1～
2)：(1～2).
Preferably, the anionic ion to reagent be dodecyl sodium sulfate, decane sulfonate, perfluorooctane sulfonate,
One or more in sodium heptanesulfonate, sodium hexanesulfonate and sodium pentanesulfonate.
Preferably, the phosphoric acid and anionic ion are to, in the aqueous solution of reagent, the concentration of the phosphoric acid is 0.03
～0.04wt%.
Preferably, the phosphoric acid and anionic ion are to, in the aqueous solution of reagent, the anionic ion is to examination
The concentration of agent is 3～4.5mmol/L.
Preferably, the flow velocity of the detection is 0.8～1.2mL/min.
Preferably, the wavelength of the detection is 300～310nm.
Preferably, the temperature of the detection is 25～35 DEG C.
Preferably, the quinacridone-type pigments intermediate treats that test sample is prepared in accordance with the following methods：
Quinacridone-type pigments intermediate is dissolved in a solvent, is obtained quinacridone-type pigments intermediate and treat test sample；Its
In, the solvent is in the mixed solution of the mixed solution and potassium hydroxide aqueous solution of sodium hydrate aqueous solution and methanol with methanol
One or two.
Preferably, the quinacridone-type pigments intermediate is that 2,5- hexichol amido p-phthalic acid methyl ester, 2,5- bis- are (right
Chloroanilino) p-phthalic acid methyl ester or bis- para-totuidine base -1,4- phthalic acid methyl ester of 2,5-.
Compared with prior art, the invention provides a kind of detection method of quinacridone-type pigments intermediate purity, leads to
Cross and quinacridone-type pigments intermediate is treated that test sample is detected by reversed-phase high-performance liquid chromatography, obtain quinacridone-type pigments
The purity of intermediate；Wherein, the mobile phase by making the detection is the aqueous solution of phosphoric acid and anionic ion to reagent
And acetonitrile；And the phosphoric acid and anionic ion is made in the aqueous solution of reagent, the concentration of the phosphoric acid is 0.02～
0.06wt%；The anionic ion is 1～5mmol/L to the concentration of reagent；And then cause to substantially increase in the detection
Impurity and intermediate reserve capability on a column, it is ensured that impurity and intermediate can be kept completely separate and come, so as to can be complete
The interference for avoiding full impurity from determining intermediate, it is ensured that the accuracy of measure.
Description of the drawings
Fig. 1 is the UV-visible spectrum of DpTTADE standard solution；
Fig. 2 is the separation chromatography that in mobile phase, phosphoric acid and SDS content are when 0.04wt% phosphoric acid and 1.5mmol/L SDS
Figure；
Fig. 3 is the separation chromatography figure that in mobile phase, phosphoric acid and SDS content are when 0.02wt% phosphoric acid and 3mmol/L SDS；
Fig. 4 is the separation chromatography figure that in mobile phase, phosphoric acid and SDS content are when 0.04wt% phosphoric acid and 3mmol/L SDS；
Fig. 5 is the separation chromatography figure that in mobile phase, phosphoric acid and SDS content are when 0.06wt% phosphoric acid and 3mmol/L SDS；
Fig. 6 is the separation chromatography that in mobile phase, phosphoric acid and SDS content are when 0.04wt% phosphoric acid and 4.5mmol/L SDS
Figure；
Fig. 7 is the standard curve of the peak area with its concentration of the DpTTADE for obtaining；
Fig. 8 is the chromatogram of No. 1 sample.
Specific embodiment
The invention provides a kind of detection method of quinacridone-type pigments intermediate purity, including：
Quinacridone-type pigments intermediate is treated that test sample is detected by reversed-phase high-performance liquid chromatography, obtains quinacridone
The purity of class Pigment Intermediates；
Wherein, the mobile phase of the detection is phosphoric acid and anionic ion aqueous solution and acetonitrile to reagent；Described
Phosphoric acid and anionic ion are to, in the aqueous solution of reagent, the concentration of the phosphoric acid is 0.02～0.06wt%；Described cloudy from
The concentration of subtype ion-pairing agent is 1～5mmol/L.
According to the present invention, quinacridone-type pigments intermediate is treated that test sample is carried out by reversed-phase high-performance liquid chromatography by the present invention
Detection, obtains the purity of quinacridone-type pigments intermediate；
Wherein, the mobile phase of the detection is phosphoric acid and anionic ion aqueous solution and acetonitrile to reagent；Described
Anionic ion is preferably dodecyl sodium sulfate, decane sulfonate, perfluorooctane sulfonate, sodium heptanesulfonate, hexane to reagent
One or more in sodium sulfonate and sodium pentanesulfonate, more preferably dodecyl sodium sulfate；The acetonitrile and the phosphoric acid
With anionic ion, (1～2) is preferably to the volume ratio of the aqueous solution of reagent：(1～2), more preferably 1：1；Described phosphorous
Acid and anionic ion are in the aqueous solution of reagent, and the concentration of the phosphoric acid is 0.02～0.06wt%, preferably 0.03～
0.04wt%；The anionic ion is 1～5mmol/L, preferably 3～4.5mmol/L to the concentration of reagent, more preferably
3.5～4mmol/L, more specifically, the phosphoric acid and anionic ion are phosphoric acid containing 0.04wt% to the aqueous solution of reagent
With 1.5mmol/L anionic ion to the aqueous solution of reagent, phosphoric acid containing 0.02wt% and 3mmol/L anionic ion to examination
The aqueous solution of agent, phosphoric acid containing 0.04wt% and 3mmol/L anionic ion to the aqueous solution of reagent, phosphoric acid containing 0.06wt% and
3mmol/L anionic ion is to the aqueous solution of reagent, phosphoric acid containing 0.04wt% and 4.5mmol/L anionic ion to reagent
Aqueous solution.
The flow velocity of the detection is preferably 0.8～1.2mL/min, more preferably 1～1.1mL/min.The ripple of the detection
Long preferably 300～310nm, more preferably 303～305nm.The column temperature of the detection is preferably 25～35 DEG C, and more preferably 30
～32 DEG C.The sample size is preferably 15～25 μ L, more preferably 20 μ L.The detection chromatographic column is C18Post (250mm ×
4.6mm,5μm).
The quinacridone-type pigments intermediate treats that test sample is prepared in accordance with the following methods：
Quinacridone-type pigments intermediate is dissolved in a solvent, is obtained quinacridone-type pigments intermediate and treat test sample；Its
In, the solvent is in the mixed solution of the mixed solution and potassium hydroxide aqueous solution of sodium hydrate aqueous solution and methanol with methanol
One or two.The concentration of the sodium hydrate aqueous solution is preferably 0.08～1.2mol/L, more preferably 1mol/L；Described
The concentration of potassium hydroxide aqueous solution is preferably 0.08～1.2mol/L, more preferably 1mol/L；The sodium hydrate aqueous solution with
The volume ratio of the methanol is preferably (1～2)：(1～2), more preferably 1：1；The potassium hydroxide aqueous solution and the methanol
Volume ratio be preferably (1～2)：(1～2), more preferably 1：1；The quinacridone-type pigments intermediate and the solvent
Amount ratio is preferably 1g:(1～1.5) L, more preferably 1g：1L.The quinacridone-type pigments intermediate is preferably 2,5- hexichol
Amido p-phthalic acid methyl ester, bis- (parachloroanilinum base) p-phthalic acid methyl ester of 2,5- or bis- para-totuidine base -1,4- benzene of 2,5-
Dicarboxylic acid methyl ester.
The invention provides a kind of detection method of quinacridone-type pigments intermediate purity, by by quinacridine ketone face
Material intermediate treats that test sample is detected by reversed-phase high-performance liquid chromatography, obtains the purity of quinacridone-type pigments intermediate；Its
In, it is phosphoric acid and anionic ion aqueous solution and acetonitrile to reagent by the mobile phase for being the detection；And make described
Phosphoric acid and anionic ion are to, in the aqueous solution of reagent, the concentration of the phosphoric acid is 0.02～0.06wt%；Described cloudy from
The concentration of subtype ion-pairing agent is 1～5mmol/L；And then cause to substantially increase impurity and intermediate in the detection in chromatograph
Reserve capability on post, it is ensured that impurity and intermediate can be kept completely separate and come, so as to avoiding impurity from determining intermediate
Interference, it is ensured that the accuracy of measure.
Technical scheme below in conjunction with the embodiment of the present invention is clearly and completely described, it is clear that described enforcement
Example is only a part of embodiment of the present invention, rather than whole embodiments.Based on the embodiment in the present invention, this area is common
The every other embodiment obtained under the premise of creative work is not made by technical staff, belongs to the model of present invention protection
Enclose.
Embodiment
The solvent of 1.1 sample dissolution
The present invention by by DpTTADE treat test sample respectively with water, 0.1mol/L HCl, 0.1mol/L NaOH, methanol,
0.1mol/L HCl+ methanol (1:1, v/v), 0.1mol/L NaOH+ methanol (1:1, v/v) mix, find only have 0.1mol/L
NaOH+ methanol (1:1, v/v) test sample dissolubility is treated best, therefore all using this solvent dissolving of 25.0mL in subsequent experimental
25.0mgDpTTADE sample, is configured to 1mg/mL testing sample storing solution, and it is standby that again with methanol is diluted to other desired concn solution
With.
1.2. the optimization of Ion-pair Rp-HPLC separation condition
By the ultraviolet-visible spectrum of DpTTADE standard solution is scanned, optimum measurement wavelength is selected.Fig. 1 is DpTTADE
The UV-visible spectrum of standard solution, it is seen that 303nm is the maximum absorption wavelength of visible region, selects this wavelength for determining
Wavelength can ensure to obtain optimum sensitivity when determining, and therefore, selection 303nm is chromatographic determination wavelength.
Different flowing impacts of the phase composition to chromatograph separating effect are investigated.Select 0.05mg/mLDpTTADE molten in experiment
Liquid sample introduction is analyzed, and mobile phase is consisted of：Acetonitrile from containing the water-soluble of the phosphoric acid of different percentage compositions and dodecyl sodium sulfate (SDS)
Liquid；The volume ratio of the two is 50:50, it is 20 μ L that flow velocity is 1.0mL/min, sample size, 30 DEG C of column temperature, and Detection wavelength is 303nm.
Phosphoric acid and dodecyl sodium sulfate (in the aqueous solution of SDS, are respectively phosphoric acid and SDS content：0.04wt% phosphoric acid and
1.5mmol/L SDS, 0.02wt% phosphoric acid and 3mmol/L SDS, 0.04wt% phosphoric acid and 3mmol/L SDS, 0.06wt% phosphorus
Acid and 3mmol/LSDS, 0.04wt% phosphoric acid and 4.5mmol/L SDS.Separation chromatography figure is shown in Fig. 2～Fig. 6.Fig. 2 is in mobile phase
Phosphoric acid and SDS content are separation chromatography figure when 0.04wt% phosphoric acid and 1.5mmol/L SDS；Fig. 3 be mobile phase in phosphoric acid and
SDS content is separation chromatography figure when 0.02wt% phosphoric acid and 3mmol/L SDS；Fig. 4 is that in mobile phase, phosphoric acid and SDS content are
Separation chromatography figure when 0.04wt% phosphoric acid and 3mmol/L SDS；Fig. 5 is that in mobile phase, phosphoric acid and SDS content are 0.06wt%
Separation chromatography figure when phosphoric acid and 3mmol/L SDS；Fig. 6 be in mobile phase phosphoric acid and SDS content be 0.04wt% phosphoric acid and
Separation chromatography figure during 4.5mmol/L SDS；It can be seen that phosphorus in the aqueous solution of phosphoric acid and dodecyl sodium sulfate
Acid and SDS content for 0.04wt% phosphoric acid with 3mmol/L SD when separate best results.
Therefore, selection chromatographic separation condition is：Mobile phase is acetonitrile and phosphoric acid containing 0.04wt% and 3mmol/L dodecyl
The aqueous solution of sodium sulfonate, volume is 50:50th, flow velocity 1.0mL/min, 20 μ L of sample size, 30 DEG C of column temperature, Detection wavelength 303nm, color
Spectrum post is DionexAcclaimTM120C18Post (250mm × 4.6mm, 5 μm)
1.3. the drafting of standard curve
6 that the DpTTADE standard solution ultra-pure water of 1mg/mL is diluted to that concentration is 0.0007-0.15mg/mL respectively
Part DpTTADE standard solution, directly in liquid chromatograph, sample introduction is analyzed, and chromatographiccondition is：Mobile phase is acetonitrile and contains
0.04wt% phosphoric acid and the aqueous solution of 3mmol/L dodecyl sodium sulfate, volume is 50:50th, flow velocity 1.0mL/min, sample size
30 DEG C of 20 μ L, column temperature, Detection wavelength 303nm, chromatographic column is DionexAcclaimTM120C18Post (250mm × 4.6mm, 5 μm)
The equal sample introduction of each concentration standard specimen 3 times, meansigma methodss A of computer chromatography peak area, draw the song of peak area A～concentration c
Line, and through method of least square linear regression processing, standard curve is obtained, as a result see the peak face that Fig. 7, Fig. 7 are the DpTTADE for obtaining
Product and the standard curve of its concentration, it can be seen that obtained linear equation is A=-0.09994+947.63c (r=
0.9999), it is seen that linear relationship is good.Detection limit (S/N=3) is 20ng/mL, and sensitivity is enough to ensure that the method directly can be used
The Accurate Determining of intermediates content in the production.
1.4. actual sample analysis
Weigh the different intermediate samples (all containing DpTTADE) of two kinds of 25mg respectively, be respectively defined as No. 1 sample (DpTTADE
Exact level be known as 73.00wt%) and No. 2 samples (DpTTADE accurately contains for 76.49wt%), by the methods of 1.1 sections
It is configured to 0.05mg/mL solution.Chromatographiccondition is：Mobile phase is acetonitrile and phosphoric acid containing 0.04wt% and 3mmol/L 12
The aqueous solution of sodium alkyl sulfonate, volume is 50:50th, flow velocity 1.0mL/min, 20 μ L of sample size, 30 DEG C of column temperature, Detection wavelength
303nm, chromatographic column is DionexAcclaimTM120C18Post (250mm × 4.6mm, 5 μm), obtains the chromatographic peak face of DpTTADE
Product, by standard curve and calculates the content of DpTTADE in raw sample, and calculates relative standard after being repeated three times
Deviation (RSD), as a result as shown in table 1.Measurement result precision is satisfactory.The chromatogram of wherein No. 1 sample is shown in that Fig. 8, Fig. 8 are
The chromatogram of No. 1 sample, it can be seen that the retention time of DpTTADE is greatly prolonged to 23.1min, and miscellaneous with various
The chromatographic peak of matter is kept completely separate and comes.
DpTTADE purity analysis in 1 two kinds of different dyes intermediate samples of table
From experimental result as can be seen that the content of DpTTADE that measures of the method for testing that the present invention is provided and theoretical content
Essentially identical, it is seen then that the accuracy height of the method for testing test that the present invention is provided.
1.5. conclusion
Embodiment with dodecyl sodium sulfate is to ion-pairing agent, there is provided one kind can Accurate Determining quinacridone pigment
The RP-HPLC method of intermediate DpTTADE.The method overcome existing ultraviolet visible spectrophotometry, common reversed-phase liquid chromatography
Method and the shortcoming poor by impurity serious interference, accuracy of measurement of acid-base titrations, can disturb impurity be effectively separated, tool
Have the advantages that accuracy of measurement is high, precision is good, sensitivity is suitable, easy to operate, analysis time is short, can be directly used for industry
Accurate, the quick measure of quinacridone pigment intermediate DpTTADE content in production, it can also be used to which quinacridone pigment is in other
Mesosome and the Accurate Determining of final products content, with high actual application value.
The explanation of above example is only intended to help and understands the method for the present invention and its core concept.It should be pointed out that right
For those skilled in the art, under the premise without departing from the principles of the invention, the present invention can also be carried out
Some improvement and modification, these improve and modification is also fallen in the protection domain of the claims in the present invention.
Claims (10)
1. a kind of detection method of quinacridone-type pigments intermediate purity, including：
Quinacridone-type pigments intermediate is treated that test sample is detected by reversed-phase high-performance liquid chromatography, obtains quinacridine ketone face
The purity of material intermediate；
Wherein, the mobile phase of the detection is phosphoric acid and anionic ion aqueous solution and acetonitrile to reagent；
The phosphoric acid and anionic ion are to, in the aqueous solution of reagent, the concentration of the phosphoric acid is 0.02～0.06wt%；
The anionic ion is 1～5mmol/L to the concentration of reagent.
2. detection method according to claim 1, it is characterised in that the acetonitrile and the phosphoric acid and anionic from
Son is (1～2) to the volume ratio of the aqueous solution of reagent：(1～2).
3. detection method according to claim 1, it is characterised in that the anionic ion is dodecyl to reagent
One or more in sodium sulfonate, decane sulfonate, perfluorooctane sulfonate, sodium heptanesulfonate, sodium hexanesulfonate and sodium pentanesulfonate.
4. detection method according to claim 1, it is characterised in that the phosphoric acid and anionic ion are to reagent
In aqueous solution, the concentration of the phosphoric acid is 0.03～0.04wt%.
5. detection method according to claim 1, it is characterised in that the phosphoric acid and anionic ion are to reagent
In aqueous solution, the anionic ion is 3～4.5mmol/L to the concentration of reagent.
6. detection method according to claim 1, it is characterised in that the flow velocity of the detection be.
7. detection method according to claim 1, it is characterised in that the wavelength of the detection be.
8. detection method according to claim 1, it is characterised in that the temperature of the detection be.
9. detection method according to claim 1, it is characterised in that the quinacridone-type pigments intermediate treat test sample by
Prepare according to following methods：
Quinacridone-type pigments intermediate is dissolved in a solvent, is obtained quinacridone-type pigments intermediate and treat test sample；Wherein, institute
State in the mixed solution of mixed solution and potassium hydroxide aqueous solution of the solvent for sodium hydrate aqueous solution and methanol with methanol
Plant or two kinds.
10. detection method according to claim 1, it is characterised in that the quinacridone-type pigments intermediate be
Hexichol amido p-phthalic acid methyl ester, bis- (parachloroanilinum base) p-phthalic acid methyl ester of 2,5- or bis- para-totuidine base -1 of 2,5-,
4- phthalic acid methyl ester.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4956464A (en) * | 1987-10-27 | 1990-09-11 | Basf Aktiengesellschaft | Preparation of dihydroquinacridones, quinacridones and quinacridonequinones |
| CN101830820A (en) * | 2010-05-17 | 2010-09-15 | 淮安苏瑞精细化工有限公司 | Method for preparing 2,5-diparamethylaniline terephthalic acid (DTTA) |
| CN102942802A (en) * | 2012-11-23 | 2013-02-27 | 江苏双乐化工颜料有限公司 | Preparing method of pigment red 122 |
| CN105693536A (en) * | 2016-03-08 | 2016-06-22 | 温州永宏科技孵化有限公司 | Preparation method for synthesizing quinacridone pigment intermediate DXTA |
-
2016
- 2016-09-19 CN CN201610831178.XA patent/CN106442780B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4956464A (en) * | 1987-10-27 | 1990-09-11 | Basf Aktiengesellschaft | Preparation of dihydroquinacridones, quinacridones and quinacridonequinones |
| CN101830820A (en) * | 2010-05-17 | 2010-09-15 | 淮安苏瑞精细化工有限公司 | Method for preparing 2,5-diparamethylaniline terephthalic acid (DTTA) |
| CN102942802A (en) * | 2012-11-23 | 2013-02-27 | 江苏双乐化工颜料有限公司 | Preparing method of pigment red 122 |
| CN105693536A (en) * | 2016-03-08 | 2016-06-22 | 温州永宏科技孵化有限公司 | Preparation method for synthesizing quinacridone pigment intermediate DXTA |
Non-Patent Citations (4)
| Title |
|---|
| PETER POLLAK: "New routes in the synthesis of quinacridone pigments", 《PROGRESS IN ORGANIC COATINGS》 * |
| 毕向东 等: "高档有机颜料--喹吖啶酮颜料化学及进展", 《化工进展》 * |
| 褚朝霞 等: "反相高效液相色谱法测定喹吖啶酮类颜料中间体2,5-二对氯苯氨基-1,4-苯二甲酸的纯度", 《分析仪器》 * |
| 褚朝霞 等: "紫外-可见分光光度计法对喹吖啶酮颜料系列中间体的纯度分析", 《染料与染色》 * |
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