WO2023279760A1 - Method for detecting content of polyvinyl alcohol by means of spectrophotometry - Google Patents
Method for detecting content of polyvinyl alcohol by means of spectrophotometry Download PDFInfo
- Publication number
- WO2023279760A1 WO2023279760A1 PCT/CN2022/080812 CN2022080812W WO2023279760A1 WO 2023279760 A1 WO2023279760 A1 WO 2023279760A1 CN 2022080812 W CN2022080812 W CN 2022080812W WO 2023279760 A1 WO2023279760 A1 WO 2023279760A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- solution
- chloride
- polyvinyl alcohol
- hydroxylamine
- reference substance
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 111
- 229920002451 polyvinyl alcohol Polymers 0.000 title claims abstract description 106
- 239000004372 Polyvinyl alcohol Substances 0.000 title claims abstract description 99
- 238000002798 spectrophotometry method Methods 0.000 title abstract description 6
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 claims abstract description 75
- 238000001514 detection method Methods 0.000 claims abstract description 36
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 20
- 239000000243 solution Substances 0.000 claims description 233
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 72
- 238000002835 absorbance Methods 0.000 claims description 63
- 239000013558 reference substance Substances 0.000 claims description 59
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 56
- 238000012360 testing method Methods 0.000 claims description 49
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 48
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 42
- 229940032296 ferric chloride Drugs 0.000 claims description 37
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 35
- 238000002360 preparation method Methods 0.000 claims description 34
- 239000012085 test solution Substances 0.000 claims description 25
- 238000010668 complexation reaction Methods 0.000 claims description 11
- 239000012088 reference solution Substances 0.000 claims description 11
- 238000000870 ultraviolet spectroscopy Methods 0.000 claims description 11
- 239000003929 acidic solution Substances 0.000 claims description 10
- 230000002378 acidificating effect Effects 0.000 claims description 9
- 239000012670 alkaline solution Substances 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- 238000012937 correction Methods 0.000 claims description 6
- RGZRSLKIOCHTSI-UHFFFAOYSA-N hydron;n-methylhydroxylamine;chloride Chemical compound Cl.CNO RGZRSLKIOCHTSI-UHFFFAOYSA-N 0.000 claims description 6
- 238000005259 measurement Methods 0.000 claims description 6
- 125000000963 oxybis(methylene) group Chemical group [H]C([H])(*)OC([H])([H])* 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 5
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 4
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 4
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- BYXUIKZQGOPKFR-UHFFFAOYSA-N hydron;n-propan-2-ylhydroxylamine;chloride Chemical compound Cl.CC(C)NO BYXUIKZQGOPKFR-UHFFFAOYSA-N 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 239000011651 chromium Substances 0.000 claims description 3
- LTZZYVWUGIPISL-UHFFFAOYSA-N ethyl(hydroxy)azanium;chloride Chemical compound [Cl-].CC[NH2+]O LTZZYVWUGIPISL-UHFFFAOYSA-N 0.000 claims description 3
- 239000011572 manganese Substances 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 229910021555 Chromium Chloride Inorganic materials 0.000 claims description 2
- 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 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 claims description 2
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- 229960002089 ferrous chloride Drugs 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- 229940099607 manganese chloride Drugs 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 235000011121 sodium hydroxide Nutrition 0.000 claims 3
- YCRHLOSLIFJDFH-UHFFFAOYSA-N chloromethane hydroxylamine Chemical compound NO.CCl YCRHLOSLIFJDFH-UHFFFAOYSA-N 0.000 claims 1
- 150000002443 hydroxylamines Chemical class 0.000 claims 1
- 239000011736 potassium bicarbonate Substances 0.000 claims 1
- 235000015497 potassium bicarbonate Nutrition 0.000 claims 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims 1
- 235000011181 potassium carbonates Nutrition 0.000 claims 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims 1
- 235000011118 potassium hydroxide Nutrition 0.000 claims 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 abstract description 92
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 5
- 125000000914 phenoxymethylpenicillanyl group Chemical group CC1(S[C@H]2N([C@H]1C(=O)*)C([C@H]2NC(COC2=CC=CC=C2)=O)=O)C 0.000 abstract description 5
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 2
- 239000000523 sample Substances 0.000 description 14
- 239000000047 product Substances 0.000 description 11
- 239000011630 iodine Substances 0.000 description 9
- 229910052740 iodine Inorganic materials 0.000 description 9
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 7
- 125000004185 ester group Chemical group 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 238000006136 alcoholysis reaction Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- NEAQRZUHTPSBBM-UHFFFAOYSA-N 2-hydroxy-3,3-dimethyl-7-nitro-4h-isoquinolin-1-one Chemical compound C1=C([N+]([O-])=O)C=C2C(=O)N(O)C(C)(C)CC2=C1 NEAQRZUHTPSBBM-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 4
- 239000004327 boric acid Substances 0.000 description 4
- -1 construction Substances 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- RLTYKOCELUYEKF-UHFFFAOYSA-N [I].OB(O)O Chemical compound [I].OB(O)O RLTYKOCELUYEKF-UHFFFAOYSA-N 0.000 description 3
- 230000000536 complexating effect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000004737 colorimetric analysis Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229940044631 ferric chloride hexahydrate Drugs 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 2
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000176 sodium gluconate Substances 0.000 description 2
- 235000012207 sodium gluconate Nutrition 0.000 description 2
- 229940005574 sodium gluconate Drugs 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- DKNPRRRKHAEUMW-UHFFFAOYSA-N Iodine aqueous Chemical compound [K+].I[I-]I DKNPRRRKHAEUMW-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- FHKYMEGVIVZQAD-UHFFFAOYSA-N [N].ON Chemical group [N].ON FHKYMEGVIVZQAD-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012490 blank solution Substances 0.000 description 1
- QNEFNFIKZWUAEQ-UHFFFAOYSA-N carbonic acid;potassium Chemical compound [K].OC(O)=O QNEFNFIKZWUAEQ-UHFFFAOYSA-N 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- KESKUDPLUKSODA-UHFFFAOYSA-N chloroethane hydroxylamine Chemical compound NO.C(C)Cl KESKUDPLUKSODA-UHFFFAOYSA-N 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000013068 control sample Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000003889 eye drop Substances 0.000 description 1
- 229940012356 eye drops Drugs 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- CPQCSJYYDADLCZ-UHFFFAOYSA-N n-methylhydroxylamine Chemical compound CNO CPQCSJYYDADLCZ-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000000546 pharmaceutical excipient Substances 0.000 description 1
- 229940124531 pharmaceutical excipient Drugs 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Images
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/33—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using ultraviolet light
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
- G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
- G01N2021/775—Indicator and selective membrane
Definitions
- the invention relates to the field of medical detection, and specifically provides a method for detecting the content of polyvinyl alcohol by spectrophotometry.
- Polyvinyl alcohol is a water-soluble polymer compound with unique strong adhesion, smoothness, oil resistance, solvent resistance, gas barrier properties, abrasion resistance and water resistance after special treatment
- PVA Polyvinyl alcohol
- it is also widely used in the production of coatings, adhesives, paper processing agents, emulsifiers, dispersants, films and other products, and its application range covers textiles, food, medicine, construction, wood processing, papermaking, Printing, agriculture, steel, polymer chemical industry and other industries.
- PVA is a polyhydroxy compound with a theoretical molecular formula of (C 2 H 4 O) n . It is usually used as a pharmaceutical excipient. At present, there is no detection method for the content of polyvinyl alcohol in domestic and foreign pharmacopoeias, and the existing reported polyethylene The detection method of alcohol content is PVA-boric acid-iodine.
- the hydroxylamine-ferric chloride chromogenic method is currently mainly used in the detection of certain substances with a single structure and exact structure, but the complex formed by it has poor stability.
- the present invention provides a method for spectrophotometrically detecting the content of polyvinyl alcohol, the method comprising using hydroxylamine chloride or hydroxylamine chloride derivatives to react with ester groups on polyvinyl alcohol polymer chains to generate isohydroxyl Xamic acid, then chelates with metal ions to form a complex with ultraviolet absorption.
- the method includes the use of hydroxylamine chloride or hydroxylamine chloride derivatives and metal ions as color reagents, and the hydroxylamine chloride derivatives are methyl hydroxylamine chloride, ethyl chloride Hydroxylamine or isopropylhydroxylamine chloride.
- the method also includes the preparation of a control solution: weigh the polyvinyl alcohol reference substance, add water to dissolve it completely, add alkaline hydroxylamine chloride or hydroxylamine chloride derivative solution, And acidic metal ion solution, namely the reference substance solution.
- the method also includes the solution preparation of the reference substance: take the polyvinyl alcohol reference substance, place it in a measuring bottle, add water to make it completely dissolve, and then take the above solution into the vial , add hydroxylamine chloride or hydroxylamine chloride derivative solution, alkaline solution, shake well, then add acidic solution and metal ion solution, dilute with water to the mark, shake well, set aside;
- the method also includes the preparation of the test solution: adding water to the polyvinyl alcohol for the test makes it completely dissolved, and then adding basic hydroxylamine chloride or hydroxylamine chloride derivatives solution and acidic metal ion solution, that is, the test solution.
- the method also includes the solution preparation of the test sample: take the polyvinyl alcohol test sample and place it in a measuring bottle, add water to make it completely dissolve, and then transfer the above solution to the vial , add hydroxylamine chloride or hydroxylamine chloride derivative solution, alkaline solution, shake well, then add acidic solution and metal ion solution, dilute with water to the mark, shake well, set aside.
- the metal ion is Fe 3+ , Fe 2+ , Mn 2+ , Cd 2+ , Cr 3+ , Cu 2+ or Pt 2+ .
- the metal ion compound is ferric chloride, ferrous chloride, manganese chloride, chromium nitrate, chromium chloride, copper sulfate or sodium chloroplatinate.
- the alkali used in the alkaline hydroxylamine chloride or hydroxylamine chloride derivative solution is sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, carbonic acid Potassium hydrogen, triethylamine or N,N-diisopropylethylamine.
- the purpose of adding alkali in the method of the present invention is to neutralize hydroxylamine chloride or hydroxylamine chloride derivatives, and the pH value is adjusted to 7-8.
- the acid used in the acidic metal ion solution is hydrochloric acid, phosphoric acid, sulfuric acid, trifluoroacetic acid or methanesulfonic acid.
- the purpose of adding acid in the method of the present invention is to form hydroxamic acid with complexing effect and adjust the pH value to 4-5.
- the method further includes: measuring the absorbance A at 498-502 nm with an ultraviolet-visible spectrophotometer.
- the method further includes: measuring the absorbance A at 500 nm with an ultraviolet-visible spectrophotometer.
- the method also includes: calculating the content of polyvinyl alcohol (C 2 H 4 O)n according to the following formula:
- a S the absorbance of the reference solution
- a u the absorbance of the test solution
- C S the concentration of the reference substance solution, mg/ml
- the method further includes:
- Solution preparation of the reference substance Weigh the polyvinyl alcohol reference substance, place it in a measuring bottle, add water to dissolve it completely, and dilute to the mark, take an appropriate amount of the above solution into a vial, add an appropriate amount of hydroxylamine chloride or hydroxylamine chloride Derivative solution, alkaline solution, shake well, then add appropriate amount of acidic solution and ferric chloride solution, dilute with water to the mark, shake well, and set aside.
- Preparation of the solution of the test product Weigh the test product of polyvinyl alcohol and place it in a measuring bottle, add water to dissolve it completely, and dilute to the mark, take an appropriate amount of the above solution into a vial, add an appropriate amount of hydroxylamine chloride or chloride Hydroxylamine derivative solution, alkaline solution, shake well, then add appropriate amount of acidic solution and ferric chloride solution, dilute with water to the mark, shake well, place
- a S the absorbance of the reference solution
- a u the absorbance of the test solution
- C S the concentration of the reference substance solution, mg/ml
- the method includes adding 1 ml or more of hydroxylamine chloride or hydroxylamine chloride derivatives.
- the method includes adding ferric chloride in an amount of 1 ml or more.
- the method includes a complexing time of 10 minutes or more.
- the method includes that the detection temperature after complexation is 25-40°C.
- the method for detecting polyvinyl alcohol content by the spectrophotometric method comprises:
- Solution preparation of the reference substance Weigh the polyvinyl alcohol reference substance, place it in a measuring bottle, add water to dissolve it completely, take an appropriate amount of the above solution into a vial, add an appropriate amount of hydroxylamine chloride or hydroxylamine chloride derivative solution, alkali neutral solution, shake well, then add an appropriate amount of acidic solution and ferric chloride solution, dilute to the mark with water, shake well, measure the absorbance As at 500nm with a UV-visible spectrophotometer
- Preparation of the solution of the test product Weigh the test product of polyvinyl alcohol and place it in a measuring bottle, add water to make it completely dissolved, then take an appropriate amount of the above solution into a vial, add an appropriate amount of hydroxylamine chloride or hydroxylamine chloride derivative solution, Alkaline solution, shake well, then add an appropriate amount of acidic solution and ferric chloride solution, dilute to the mark with water, shake well, measure the absorbance Au at 500nm with an ultraviolet - visible spectrophotometer
- a S the absorbance of the reference solution
- a u the absorbance of the test solution
- C S the concentration of the reference substance solution, mg/ml
- the hydroxylamine chloride derivatives are methyl hydroxylamine chloride, ethyl hydroxylamine chloride or isopropyl hydroxylamine chloride.
- the method further includes:
- Solution preparation of the reference substance Weigh 56 mg of polyvinyl alcohol reference substance, place it in a measuring bottle, add water to make it completely dissolved, then take 5 ml of the above solution into a vial, and accurately measure 1.25 mol/L hydroxylamine chloride solution 1ml, 1ml of 3.5mol/L sodium hydroxide solution, then precisely measure 2ml of 2.5mol/L hydrochloric acid solution, 1ml of ferric chloride solution, shake well, place for 10min, and set aside;
- Solution preparation of the test product Weigh 56 mg of the test product of polyvinyl alcohol, place it in a 100ml measuring bottle, add water to make it completely dissolved, then take 5 ml of the above solution into the vial, and accurately measure 1.25mol/L hydroxylamine chloride Solution 1ml, 3.5mol/L sodium hydroxide solution 1ml, and then accurately measure 2.5mol/L hydrochloric acid solution 2ml, ferric chloride solution 1ml, shake well, stand for 10min, and set aside.
- polyvinyl alcohol structural formula expression mode is The prior art utilizes the hydroxyl group in the structure to form a gel with boric acid, and then forms a complex with ultraviolet absorption with iodine.
- the present invention uses the nucleophilic substitution reaction between the ester group of the non-alcoholyzed part and the lone pair of electrons on the nitrogen atom of hydroxylamine to generate hydroxamic acid and iron ions to form a complex with ultraviolet absorption.
- the two principles are different.
- the use of PVA-boric acid-iodine method is mainly used to detect the content of PVA as a chemical raw material, and the accuracy of the detection results is not high, while the hydroxylamine-iron trichloride used in the present invention
- the method is mainly used to detect the content of PVA when it is used as a medicine. It has high requirements for the accuracy of the detection results, the stability and reproducibility of the detection method, and it is unexpectedly found that this method can be applied to all alcoholysis
- the detection of polyvinyl alcohol has a wide range of applications.
- the R can be hydrogen, methyl, ethyl and isopropyl
- the M can be Fe 3+ , Fe 2+ , Mn 2+ , Cd 2+ , Cr 3+ , Cu 2+ , or Pt 2+ .
- the present invention realizes the application of hydroxylamine-ferric chloride to the determination of polyvinyl alcohol content, especially the content determination when polyvinyl alcohol is used as medicine, and uses the hydroxyl on polyvinyl alcohol and boric acid to form a gel with the prior art , compared with iodine to form a complex with hydrogen bonds, the present invention utilizes the non-alcoholyzed ester group on the polyvinyl alcohol and the lone pair of electrons on the hydroxylamine nitrogen atom to undergo a nucleophilic substitution reaction to generate hydroxamic acid, and then react with iron Ions form complexes with covalent bonds, which are more stable. It is applicable to all PVAs with incomplete alcoholysis (that is, it is applicable to the content determination of all PVAs whose degree of alcoholysis is below 98%).
- the method of the present invention has good specificity and is applicable to the detection of all PVAs that have not been completely alcoholysed; the method has high accuracy and good reproducibility; the method is not affected by the degree of polymerization, long-chain structure and hydroxyl molar concentration of PVA, High versatility.
- the principle of the polyvinyl alcohol content detection method of the present invention is to use the residual ester group on the polyvinyl alcohol polymer chain to react with hydroxylamine to form hydroxamic acid, and then chelate with metal ions to form a complex with ultraviolet absorption.
- the principle has been applied to the content detection of certain substances at present, but they are all used for the content detection of substances with a single structure and exact structure, and the complexes formed have poor stability.
- Fig. 1 the linear test result figure in embodiment 2;
- Fig. 2 In embodiment 7, the impact of the addition amount of hydroxylamine chloride solution on the absorbance of polyvinyl alcohol solution;
- Fig. 3 the influence of 0.5mol/L ferric chloride solution addition amount on polyvinyl alcohol absorbance in embodiment 7;
- Fig. 4 the impact of complexing time on the absorbance of polyvinyl alcohol solution in embodiment 7;
- Fig. 5 Effect of complexation temperature on absorbance of polyvinyl alcohol solution in Example 7.
- Instrument electronic balance (manufacturer/model: Mettler Toledo/AB135-S); ultraviolet-visible spectrophotometer (manufacturer/model: Shimadzu/UV-2600)
- Reagent hydroxylamine chloride (source/batch number: Xilong Science Co., Ltd./2003141); sodium hydroxide (source/batch number: Xilong Science Co., Ltd./52009136); hydrochloric acid (Xilong Science Co., Ltd./180303); Ferric chloride hexahydrate (Xilong Science Co., Ltd./2005221)
- Hydroxylamine chloride solution Take about 8.68g of Hydroxylamine chloride, weigh it accurately, put it in a 100ml measuring bottle, add an appropriate amount of water to dissolve it, dilute to the mark with water, and shake well.
- 3.5mol/L sodium hydroxide solution Take about 14g of sodium hydroxide, weigh it accurately, add water to dissolve it to 100ml, and shake well.
- hydrochloric acid solution accurately measure 20.8ml concentrated hydrochloric acid (molar concentration is 12mol/L), dilute with water to 100ml, shake well
- Ferric chloride solution Take about 6.76g of ferric chloride hexahydrate, weigh it accurately, put it in a 50ml measuring bottle, add water to dissolve and dilute to the mark, shake well
- Blank solution precisely measure 5ml of water into a 30ml vial, then precisely measure 1ml of 1.25mol/L hydroxylamine chloride solution, 1ml of 3.5mol/L sodium hydroxide solution, shake well, then precisely measure 2.5mol/L hydrochloric acid solution 2ml, 1ml of ferric chloride solution, shake well and let stand for 10min.
- Solution preparation of reference substance Weigh 56 mg of polyvinyl alcohol (batch number: 465200915, content 99.6%) reference substance, place it in a 100ml measuring bottle, add water to make it completely dissolve, then take 5ml of the above solution into a 30ml vial, and accurately measure Take 1ml of 1.25mol/L hydroxylamine chloride solution, 1ml of 3.5mol/L sodium hydroxide solution, then precisely measure 2ml of 2.5mol/L hydrochloric acid solution, 1ml of ferric chloride solution, shake well, and let stand for 10min.
- polyvinyl alcohol batch number: 465200915, content 99.6%
- Solution preparation of the test product Weigh 56mg of polyvinyl alcohol test product (batch number 465190628), place it in a 100ml measuring bottle, add water to dissolve it completely, take 5ml of the above solution into a 30ml vial, and accurately measure 1.25mol /L hydroxylamine chloride solution 1ml, 3.5mol/L sodium hydroxide solution 1ml, and then accurately measure 2.5mol/L hydrochloric acid solution 2ml, ferric chloride solution 1ml, shake well, let stand for 10min.
- Absorbance A was measured at 500 nm with a UV-Vis spectrophotometer ,
- a S the absorbance of the reference solution
- a u the absorbance of the test solution
- C S the concentration of the reference substance solution, mg/ml
- methylhydroxylamine chloride solution take about 10.37g of methylhydroxylamine chloride, accurately weigh it, put it in a 100ml measuring bottle, add an appropriate amount of water to dissolve it, dilute with water to the mark, and shake well
- Example 1-1 The rest of the solution preparation was carried out according to Example 1-1. After replacing the hydroxylamine chloride solution with methyl hydroxylamine chloride solution, the content of the polyvinyl alcohol test sample (batch number 465190628) was detected according to the test procedure of Example 1-1.
- the methyl hydroxylamine chloride-ferric chloride method is accurate in determining the content of polyvinyl alcohol.
- Detection Take an appropriate amount of the above solutions respectively, and place them in an ultraviolet-visible spectrophotometer to detect the absorbance value at a wavelength of 500 nm.
- Detection Take an appropriate amount of the above solutions respectively, and place them in an ultraviolet-visible spectrophotometer to detect the absorbance value at a wavelength of 500 nm.
- the test results are shown in Table 2: the average content of the repeated test is 98.6%, and the RSD is 1.0%; the RSD of the content of 6 samples of intermediate precision is 1.0%, and the RSD of the content of 12 samples is 0.7%.
- Embodiment 4 sample addition recovery rate
- test solution Weigh about 56mg of polyvinyl alcohol for the test, put it in a 100ml measuring bottle, add water to dissolve it completely, and then dilute to the mark; take 5ml of the above solution into a 30ml vial, and accurately measure 1.25mol 1ml of /L hydroxylamine chloride solution, 1ml of 3.5mol/L sodium hydroxide solution, shake well, then accurately measure 2ml of 2.5mol/L hydrochloric acid solution, 1ml of ferric chloride solution, shake well, let stand for 10min, prepare 3 parts in parallel sample.
- control sample solution Weigh an appropriate amount of polyvinyl alcohol reference substance, dissolve it in water in a 50ml measuring bottle, add an appropriate amount of the test solution, and dilute to the scale; prepare different concentration levels of 80%, 100%, and 120% of the sample solution. Sequentially take 5ml of the above-mentioned solutions of different concentrations into 30ml vials, accurately measure 1ml of 1.25mol/L hydroxylamine chloride solution, 1ml of 3.5mol/L sodium hydroxide solution, and shake well; then precisely measure 2.5mol/L hydrochloric acid Solution 2ml, ferric chloride solution 1ml, shake well, stand for 10min. Three samples were prepared in parallel.
- Cs the concentration of the reference substance solution, mg/mL
- Ws content of polyvinyl alcohol reference substance, 99.6%
- Ms the weight of the reference substance weighed at each concentration, mg
- test solution Weigh about 56 mg of 3 batches of the test (batch numbers are 465190628, 46520111202, 46520111801 respectively), put it in a 100ml measuring bottle, add water to dissolve it completely, and dilute to the mark; take 5ml of the above solution to In a 30ml vial, accurately measure 1ml of 1.25mol/L hydroxylamine chloride solution, 1ml of 3.5mol/L sodium hydroxide solution, shake well, then precisely measure 2ml of 2.5mol/L hydrochloric acid solution, 1ml of ferric chloride solution, Shake well and let stand for 10min. Prepare 2 copies in parallel.
- a S the absorbance of the reference solution
- a u the absorbance of the test solution
- C S the concentration of the reference substance solution, mg/ml
- test sample (batch number: 465190628, its content is 99.2% by weight conservation method) solution by the same method as above, and measure its absorbance Au at 670nm.
- the batch content of 465190628 was determined to be 93%.
- test sample (batch number: 465190628, its content is 99.2% by weight conservation method) solution by the same method as above, and measure its absorbance Au at 500nm.
- the content of batch 465190628 was determined to be 99.22%. It can be seen that the result determined by this method is more accurate.
- Embodiment 7 influence factor test
- Sample preparation Weigh about 56mg of polyvinyl alcohol (lot number: 465190628), put it in a 100ml measuring bottle, add water to dissolve it completely, and dilute to the mark; take 5ml of the above solution into a 30ml vial, and add different volumes of 1.25mol/L hydroxylamine chloride solution, 1ml of 3.5mol/L sodium hydroxide solution, shake well, then add 2ml of 2.5mol/L hydrochloric acid solution, 1ml of ferric chloride solution, shake well, let stand for 10min. Seven samples were prepared in parallel.
- Sample preparation Weigh about 56mg of polyvinyl alcohol (batch number: 465190628), put it in a 100ml measuring bottle, add water to dissolve it completely, and dilute to the mark; take 5ml of the above solution into a 30ml vial, add 1.25mol/L chloride Prepare 7 samples in parallel with 1ml of hydroxylamine solution, add 1ml of 3.5mol/L sodium hydroxide solution and 2ml of 2.5mol/L hydrochloric acid solution respectively, add different volumes of 0.5mol/L ferric chloride solution according to Table 8, and shake well , placed for 10min.
- Detection Take an appropriate amount of the above solutions respectively, and place them in an ultraviolet-visible spectrophotometer to detect the absorbance value at a wavelength of 500 nm.
- Sample preparation Weigh about 56mg of polyvinyl alcohol (batch number: 465190628), put it in a 100ml measuring bottle, add water to dissolve it completely, and dilute to the mark; take 5ml of the above solution into a 30ml vial, add 1.25mol/L chloride Prepare 7 samples in parallel with 1ml of hydroxylamine solution, add 1ml of 3.5mol/L sodium hydroxide solution, 2ml of 2.5mol/L hydrochloric acid solution, and 1ml of ferric chloride solution, shake well, and place for different times according to Table 9.
- Sample preparation Weigh about 56mg of polyvinyl alcohol (batch number: 465190628), put it in a 100ml measuring bottle, add water to dissolve it completely, and dilute to the mark; take 5ml of the above solution into a 30ml vial, add 1.25mol/L chloride Prepare 7 samples in parallel with 1ml of hydroxylamine solution, add 1ml of 3.5mol/L sodium hydroxide solution, 2ml of 2.5mol/L hydrochloric acid solution, and 1ml of ferric chloride solution, shake well, and place at the temperature described in Table 10 for 10min.
- Detection Take an appropriate amount of the above solutions respectively, and place them in an ultraviolet-visible spectrophotometer to detect their absorbance at a wavelength of 500 nm.
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Abstract
The present invention relates to the field of medical detection. Specifically provided is a method for detecting the content of polyvinyl alcohol by means of spectrophotometry. In the method, hydroxylamine chloride or hydroxylamine chloride derivatives and metal ions are used as chromogenic agents to detect the content of medicinal polyvinyl alcohol, and the method has a good specificity and is suitable for the detection of all PVAs that are not completely alcoholized. The method has a high accuracy and a good reproducibility, is not affected by the polymerization degrees of the PVAs, a long chain structure and a hydroxyl molar concentration, has a high universality, and successfully meets the need for accurately detecting the content of medicinal polyvinyl alcohol in the industry. The method for detecting the content of medicinal polyvinyl alcohol is developed, which fills the gap in terms of detecting the content of medicinal polyvinyl alcohol in the industry.
Description
本发明涉及医药检测领域，具体提供一种分光光度检测法聚乙烯醇含量的方法。The invention relates to the field of medical detection, and specifically provides a method for detecting the content of polyvinyl alcohol by spectrophotometry.
聚乙烯醇(PVA)是一种具有水溶性的高分子化合物，具有独特的强力粘接性、平滑性、耐油性、耐溶剂性、气体阻绝性、耐磨性以及经特殊处理具有的耐水性，除了作纤维原料外，还被大量用于生产涂料、粘合剂、纸品加工剂、乳化剂、分散剂、薄膜等产品，应用范围遍及纺织、食品、医药、建筑、木材加工、造纸、印刷、农业、钢铁、高分子化工等行业。Polyvinyl alcohol (PVA) is a water-soluble polymer compound with unique strong adhesion, smoothness, oil resistance, solvent resistance, gas barrier properties, abrasion resistance and water resistance after special treatment In addition to being used as fiber raw materials, it is also widely used in the production of coatings, adhesives, paper processing agents, emulsifiers, dispersants, films and other products, and its application range covers textiles, food, medicine, construction, wood processing, papermaking, Printing, agriculture, steel, polymer chemical industry and other industries.
PVA是一种多羟基化合物，理论分子式为(C
2H
4O)
n，通常作为药用辅料使用，目前国内外药典均没有收载聚乙烯醇含量的检测方法，而现有报道的聚乙烯醇含量检测方法为PVA-硼酸-碘。
PVA is a polyhydroxy compound with a theoretical molecular formula of (C 2 H 4 O) n . It is usually used as a pharmaceutical excipient. At present, there is no detection method for the content of polyvinyl alcohol in domestic and foreign pharmacopoeias, and the existing reported polyethylene The detection method of alcohol content is PVA-boric acid-iodine.
徐荣等人发表了分光光度法测定纸品中聚乙烯醇含量，其采用了PVA-硼酸-碘的检测方法检测聚乙烯醇的含量。Xu Rong and others published a spectrophotometric method for determining the content of polyvinyl alcohol in paper products, which adopted the detection method of PVA-boric acid-iodine to detect the content of polyvinyl alcohol.
韩加怡等人发表了聚乙烯醇滴眼液含量测定的方法学研究，其公开了采用了PVA-硼酸-碘的检测方法检测聚乙烯醇的含量的方法Han Jiayi and others published a methodological study on the determination of polyvinyl alcohol eye drops content, which disclosed a method for detecting the content of polyvinyl alcohol using the detection method of PVA-boric acid-iodine
刘优昌等人发表了纺织浆料中聚乙烯醇(PVA)含量测定方法探讨，其公开了采用了PVA-硼酸-碘的检测方法检测聚乙烯醇的含量。Liu Youchang and others published a discussion on the determination method of polyvinyl alcohol (PVA) in textile pulp, which disclosed the detection method of PVA-boric acid-iodine to detect the content of polyvinyl alcohol.
上述已知PVA-硼酸-碘方法中利用的是PVA结构上的羟基与硼酸形成凝胶，再与碘以氢键形成络合物。该方法存在着络合物不稳定，导致检测结果不准确、重现性差的缺点。In the above-mentioned known PVA-boric acid-iodine method, the hydroxyl group on the PVA structure forms a gel with boric acid, and then forms a complex with iodine by hydrogen bonding. This method has the disadvantages that the complex is unstable, resulting in inaccurate detection results and poor reproducibility.
羟胺-三氯化铁显色法目前主要应用于某些结构单一、结构确切的物质检测，但其形成的络合物稳定性差。The hydroxylamine-ferric chloride chromogenic method is currently mainly used in the detection of certain substances with a single structure and exact structure, but the complex formed by it has poor stability.
例如翁艳军等人发表了葡萄糖酸钠的分光光度法测定，该方法利用葡萄糖酸钠在强酸性条件下形成内脂，通过羟胺-三氯化铁显色法生成红棕色异羟肟酸-Fe
3+络合物，进行分光光度检测。该方法技术缺陷如其在结论部分所述，实验发现，异羟肟酸-Fe3+络合物稳定性较差，只能在显色后10min内进行检测。
For example, Weng Yanjun and others published the spectrophotometric determination of sodium gluconate, which uses sodium gluconate to form lactone under strong acidic conditions, and generates reddish-brown hydroxamic acid-Fe3 through the hydroxylamine - ferric chloride color method + complex, for spectrophotometric detection. The technical defect of this method is as mentioned in the conclusion part. The experiment found that the hydroxamic acid-Fe3+ complex has poor stability and can only be detected within 10 minutes after color development.
叶能权等人发表了一种羟胺-氯化铁比色法测定空气中的丙烯酰胺，该现有技术采用羟胺-氯化铁法测定丙烯酰胺。该方法的技术缺陷如其在该文献中披露，显色的稳定性在30min内吸光度基本保持不变，显色后20min内比色完毕最好。说明形成的络合物不稳定。Ye Nengquan et al. published a hydroxylamine-ferric chloride colorimetric method for the determination of acrylamide in the air. This prior art uses the hydroxylamine-ferric chloride method for the determination of acrylamide. The technical defect of this method is as disclosed in this document, the stability of the color development is that the absorbance remains basically unchanged within 30 minutes, and it is best to complete the colorimetry within 20 minutes after the color development. It shows that the complex formed is unstable.
综上，目前还尚未发现聚乙烯醇含量更为有效的检测方法，准确的、稳定的、重现性好的检测高分子聚乙烯醇作为药品原料药使用时的含量的方法，是业内急需的。In summary, no more effective detection method for polyvinyl alcohol content has yet been found. An accurate, stable, and reproducible method for detecting the content of high-molecular polyvinyl alcohol when used as a pharmaceutical raw material is urgently needed in the industry .
发明内容Contents of the invention
针对以上技术现状，本发明提供一种分光光度法检测聚乙烯醇含量的方法，所述方法包括采用氯化羟胺或氯化羟胺衍生物和聚乙烯醇高分子链上的酯基反应生成异羟肟酸，再与金属离子螯合形成具有紫外吸收的络合物。Aiming at the above technical situation, the present invention provides a method for spectrophotometrically detecting the content of polyvinyl alcohol, the method comprising using hydroxylamine chloride or hydroxylamine chloride derivatives to react with ester groups on polyvinyl alcohol polymer chains to generate isohydroxyl Xamic acid, then chelates with metal ions to form a complex with ultraviolet absorption.
本发明方法中，作为实施方案之一，所述方法包括采用氯化羟胺或氯化羟胺衍生物和金属离子为显色剂，所述氯化羟胺衍生物为甲基氯化羟胺、乙基氯化羟胺或异丙基氯化羟胺。In the method of the present invention, as one of the embodiments, the method includes the use of hydroxylamine chloride or hydroxylamine chloride derivatives and metal ions as color reagents, and the hydroxylamine chloride derivatives are methyl hydroxylamine chloride, ethyl chloride Hydroxylamine or isopropylhydroxylamine chloride.
本发明方法中，作为实施方案之一，所述方法还包括对照溶液的制备：称取聚乙烯醇对照品，加水使其完全溶解，加入碱性的氯化羟胺或氯化羟胺衍生物溶液，及酸性的金属离子溶液，即得对照品溶液。In the method of the present invention, as one of the embodiments, the method also includes the preparation of a control solution: weigh the polyvinyl alcohol reference substance, add water to dissolve it completely, add alkaline hydroxylamine chloride or hydroxylamine chloride derivative solution, And acidic metal ion solution, namely the reference substance solution.
本发明方法中，作为实施方案之一，所述方法还包括对照品的溶液配制：称取聚乙烯醇对照品，置于量瓶中，加水使其完全溶解后，取上述溶液至西林瓶中，加入氯化羟胺或氯化羟胺衍生物溶液、碱性溶液，摇匀，再加入酸性溶液及金属离子溶液，用水稀释至刻度，摇匀，备用；In the method of the present invention, as one of the embodiments, the method also includes the solution preparation of the reference substance: take the polyvinyl alcohol reference substance, place it in a measuring bottle, add water to make it completely dissolve, and then take the above solution into the vial , add hydroxylamine chloride or hydroxylamine chloride derivative solution, alkaline solution, shake well, then add acidic solution and metal ion solution, dilute with water to the mark, shake well, set aside;
本发明方法中，作为实施方案之一，所述方法还包括供试品溶液的制备：将聚乙烯醇供试品加水使其完全溶解，然后加入碱性的氯化羟胺 或氯化羟胺衍生物溶液及酸性的金属离子溶液，即得供试品溶液。In the method of the present invention, as one of the embodiments, the method also includes the preparation of the test solution: adding water to the polyvinyl alcohol for the test makes it completely dissolved, and then adding basic hydroxylamine chloride or hydroxylamine chloride derivatives solution and acidic metal ion solution, that is, the test solution.
本发明方法中，作为实施方案之一，所述方法还包括供试品的溶液配制：称取聚乙烯醇供试品置于量瓶中，加水使其完全溶解后，取上述溶液至西林瓶中，加入氯化羟胺或氯化羟胺衍生物溶液、碱性溶液，摇匀，再加入酸性溶液及金属离子溶液，用水稀释至刻度，摇匀，备用。In the method of the present invention, as one of the embodiments, the method also includes the solution preparation of the test sample: take the polyvinyl alcohol test sample and place it in a measuring bottle, add water to make it completely dissolve, and then transfer the above solution to the vial , add hydroxylamine chloride or hydroxylamine chloride derivative solution, alkaline solution, shake well, then add acidic solution and metal ion solution, dilute with water to the mark, shake well, set aside.
本发明方法中，作为实施方案之一，所述金属离子为Fe
3+、Fe
2+、Mn
2+、Cd
2+、Cr
3+、Cu
2+或Pt
2+。
In the method of the present invention, as one of the embodiments, the metal ion is Fe 3+ , Fe 2+ , Mn 2+ , Cd 2+ , Cr 3+ , Cu 2+ or Pt 2+ .
本发明方法中，作为实施方案之一，所述金属离子化合物为三氯化铁、氯化亚铁、氯化锰、硝酸铬、氯化铬、硫酸铜或氯铂酸钠。In the method of the present invention, as one of the embodiments, the metal ion compound is ferric chloride, ferrous chloride, manganese chloride, chromium nitrate, chromium chloride, copper sulfate or sodium chloroplatinate.
本发明方法中，作为实施方案之一，所述碱性的氯化羟胺或氯化羟胺衍生物溶液中所用的碱为氢氧化钠、氢氧化钾、碳酸钠、碳酸钾、碳酸氢钠、碳酸氢钾、三乙胺或N,N-二异丙基乙胺。In the method of the present invention, as one of the embodiments, the alkali used in the alkaline hydroxylamine chloride or hydroxylamine chloride derivative solution is sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, carbonic acid Potassium hydrogen, triethylamine or N,N-diisopropylethylamine.
本发明方法中加碱的目的是中和氯化羟胺或氯化羟胺衍生物，pH值调节至7～8。The purpose of adding alkali in the method of the present invention is to neutralize hydroxylamine chloride or hydroxylamine chloride derivatives, and the pH value is adjusted to 7-8.
本发明方法中，作为实施方案之一，所述酸性的金属离子溶液中所用的酸为盐酸、磷酸、硫酸、三氟乙酸或甲磺酸。In the method of the present invention, as one of the embodiments, the acid used in the acidic metal ion solution is hydrochloric acid, phosphoric acid, sulfuric acid, trifluoroacetic acid or methanesulfonic acid.
本发明方法中加酸的目的是形成具有络合作用的异肟酸pH值调节至4～5。The purpose of adding acid in the method of the present invention is to form hydroxamic acid with complexing effect and adjust the pH value to 4-5.
本发明方法中，作为实施方案之一，所述方法还包括：用紫外可见分光光度计，在498-502nm处测定吸收度A。In the method of the present invention, as one of the embodiments, the method further includes: measuring the absorbance A at 498-502 nm with an ultraviolet-visible spectrophotometer.
本发明方法中，作为实施方案之一，所述方法还包括：用紫外可见分光光度计，在500nm处测定吸收度A。In the method of the present invention, as one of the embodiments, the method further includes: measuring the absorbance A at 500 nm with an ultraviolet-visible spectrophotometer.
本发明方法中，作为实施方案之一，所述方法还包括：按以下公式计算聚乙烯醇(C
2H
4O)n的含量：
In the method of the present invention, as one of the embodiments, the method also includes: calculating the content of polyvinyl alcohol (C 2 H 4 O)n according to the following formula:
RF＝(C
S×W
S)/A
S
RF＝(C S ×W S )/A S
公式中：formula:
A
S：对照品溶液的吸光度；
A S : the absorbance of the reference solution;
A
u：供试品溶液的吸光度；
A u : the absorbance of the test solution;
C
S：对照品溶液的浓度，mg/ml；
C S : the concentration of the reference substance solution, mg/ml;
C
u：供试品溶液的浓度，mg/ml；
C u : the concentration of the test solution, mg/ml;
W
S：对照品的含量，％；
WS : content of reference substance, %;
RF：对照品溶液浓度校正因子；RF: correction factor for the concentration of the reference substance solution;
本发明方法中，作为实施方案之一，所述方法还包括：In the method of the present invention, as one of the embodiments, the method further includes:
对照品的溶液配制：称取聚乙烯醇对照品，置于量瓶中，加水使其完全溶解后，并稀释至刻度，取上述溶液适量至西林瓶中，加入适量氯化羟胺或氯化羟胺衍生物溶液、碱性溶液，摇匀，再加入适量酸性溶液及三氯化铁溶液，用水稀释至刻度，摇匀，放置。Solution preparation of the reference substance: Weigh the polyvinyl alcohol reference substance, place it in a measuring bottle, add water to dissolve it completely, and dilute to the mark, take an appropriate amount of the above solution into a vial, add an appropriate amount of hydroxylamine chloride or hydroxylamine chloride Derivative solution, alkaline solution, shake well, then add appropriate amount of acidic solution and ferric chloride solution, dilute with water to the mark, shake well, and set aside.
用紫外可见分光光度计，在500nm处测定吸收度A
s；
Measure the absorbance A s at 500nm with a UV-Vis spectrophotometer;
供试品的溶液配制：称取聚乙烯醇供试品置于量瓶中，加水使其完全溶解后，并稀释至刻度，取上述溶液适量至西林瓶中，加入适量氯化羟胺或氯化羟胺衍生物溶液、碱性溶液，摇匀，再加入适量酸性溶液及三氯化铁溶液，用水稀释至刻度，摇匀，放置Preparation of the solution of the test product: Weigh the test product of polyvinyl alcohol and place it in a measuring bottle, add water to dissolve it completely, and dilute to the mark, take an appropriate amount of the above solution into a vial, add an appropriate amount of hydroxylamine chloride or chloride Hydroxylamine derivative solution, alkaline solution, shake well, then add appropriate amount of acidic solution and ferric chloride solution, dilute with water to the mark, shake well, place
检测：用紫外可见分光光度计，在500nm处测定吸收度A
u
Detection: Use a UV - Vis spectrophotometer to measure the absorbance Au at 500nm
按以下公式计算聚乙烯醇(C
2H
4O)n的含量：
Calculate the content of polyvinyl alcohol ( C2H4O )n according to the following formula:
RF＝(C
S×W
S)/A
S
RF＝(C S ×W S )/A S
公式中：formula:
A
S：对照品溶液的吸光度；
A S : the absorbance of the reference solution;
A
u：供试品溶液的吸光度；
A u : the absorbance of the test solution;
C
S：对照品溶液的浓度，mg/ml；
C S : the concentration of the reference substance solution, mg/ml;
C
u：供试品溶液的浓度，mg/ml；
C u : the concentration of the test solution, mg/ml;
W
S：对照品的含量，％；
WS : content of reference substance, %;
RF：对照品溶液浓度校正因子；RF: correction factor for the concentration of the reference substance solution;
本发明方法中，作为实施方案之一，所述方法中包括加入氯化羟胺或氯化羟胺衍生物的在1ml或1ml以上。In the method of the present invention, as one of the embodiments, the method includes adding 1 ml or more of hydroxylamine chloride or hydroxylamine chloride derivatives.
本发明方法中，作为实施方案之一，所述方法中包括加入三氯化铁的量在1ml或1ml以上。In the method of the present invention, as one of the embodiments, the method includes adding ferric chloride in an amount of 1 ml or more.
本发明方法中，作为实施方案之一，所述方法中包括络合时间在10min或10min以上。In the method of the present invention, as one of the embodiments, the method includes a complexing time of 10 minutes or more.
本发明方法中，作为实施方案之一，所述方法中包括络合后进行检 测温度为25～40℃。In the method of the present invention, as one of the embodiments, the method includes that the detection temperature after complexation is 25-40°C.
本发明方法中，作为实施方案之一，所述分光光度法检测聚乙烯醇含量的方法包括：In the method of the present invention, as one of the embodiments, the method for detecting polyvinyl alcohol content by the spectrophotometric method comprises:
对照品的溶液配制：称取聚乙烯醇对照品，置于量瓶中，加水使其完全溶解后，取上述溶液适量至西林瓶中，加入适量氯化羟胺或氯化羟胺衍生物溶液、碱性溶液，摇匀，再加入适量酸性溶液及三氯化铁溶液，用水稀释至刻度，摇匀，用紫外可见分光光度计，在500nm处测定吸光度AsSolution preparation of the reference substance: Weigh the polyvinyl alcohol reference substance, place it in a measuring bottle, add water to dissolve it completely, take an appropriate amount of the above solution into a vial, add an appropriate amount of hydroxylamine chloride or hydroxylamine chloride derivative solution, alkali neutral solution, shake well, then add an appropriate amount of acidic solution and ferric chloride solution, dilute to the mark with water, shake well, measure the absorbance As at 500nm with a UV-visible spectrophotometer
供试品的溶液配制：称取聚乙烯醇供试品置于量瓶中，加水使其完全溶解后，取上述溶液适量至西林瓶中，加入适量氯化羟胺或氯化羟胺衍生物溶液、碱性溶液，摇匀，再加入适量酸性溶液及三氯化铁溶液，用水稀释至刻度，摇匀，用紫外可见分光光度计，在500nm处测定吸收度A
u
Preparation of the solution of the test product: Weigh the test product of polyvinyl alcohol and place it in a measuring bottle, add water to make it completely dissolved, then take an appropriate amount of the above solution into a vial, add an appropriate amount of hydroxylamine chloride or hydroxylamine chloride derivative solution, Alkaline solution, shake well, then add an appropriate amount of acidic solution and ferric chloride solution, dilute to the mark with water, shake well, measure the absorbance Au at 500nm with an ultraviolet - visible spectrophotometer
按以下公式计算聚乙烯醇(C
2H
4O)n的含量：
Calculate the content of polyvinyl alcohol ( C2H4O )n according to the following formula:
RF＝(C
S×W
S)/A
S
RF＝(C S ×W S )/A S
公式中：formula:
A
S：对照品溶液的吸光度；
A S : the absorbance of the reference solution;
A
u：供试品溶液的吸光度；
A u : the absorbance of the test solution;
C
S：对照品溶液的浓度，mg/ml；
C S : the concentration of the reference substance solution, mg/ml;
C
u：供试品溶液的浓度，mg/ml；
C u : the concentration of the test solution, mg/ml;
W
S：对照品的含量，％；
WS : content of reference substance, %;
RF：对照品溶液浓度校正因子；RF: correction factor for the concentration of the reference substance solution;
所述氯化羟胺衍生物为甲基氯化羟胺、乙基氯化羟胺或异丙基氯化羟胺。The hydroxylamine chloride derivatives are methyl hydroxylamine chloride, ethyl hydroxylamine chloride or isopropyl hydroxylamine chloride.
本发明方法中，作为实施方案之一，所述方法还包括：In the method of the present invention, as one of the embodiments, the method further includes:
所述对照品的溶液配制：称取聚乙烯醇对照品56mg，置于量瓶中，加水使其完全溶解后，取上述溶液5ml至西林瓶中，精密量取1.25mol/L氯化羟胺溶液1ml，3.5mol/L氢氧化钠溶液1ml，再精密量取2.5mol/L盐酸溶液2ml，三氯化铁溶液1ml，摇匀，放置10min，备用；Solution preparation of the reference substance: Weigh 56 mg of polyvinyl alcohol reference substance, place it in a measuring bottle, add water to make it completely dissolved, then take 5 ml of the above solution into a vial, and accurately measure 1.25 mol/L hydroxylamine chloride solution 1ml, 1ml of 3.5mol/L sodium hydroxide solution, then precisely measure 2ml of 2.5mol/L hydrochloric acid solution, 1ml of ferric chloride solution, shake well, place for 10min, and set aside;
供试品的溶液配制：称取聚乙烯醇供试品56mg，置于100ml量瓶中， 加水使其完全溶解后，取上述溶液5ml至西林瓶中，精密量取1.25mol/L氯化羟胺溶液1ml，3.5mol/L氢氧化钠溶液1ml，再精密量取2.5mol/L盐酸溶液2ml，三氯化铁溶液1ml，摇匀，放置10min，备用。Solution preparation of the test product: Weigh 56 mg of the test product of polyvinyl alcohol, place it in a 100ml measuring bottle, add water to make it completely dissolved, then take 5 ml of the above solution into the vial, and accurately measure 1.25mol/L hydroxylamine chloride Solution 1ml, 3.5mol/L sodium hydroxide solution 1ml, and then accurately measure 2.5mol/L hydrochloric acid solution 2ml, ferric chloride solution 1ml, shake well, stand for 10min, and set aside.
本发明方法中，聚乙烯醇结构式表示方式为
现有技术利用结构上的羟基与硼酸形成凝胶，再与碘形成具有紫外吸收的络合物。而本发明是利用未醇解部分的酯基与羟胺氮原子上的孤对电子发生亲核取代反应，生成异羟肟酸与铁离子生成具有紫外吸收的络合物。两者原理不同，现有技术中使用PVA-硼酸-碘法主要是用于检测PVA作为化工原料时的含量，对检测结果的准确度要求不高，而本发明利用的羟胺-三氯化铁法主要是用于检测PVA作为药用时的含量，其对检测结果的准确性、检测方法的稳定性及重现性均要求很高，且意外发现该方法可以适用于所有未完全醇解的聚乙烯醇的检测，适用范围较广。
In the inventive method, polyvinyl alcohol structural formula expression mode is The prior art utilizes the hydroxyl group in the structure to form a gel with boric acid, and then forms a complex with ultraviolet absorption with iodine. However, the present invention uses the nucleophilic substitution reaction between the ester group of the non-alcoholyzed part and the lone pair of electrons on the nitrogen atom of hydroxylamine to generate hydroxamic acid and iron ions to form a complex with ultraviolet absorption. The two principles are different. In the prior art, the use of PVA-boric acid-iodine method is mainly used to detect the content of PVA as a chemical raw material, and the accuracy of the detection results is not high, while the hydroxylamine-iron trichloride used in the present invention The method is mainly used to detect the content of PVA when it is used as a medicine. It has high requirements for the accuracy of the detection results, the stability and reproducibility of the detection method, and it is unexpectedly found that this method can be applied to all alcoholysis The detection of polyvinyl alcohol has a wide range of applications.
聚乙烯醇的合成过程为：The synthesis process of polyvinyl alcohol is:
含量测定原理：Content determination principle:
所述的R可以为氢、甲基、乙基及异丙基；The R can be hydrogen, methyl, ethyl and isopropyl;
所述的M可以为Fe
3+、Fe
2+、Mn
2+、Cd
2+、Cr
3+、Cu
2+、或Pt
2+。
The M can be Fe 3+ , Fe 2+ , Mn 2+ , Cd 2+ , Cr 3+ , Cu 2+ , or Pt 2+ .
本发明实现了将羟胺-三氯化铁应用于聚乙烯醇含量的测定，尤其是当聚乙烯醇作为药用时的含量测定，与现有技术利用聚乙烯醇上的羟基与硼酸形成凝胶，再与碘以氢键形成络合物相比，本发明利用聚乙烯醇上未醇解的酯基与羟胺氮原子上的孤对电子发生亲核取代反应生成异羟肟酸，再与铁离子以共价键形成络合物，该络合物更加稳定。适用于所有不完全醇解的PVA(即适用于醇解度在98％以下的所有PVA的含量测定)。The present invention realizes the application of hydroxylamine-ferric chloride to the determination of polyvinyl alcohol content, especially the content determination when polyvinyl alcohol is used as medicine, and uses the hydroxyl on polyvinyl alcohol and boric acid to form a gel with the prior art , compared with iodine to form a complex with hydrogen bonds, the present invention utilizes the non-alcoholyzed ester group on the polyvinyl alcohol and the lone pair of electrons on the hydroxylamine nitrogen atom to undergo a nucleophilic substitution reaction to generate hydroxamic acid, and then react with iron Ions form complexes with covalent bonds, which are more stable. It is applicable to all PVAs with incomplete alcoholysis (that is, it is applicable to the content determination of all PVAs whose degree of alcoholysis is below 98%).
本发明方法具有专属性好，适用于未完全醇解的所有PVA的检测；该方法准确性高，重现性好；本方法不受PVA的聚合度、长链结构及羟基摩尔浓度的影响，通用性高。The method of the present invention has good specificity and is applicable to the detection of all PVAs that have not been completely alcoholysed; the method has high accuracy and good reproducibility; the method is not affected by the degree of polymerization, long-chain structure and hydroxyl molar concentration of PVA, High versatility.
另外，本发明的聚乙烯醇含量检测方法原理是利用聚乙烯醇高分子链上残留的酯基与羟胺反应形成异羟肟酸，再与金属离子螯合形成具有紫外吸收的络合物，该原理在目前某些物质的含量检测上已有应用，但均是用于结构单一、结构确切的物质的含量检测，而且形成的络合物稳定性差。In addition, the principle of the polyvinyl alcohol content detection method of the present invention is to use the residual ester group on the polyvinyl alcohol polymer chain to react with hydroxylamine to form hydroxamic acid, and then chelate with metal ions to form a complex with ultraviolet absorption. The principle has been applied to the content detection of certain substances at present, but they are all used for the content detection of substances with a single structure and exact structure, and the complexes formed have poor stability.
图1：实施例2中的线性试验结果图；Fig. 1: the linear test result figure in embodiment 2;
图2：实施例7中氯化羟胺溶液加入量对聚乙烯醇溶液吸光度的影响；Fig. 2: In embodiment 7, the impact of the addition amount of hydroxylamine chloride solution on the absorbance of polyvinyl alcohol solution;
图3：实施例7中0.5mol/L氯化铁溶液加入量对聚乙烯醇吸光度的影响；Fig. 3: the influence of 0.5mol/L ferric chloride solution addition amount on polyvinyl alcohol absorbance in embodiment 7;
图4：实施例7中络合时间对聚乙烯醇溶液吸光度的影响；Fig. 4: the impact of complexing time on the absorbance of polyvinyl alcohol solution in embodiment 7;
图5：实施例7中络合温度对聚乙烯醇溶液吸光度的影响。Fig. 5: Effect of complexation temperature on absorbance of polyvinyl alcohol solution in Example 7.
以下实施例和试验例用于进一步阐述本发明，但不以任何的方式限制本发明的有效范围。The following examples and test examples are used to further illustrate the present invention, but do not limit the effective scope of the present invention in any way.
以下实施例中的主要仪器、试剂和样品如下：Main instruments, reagents and samples in the following examples are as follows:
仪器：电子天平(厂家/型号：Mettler Toledo/AB135-S)；紫外-可见分光光度计(厂家/型号：岛津/UV-2600)Instrument: electronic balance (manufacturer/model: Mettler Toledo/AB135-S); ultraviolet-visible spectrophotometer (manufacturer/model: Shimadzu/UV-2600)
试剂：氯化羟胺(来源/批号：西陇科学股份有限公司/2003141)；氢氧化钠(来源/批号：西陇科学股份有限公司/52009136)；盐酸(西陇科学股份有限公司/180303)；六水合三氯化铁(西陇科学股份有限公司/2005221)Reagent: hydroxylamine chloride (source/batch number: Xilong Science Co., Ltd./2003141); sodium hydroxide (source/batch number: Xilong Science Co., Ltd./52009136); hydrochloric acid (Xilong Science Co., Ltd./180303); Ferric chloride hexahydrate (Xilong Science Co., Ltd./2005221)
样品：聚乙烯醇工作对照品(来源/批号/含量：珠海联邦制药股份有限公司/465200915/99.6％)Sample: Polyvinyl alcohol working reference substance (source/batch number/content: Zhuhai United Laboratories Co., Ltd./465200915/99.6%)
原料药：聚乙烯醇(来源/批号：珠海联邦制药股份有限公司/465190628、46520111202、46520111801)API: polyvinyl alcohol (source/batch number: Zhuhai United Laboratories Co., Ltd./465190628, 46520111202, 46520111801)
实施例1-1含量检测Example 1-1 content detection
溶液配制：Solution preparation:
1.25mol/L氯化羟胺溶液：取氯化羟胺约8.68g，精密称定，置100ml量瓶中，加适量水使其溶解，用水稀释至刻度，摇匀。1.25mol/L Hydroxylamine chloride solution: Take about 8.68g of Hydroxylamine chloride, weigh it accurately, put it in a 100ml measuring bottle, add an appropriate amount of water to dissolve it, dilute to the mark with water, and shake well.
3.5mol/L氢氧化钠溶液：取氢氧化钠约14g，精密称定，加水使溶解成100ml，摇匀。3.5mol/L sodium hydroxide solution: Take about 14g of sodium hydroxide, weigh it accurately, add water to dissolve it to 100ml, and shake well.
2.5mol/L盐酸溶液：精密量取20.8ml浓盐酸(摩尔浓度为12mol/L)，加水稀释至100ml，摇匀2.5mol/L hydrochloric acid solution: accurately measure 20.8ml concentrated hydrochloric acid (molar concentration is 12mol/L), dilute with water to 100ml, shake well
三氯化铁溶液：取六水合三氯化铁约6.76g，精密称定，置50ml量瓶中，加水溶解并稀释至刻度，摇匀Ferric chloride solution: Take about 6.76g of ferric chloride hexahydrate, weigh it accurately, put it in a 50ml measuring bottle, add water to dissolve and dilute to the mark, shake well
空白溶液：精密量取水5ml至30ml西林瓶中，再精密量取1.25mol/L氯化羟胺溶液1ml，3.5mol/L氢氧化钠溶液1ml，摇匀，再精密量取2.5mol/L盐酸溶液2ml，三氯化铁溶液1ml，摇匀，放置10min。Blank solution: precisely measure 5ml of water into a 30ml vial, then precisely measure 1ml of 1.25mol/L hydroxylamine chloride solution, 1ml of 3.5mol/L sodium hydroxide solution, shake well, then precisely measure 2.5mol/L hydrochloric acid solution 2ml, 1ml of ferric chloride solution, shake well and let stand for 10min.
对照品的溶液配制：称取聚乙烯醇(批号：465200915，含量99.6％)对照品56mg，置于100ml量瓶中，加水使其完全溶解后，取上述溶液5ml至30ml西林瓶中，精密量取1.25mol/L氯化羟胺溶液1ml，3.5mol/L氢氧化钠溶液1ml，再精密量取2.5mol/L盐酸溶液2ml，三氯化铁溶液1ml，摇匀，放置10min。Solution preparation of reference substance: Weigh 56 mg of polyvinyl alcohol (batch number: 465200915, content 99.6%) reference substance, place it in a 100ml measuring bottle, add water to make it completely dissolve, then take 5ml of the above solution into a 30ml vial, and accurately measure Take 1ml of 1.25mol/L hydroxylamine chloride solution, 1ml of 3.5mol/L sodium hydroxide solution, then precisely measure 2ml of 2.5mol/L hydrochloric acid solution, 1ml of ferric chloride solution, shake well, and let stand for 10min.
供试品的溶液配制：称取聚乙烯醇供试品(批号465190628)56mg，置于100ml量瓶中，加水使其完全溶解后，取上述溶液5ml至30ml西林瓶中，精密量取1.25mol/L氯化羟胺溶液1ml，3.5mol/L氢氧化钠溶液1ml，再精密量取2.5mol/L盐酸溶液2ml，三氯化铁溶液1ml，摇匀，放置10min。Solution preparation of the test product: Weigh 56mg of polyvinyl alcohol test product (batch number 465190628), place it in a 100ml measuring bottle, add water to dissolve it completely, take 5ml of the above solution into a 30ml vial, and accurately measure 1.25mol /L hydroxylamine chloride solution 1ml, 3.5mol/L sodium hydroxide solution 1ml, and then accurately measure 2.5mol/L hydrochloric acid solution 2ml, ferric chloride solution 1ml, shake well, let stand for 10min.
吸光度的检测及含量计算：Absorbance detection and content calculation:
用紫外可见分光光度计，在500nm处测定吸收度A
，
Absorbance A was measured at 500 nm with a UV-Vis spectrophotometer ,
按以下公式计算聚乙烯醇(C
2H
4O)n的含量：
Calculate the content of polyvinyl alcohol ( C2H4O )n according to the following formula:
RF＝(C
S×W
S)/A
S
RF＝(C S ×W S )/A S
公式中：formula:
A
S：对照品溶液的吸光度；
A S : the absorbance of the reference solution;
A
u：供试品溶液的吸光度；
A u : the absorbance of the test solution;
C
S：对照品溶液的浓度，mg/ml；
C S : the concentration of the reference substance solution, mg/ml;
C
u：供试品溶液的浓度，mg/ml；
C u : the concentration of the test solution, mg/ml;
W
S：对照品的含量，％；
WS : content of reference substance, %;
RF：对照品溶液浓度校正因子；RF: correction factor for the concentration of the reference substance solution;
检测结果：Test results:
对照溶液检测结果Test results of the control solution
供试品溶液检测结果Test result of test solution
结论：采用氯化羟胺-三氯化铁法测定聚乙烯醇含量的方法准确Conclusion: The method for determining the content of polyvinyl alcohol by the hydroxylamine chloride-ferric chloride method is accurate
实施例1-2含量检测Example 1-2 content detection
溶液配制Solution preparation
1.25mol/L甲基氯化羟胺溶液：取甲基氯化羟胺约10.37g，精密称定，置100ml量瓶中，加适量水使其溶解，用水稀释至刻度，摇匀1.25mol/L methylhydroxylamine chloride solution: take about 10.37g of methylhydroxylamine chloride, accurately weigh it, put it in a 100ml measuring bottle, add an appropriate amount of water to dissolve it, dilute with water to the mark, and shake well
其余的溶液配制按照实施例1-1进行，将氯化羟胺溶液替换为甲基氯化羟胺溶液之后，按照实施例1-1的试验步骤检测聚乙烯醇供试品(批号465190628)的含量。The rest of the solution preparation was carried out according to Example 1-1. After replacing the hydroxylamine chloride solution with methyl hydroxylamine chloride solution, the content of the polyvinyl alcohol test sample (batch number 465190628) was detected according to the test procedure of Example 1-1.
检测结果Test results
对照溶液检测结果Test results of the control solution
供试品溶液检测结果Test result of test solution
结论：采用甲基氯化羟胺-三氯化铁法测定聚乙烯醇含量的方法准确。Conclusion: The methyl hydroxylamine chloride-ferric chloride method is accurate in determining the content of polyvinyl alcohol.
实施例2、线性试验Embodiment 2, linearity test
溶液的配制Preparation of solution
取聚乙烯醇对照品(批号：465200915)约280mg,置100ml量瓶中,加水使其完全溶解后，用水稀释至刻度，摇匀；取上述溶液，用水稀释成150％、120％、100％、80％、60％不同浓度水平的溶液。依次取上述不同浓度水平的溶液5ml至30ml西林瓶中，精密量取1.25mol/L氯化羟胺溶液1ml，3.5mol/L氢氧化钠溶液1ml，摇匀；再精密量取2.5mol/L盐酸溶液2ml，酸性三氯化铁溶液1ml，摇匀，放置10min。Take about 280mg of polyvinyl alcohol reference substance (batch number: 465200915), put it in a 100ml measuring bottle, add water to dissolve it completely, dilute to the mark with water, and shake well; take the above solution and dilute it with water to 150%, 120%, 100% , 80%, 60% solutions with different concentration levels. Sequentially take 5ml of the above-mentioned solutions of different concentrations into 30ml vials, accurately measure 1ml of 1.25mol/L hydroxylamine chloride solution, 1ml of 3.5mol/L sodium hydroxide solution, and shake well; then precisely measure 2.5mol/L hydrochloric acid Solution 2ml, acidic ferric chloride solution 1ml, shake well, stand for 10min.
检测：分别取上述溶液适量，置于紫外-可见分光光度仪中检测其吸光度值，波长为500nm。Detection: Take an appropriate amount of the above solutions respectively, and place them in an ultraviolet-visible spectrophotometer to detect the absorbance value at a wavelength of 500 nm.
检测结果及计算：Test results and calculations:
检测结果见表1和图1.以吸光度(A)对浓度(C)作出标准回归曲线，得回归方程A＝aC+b，用y代替A，x代替C，可得线性方程为y＝0.8726x+0.0100，相关系数r为0.9997，y轴截距95％的置信区间为[-0.0107,0.0308]The test results are shown in Table 1 and Figure 1. Make a standard regression curve with absorbance (A) to concentration (C), get the regression equation A=aC+b, replace A with y, and replace C with x, and the linear equation can be y=0.8726 x+0.0100, the correlation coefficient r is 0.9997, and the 95% confidence interval for the y-intercept is [-0.0107,0.0308]
表1线性试验结果Table 1 Linearity test results
结论：结果表明聚乙烯醇在0.3360mg/ml～0.8399mg/ml(含量值：60％～150％)，吸光度与浓度成良好的线性关系。Conclusion: The results show that the absorbance of polyvinyl alcohol has a good linear relationship with the concentration at 0.3360mg/ml～0.8399mg/ml (content value: 60%～150%).
实施例3、精密度测试Embodiment 3, precision test
溶液的配制Preparation of solution
称取聚乙烯醇供试品(批号：465190628)约56mg，置100ml量瓶中,加水使其完全溶解后，稀释至刻度；取上述溶液5ml至30ml西林瓶中， 精密量取1.25mol/L氯化羟胺溶液1ml，3.5mol/L氢氧化钠溶液1ml，再精密量取2.5mol/L盐酸溶液2ml，三氯化铁溶液1ml，摇匀，放置10min，平行配制6份。Weigh about 56mg of polyvinyl alcohol for testing (batch number: 465190628), put it in a 100ml measuring bottle, add water to dissolve it completely, and then dilute to the mark; take 5ml of the above solution into a 30ml vial, and accurately measure 1.25mol/L Hydroxylamine chloride solution 1ml, 3.5mol/L sodium hydroxide solution 1ml, and then accurately measure 2.5mol/L hydrochloric acid solution 2ml, ferric chloride solution 1ml, shake well, stand for 10min, and prepare 6 parts in parallel.
检测：分别取上述溶液适量，置于紫外-可见分光光度仪中检测其吸光度值，波长为500nm。Detection: Take an appropriate amount of the above solutions respectively, and place them in an ultraviolet-visible spectrophotometer to detect the absorbance value at a wavelength of 500 nm.
检测结果及含量计算：Test results and content calculation:
检测结果如表2所示：重复试验的平均含量为98.6％，RSD为1.0％；中间精密度的6份样品含量的RSD为1.0％，12份样品含量的RSD为0.7％。The test results are shown in Table 2: the average content of the repeated test is 98.6%, and the RSD is 1.0%; the RSD of the content of 6 samples of intermediate precision is 1.0%, and the RSD of the content of 12 samples is 0.7%.
表2重复性试验结果Table 2 Repeatability test results
表3中间精密度试验结果Table 3 Intermediate precision test results
结论：结果显示该方法的重复性和中间精密度结果均符合可接受标准，表明该方法精密度良好，不会因为实验者、实验时间的改变而对实验结果造成影响。Conclusion: The results show that the repeatability and intermediate precision of the method meet the acceptable standards, indicating that the method has good precision and will not affect the experimental results due to changes in experimenters and experiment time.
实施例4、加样回收率Embodiment 4, sample addition recovery rate
4.1供试品溶液配制：称取聚乙烯醇供试品约56mg，置100ml量瓶中,加水使其完全溶解后，稀释至刻度；取上述溶液5ml至30ml西林瓶中，精密量取1.25mol/L氯化羟胺溶液1ml，3.5mol/L氢氧化钠溶液1ml，摇匀，再精密量取2.5mol/L盐酸溶液2ml，三氯化铁溶液1ml，摇匀，放置10min，平行制备3份样品。4.1 Preparation of the test solution: Weigh about 56mg of polyvinyl alcohol for the test, put it in a 100ml measuring bottle, add water to dissolve it completely, and then dilute to the mark; take 5ml of the above solution into a 30ml vial, and accurately measure 1.25mol 1ml of /L hydroxylamine chloride solution, 1ml of 3.5mol/L sodium hydroxide solution, shake well, then accurately measure 2ml of 2.5mol/L hydrochloric acid solution, 1ml of ferric chloride solution, shake well, let stand for 10min, prepare 3 parts in parallel sample.
4.2对照品溶液配制：称取聚乙烯醇对照品约56mg，置100ml量瓶中,加水使其完全溶解后，稀释至刻度；取上述溶液5ml至30ml西林瓶中，精密量取1.25mol/L氯化羟胺溶液1ml，3.5mol/L氢氧化钠溶液1ml，摇匀，再精密量取2.5mol/L盐酸溶液2ml，三氯化铁溶液1ml，摇匀，放置10min，平行制备6份样品。4.2 Preparation of reference substance solution: Weigh about 56mg of polyvinyl alcohol reference substance, put it in a 100ml measuring bottle, add water to dissolve it completely, and dilute to the mark; take 5ml of the above solution into a 30ml vial, and accurately measure 1.25mol/L Take 1ml of hydroxylamine chloride solution, 1ml of 3.5mol/L sodium hydroxide solution, shake well, then precisely measure 2ml of 2.5mol/L hydrochloric acid solution, 1ml of ferric chloride solution, shake well, let stand for 10min, and prepare 6 samples in parallel.
4.3对照加样溶液配制：分别称取聚乙烯醇对照品适量，置50ml量瓶中用水溶解后，加入适量供试品溶液，稀释至刻度；配制成80％、100％、120％不同浓度水平的加样溶液。依次取上述不同浓度水平的溶液5ml至30ml西林瓶中，精密量取1.25mol/L氯化羟胺溶液1ml，3.5mol/L氢氧化钠溶液1ml，摇匀；再精密量取2.5mol/L盐酸溶液2ml，三氯化铁溶液1ml，摇匀，放置10min。平行制备3份样品。4.3 Preparation of control sample solution: Weigh an appropriate amount of polyvinyl alcohol reference substance, dissolve it in water in a 50ml measuring bottle, add an appropriate amount of the test solution, and dilute to the scale; prepare different concentration levels of 80%, 100%, and 120% of the sample solution. Sequentially take 5ml of the above-mentioned solutions of different concentrations into 30ml vials, accurately measure 1ml of 1.25mol/L hydroxylamine chloride solution, 1ml of 3.5mol/L sodium hydroxide solution, and shake well; then precisely measure 2.5mol/L hydrochloric acid Solution 2ml, ferric chloride solution 1ml, shake well, stand for 10min. Three samples were prepared in parallel.
检测：分别取上述溶液适量，置于紫外-可见分光光度仪中检测其吸光度值，波长为500nmDetection: Take an appropriate amount of the above solutions respectively, and place them in a UV-visible spectrophotometer to detect the absorbance value at a wavelength of 500nm
4.4回收率计算4.4 Calculation of recovery rate
计算公式：RF＝(C
S×W
S)/A
S；
Pu
1＝RF×Au
1/Cu×100％；
Calculation formula: RF=(C S ×W S )/A S ; Pu 1 =RF×Au 1 /Cu×100%;
公式中：formula:
As：对照品溶液的吸光度；As: the absorbance of the reference substance solution;
Au1：供试品溶液的吸光度Au1: absorbance of the test solution
Cs：对照品溶液的浓度，mg/mL；Cs: the concentration of the reference substance solution, mg/mL;
Cu：供试品溶液的浓度，mg/mLCu: the concentration of the test solution, mg/mL
Ws：聚乙烯醇对照品的含量，99.6％；Ws: content of polyvinyl alcohol reference substance, 99.6%;
Au2：各浓度对照品加样溶液的吸光度Au2: Absorbance of each concentration of reference substance loading solution
Ms：各浓度称取的对照品的重量，mg；Ms: the weight of the reference substance weighed at each concentration, mg;
Pu：供试品中聚乙烯醇的含量Pu: the content of polyvinyl alcohol in the test product
表4回收率试验结果Table 4 recovery test result
4.5结果与结论：实验结果如表4所示，结果显示各浓度水平下聚乙烯醇的含量回收率为98.72％～100.57％，均在可接受的范围内(98.0％～4.5 Results and conclusions: The experimental results are shown in Table 4. The results show that the recovery rate of polyvinyl alcohol content at each concentration level is 98.72% to 100.57%, all within the acceptable range (98.0% to 100.57%).
102.0％)，9份测试结果的RSD≤5.0％，回收率平均值的95％置信区间为 [99.1％,99.9％]，也在可接受的范围内(98.0％～102.0％)，表明该方法准确度良好。102.0%), the RSD of 9 test results≤5.0%, and the 95% confidence interval of the average recovery rate was [99.1%, 99.9%], which was also within the acceptable range (98.0%～102.0%), indicating that the method Accuracy is good.
实施例5、样品测试Embodiment 5, sample test
5.1供试品溶液配制：分别称取3批供试品(批号分别为465190628、46520111202、46520111801)约56mg，置100ml量瓶中,加水使其完全溶解后，稀释至刻度；取上述溶液5ml至30ml西林瓶中，精密量取1.25mol/L氯化羟胺溶液1ml，3.5mol/L氢氧化钠溶液1ml，摇匀，再精密量取2.5mol/L盐酸溶液2ml，三氯化铁溶液1ml，摇匀，放置10min。平行制备2份。5.1 Preparation of the test solution: Weigh about 56 mg of 3 batches of the test (batch numbers are 465190628, 46520111202, 46520111801 respectively), put it in a 100ml measuring bottle, add water to dissolve it completely, and dilute to the mark; take 5ml of the above solution to In a 30ml vial, accurately measure 1ml of 1.25mol/L hydroxylamine chloride solution, 1ml of 3.5mol/L sodium hydroxide solution, shake well, then precisely measure 2ml of 2.5mol/L hydrochloric acid solution, 1ml of ferric chloride solution, Shake well and let stand for 10min. Prepare 2 copies in parallel.
5.2对照品溶液配制：称取聚乙烯醇对照品约56mg，置100ml量瓶中,加水使其完全溶解后，稀释至刻度；取上述溶液5ml至30ml西林瓶中，精密量取1.25mol/L氯化羟胺溶液1ml，3.5mol/L氢氧化钠溶液1ml，摇匀，再精密量取2.5mol/L盐酸溶液2ml，三氯化铁溶液1ml，摇匀，放置10min。平行制备6份5.2 Preparation of reference substance solution: Weigh about 56mg of polyvinyl alcohol reference substance, put it in a 100ml measuring bottle, add water to dissolve it completely, and then dilute to the mark; take 5ml of the above solution into a 30ml vial, and accurately measure 1.25mol/L Take 1ml of hydroxylamine chloride solution, 1ml of 3.5mol/L sodium hydroxide solution, shake well, then accurately measure 2ml of 2.5mol/L hydrochloric acid solution, 1ml of ferric chloride solution, shake well, and let stand for 10min. Prepare 6 copies in parallel
检测：分别取上述溶液适量，置于紫外-可见分光光度仪中检测其吸光度值，波长为500nmDetection: Take an appropriate amount of the above solutions respectively, and place them in a UV-visible spectrophotometer to detect the absorbance value at a wavelength of 500nm
5.3含量计算：5.3 Calculation of content:
按以下公式计算聚乙烯醇(C
2H
4O)n(C
4H
6O
2)m的含量：
Calculate the content of polyvinyl alcohol (C 2 H 4 O) n (C 4 H 6 O 2 ) m according to the following formula:
RF＝(C
S×W
S)/A
S
RF＝(C S ×W S )/A S
公式中：formula:
A
S：对照品溶液的吸光度；
A S : the absorbance of the reference solution;
A
u：供试品溶液的吸光度；
A u : the absorbance of the test solution;
C
S：对照品溶液的浓度，mg/ml；
C S : the concentration of the reference substance solution, mg/ml;
C
u：供试品溶液的浓度，mg/ml；
C u : the concentration of the test solution, mg/ml;
W
S：对照品的含量，％；
WS : content of reference substance, %;
RF：对照品溶液吸光度响应值；RF: Absorbance response value of the reference solution;
表5样品测试结果Table 5 sample test results
5.4结果与结论：实验结果如表5所示，结果显示，3批聚乙烯醇平均含量分别为99.4％、98.3％及98.8％，均符合药用要求。5.4 Results and conclusions: The experimental results are shown in Table 5. The results show that the average content of the three batches of polyvinyl alcohol is 99.4%, 98.3% and 98.8%, all of which meet the requirements for medicinal use.
实施例6、对比试验Embodiment 6, comparative test
1)硼酸-碘法1) Boric acid-iodine method
称取聚乙烯醇对照品(批号：465200915，含量99.6％)140mg，置于100mL量瓶中，加入适量的水，完全溶解后，用水稀释至刻度；取上述溶液10mL于100mL量瓶中，用水稀释至刻度；再取稀释后的溶液3ml于25mL量瓶中，依次加入12.5mL 4％硼酸溶液、2mL碘-碘化钾溶液，摇匀，用水稀释至刻度，静置20分钟后，用0.8μm微孔滤膜过滤，取滤液，在670nm处测定其吸光度As。Weigh 140mg of polyvinyl alcohol reference substance (batch number: 465200915, content 99.6%), put it in a 100mL measuring bottle, add an appropriate amount of water, after it is completely dissolved, dilute with water to the mark; take 10mL of the above solution in a 100mL measuring bottle, and Dilute to the mark; then take 3ml of the diluted solution in a 25mL measuring bottle, add 12.5mL of 4% boric acid solution and 2mL of iodine-potassium iodide solution in sequence, shake well, dilute to the mark with water, and after standing for 20 minutes, use a 0.8μm micrometer Filter through a pore filter, take the filtrate, and measure its absorbance As at 670nm.
按上述同样的方法制备供试品(批号：465190628，通过重量守恒法测定其含量为99.2％)溶液，在670nm处测定其吸光度Au。Prepare the test sample (batch number: 465190628, its content is 99.2% by weight conservation method) solution by the same method as above, and measure its absorbance Au at 670nm.
同样按以下公式计算聚乙烯醇(C
2H
4O)n的含量：
Also calculate the content of polyvinyl alcohol ( C2H4O )n according to the following formula:
RF＝(C
S×W
S)/A
S
RF＝(C S ×W S )/A S
依据上述方法测定465190628批次含量为93％。According to the above method, the batch content of 465190628 was determined to be 93%.
2)本发明2) The present invention
称取聚乙烯醇对照品(批号：465200915，含量99.6％)约56mg，置100ml量瓶中，加水完全溶解后，稀释至刻度；取上述溶液5ml至30ml西林瓶中，精密量取1.25mol/L氯化羟胺溶液1ml，3.5mol/L氢氧化钠溶液1ml，摇匀，再精密量取2.5mol/L盐酸溶液2ml，三氯化铁溶液1ml， 摇匀，放置10min，在500nm处测定其吸光度As。Weigh about 56mg of polyvinyl alcohol reference substance (batch number: 465200915, content 99.6%), put it in a 100ml measuring bottle, add water to dissolve it completely, and dilute to the mark; take 5ml of the above solution into a 30ml vial, and accurately measure 1.25mol/ 1 ml of L hydroxylamine chloride solution, 1 ml of 3.5 mol/L sodium hydroxide solution, shake well, then accurately measure 2 ml of 2.5 mol/L hydrochloric acid solution, 1 ml of ferric chloride solution, shake well, leave for 10 min, and measure their concentration at 500 nm. Absorbance As.
按上述同样的方法制备供试品(批号：465190628，通过重量守恒法测定其含量为99.2％)溶液，在500nm处测定其吸光度Au。Prepare the test sample (batch number: 465190628, its content is 99.2% by weight conservation method) solution by the same method as above, and measure its absorbance Au at 500nm.
同样按以下公式计算聚乙烯醇(C
2H
4O)n的含量：
Also calculate the content of polyvinyl alcohol ( C2H4O )n according to the following formula:
RF＝(C
S×W
S)/A
S
RF＝(C S ×W S )/A S
依据上述方法测定465190628批次含量为99.22％，可见本方法测定的结果更加准确。According to the above method, the content of batch 465190628 was determined to be 99.22%. It can be seen that the result determined by this method is more accurate.
此外，我们还对不同批号、不同醇解度、不同分子量范围做了比较，结果如表6所示。In addition, we also compared different batch numbers, different degrees of alcoholysis, and different molecular weight ranges, and the results are shown in Table 6.
表6硼酸-碘法与本发明含量检测结果对比Table 6 boric acid-iodine method compares with content detection result of the present invention
| 批号batch number | 分子量范围Molecular weight range | 醇解度Degree of alcoholysis | 硼酸-碘法boric acid-iodine method | 本发明this invention | 实际含量Actual content |
| 4652004140146520041401 | 10～11万100,000 to 110,000 | 87％87% | 91.3％91.3% | 99.6％99.6% | 99.1％99.1% |
| 4652004220246520042202 | 10～11万100,000 to 110,000 | 88％88% | 90.4％90.4% | 98.9％98.9% | 99.2％99.2% |
| 4652004290146520042901 | 10～11万100,000 to 110,000 | 87％87% | 87.6％87.6% | 99.7％99.7% | 99.6％99.6% |
| 465200915465200915 | 10～11万100,000 to 110,000 | 86％86% | 93％93% | 99.6％99.6% | 99.4％99.4% |
| 4652011210146520112101 | 5～6万50,000 to 60,000 | 95％95% | 91％91% | 99.5％99.5% | 99.6％99.6% |
| 4652011220146520112201 | 5～6万50,000 to 60,000 | 94％94% | 86％86% | 98.6％98.6% | 99.3％99.3% |
| 4652011290146520112901 | 5～6万50,000 to 60,000 | 96％96% | 89％89% | 99.1％99.1% | 99.7％99.7% |
| 4652012070246520120702 | 5～6万50,000 to 60,000 | 95％95% | 90％90% | 98.9％98.9% | 99.2％99.2% |
| 4652103080146521030801 | 2～3万20,000 to 30,000 | 87％87% | 89.6％89.6% | 99.3％99.3% | 99.8％99.8% |
| 4652103080146521030801 | 2～3万20,000 to 30,000 | 88％88% | 92.1％92.1% | 99.6％99.6% | 99.5％99.5% |
| 4652103080146521030801 | 2～3万20,000 to 30,000 | 87％87% | 88.6％88.6% | 99.2％99.2% | 99.7％99.7% |
| 4652103080146521030801 | 2～3万20,000 to 30,000 | 87％87% | 90.7％90.7% | 99.6％99.6% | 99.2％99.2% |
注：实际含量计算：100％-炽灼残渣-溶媒残留-水分Note: Calculation of actual content: 100%-residue on ignition-residual solvent-moisture
结论：结果显示，采用本方法测定的聚乙烯醇含量更加准确。Conclusion: The results show that the content of polyvinyl alcohol determined by this method is more accurate.
实施例7影响因素试验Embodiment 7 influence factor test
7.1氯化羟胺溶液加入量对聚乙烯醇溶液吸光度的影响7.1 The effect of the addition amount of hydroxylamine chloride solution on the absorbance of polyvinyl alcohol solution
样品制备：称取聚乙烯醇(批号：465190628)约56mg，置100ml量瓶中，加水使其完全溶解后，稀释至刻度；取上述溶液5ml至30ml西林瓶中，按表7加入不同体积的1.25mol/L氯化羟胺溶液，3.5mol/L氢氧化钠溶液1ml，摇匀，再加入2.5mol/L盐酸溶液2ml，三氯化铁溶液1ml，摇匀，放置10min。平行制备7份样品。Sample preparation: Weigh about 56mg of polyvinyl alcohol (lot number: 465190628), put it in a 100ml measuring bottle, add water to dissolve it completely, and dilute to the mark; take 5ml of the above solution into a 30ml vial, and add different volumes of 1.25mol/L hydroxylamine chloride solution, 1ml of 3.5mol/L sodium hydroxide solution, shake well, then add 2ml of 2.5mol/L hydrochloric acid solution, 1ml of ferric chloride solution, shake well, let stand for 10min. Seven samples were prepared in parallel.
检测：分别取上述溶液适量，置于紫外-可见分光光度仪中检测其吸光度，波长为500nmDetection: Take an appropriate amount of the above solutions respectively, and place them in a UV-visible spectrophotometer to detect their absorbance with a wavelength of 500nm
实验结果：结果如表7和图2所示Experimental results: the results are shown in Table 7 and Figure 2
表7Table 7
| 氯化羟胺加入量(ml)The amount of hydroxylamine chloride added (ml) | 吸光度Absorbance |
| 0.250.25 | 0.16340.1634 |
| 0.500.50 | 0.21780.2178 |
| 0.750.75 | 0.41680.4168 |
| 1.01.0 | 0.50120.5012 |
| 1.251.25 | 0.51140.5114 |
| 1.51.5 | 0.50680.5068 |
| 2.02.0 | 0.50790.5079 |
结论：随着氯化羟胺加入量的增加，吸光度也随之增大，说明还有聚乙烯醇还残留有酯基没有反应完全，当加入量大于等于1ml时，吸光度不再增大，说明酯基已经反应完全。Conclusion: As the amount of hydroxylamine chloride increases, the absorbance also increases, indicating that there are still ester groups in polyvinyl alcohol that have not reacted completely. When the amount added is greater than or equal to 1ml, the absorbance does not increase anymore, indicating that the ester groups base has reacted completely.
7.2三氯化铁溶液加入量对聚乙烯醇溶液吸光度的影响7.2 The effect of the amount of ferric chloride solution added on the absorbance of polyvinyl alcohol solution
样品制备：称取聚乙烯醇(批号：465190628)约56mg，置100ml量瓶中，加水使其完全溶解后，稀释至刻度；取上述溶液5ml至30ml西林瓶中，加入1.25mol/L氯化羟胺溶液1ml，平行制备7份样品，分别加入3.5mol/L氢氧化钠溶液1ml，2.5mol/L盐酸溶液2ml后，按表8加入不同体积的0.5mol/L三氯化铁溶液，摇匀，放置10min。Sample preparation: Weigh about 56mg of polyvinyl alcohol (batch number: 465190628), put it in a 100ml measuring bottle, add water to dissolve it completely, and dilute to the mark; take 5ml of the above solution into a 30ml vial, add 1.25mol/L chloride Prepare 7 samples in parallel with 1ml of hydroxylamine solution, add 1ml of 3.5mol/L sodium hydroxide solution and 2ml of 2.5mol/L hydrochloric acid solution respectively, add different volumes of 0.5mol/L ferric chloride solution according to Table 8, and shake well , placed for 10min.
检测：分别取上述溶液适量，置于紫外-可见分光光度仪中检测其吸光度值，波长为500nm。Detection: Take an appropriate amount of the above solutions respectively, and place them in an ultraviolet-visible spectrophotometer to detect the absorbance value at a wavelength of 500 nm.
实验结果：结果如表8及图3所示。Experimental results: The results are shown in Table 8 and Figure 3.
表8Table 8
| 0.5mol/L三氯化铁溶液加入量0.5mol/L ferric chloride solution addition amount | 吸光度Absorbance |
| 0.50ml0.50ml | 0.32410.3241 |
| 0.75ml0.75ml | 0.45120.4512 |
| 0.90ml0.90ml | 0.49970.4997 |
| 1.0ml1.0ml | 0.51200.5120 |
| 1.25ml1.25ml | 0.51370.5137 |
| 1.50ml1.50ml | 0.51390.5139 |
| 1.75ml1.75ml | 0.51260.5126 |
结论：实验结果显示，随着三氯化铁溶液加入量的增加，聚乙烯醇溶液的吸光度值逐渐增大，说明络合物的浓度不断增大；当三氯化铁溶液加入量大于等于1ml时，聚乙烯醇溶液的吸光度基本保持不变，说明络合物的浓度达到最大值。Conclusion: The experimental results show that with the increase of the amount of ferric chloride solution added, the absorbance value of polyvinyl alcohol solution increases gradually, indicating that the concentration of the complex is constantly increasing; when the amount of ferric chloride solution added is greater than or equal to 1ml , the absorbance of the polyvinyl alcohol solution remained basically unchanged, indicating that the concentration of the complex reached the maximum.
7.3络合时间对聚乙烯醇溶液吸光度的影响7.3 The effect of complexation time on the absorbance of polyvinyl alcohol solution
样品制备：称取聚乙烯醇(批号：465190628)约56mg，置100ml量瓶中，加水使其完全溶解后，稀释至刻度；取上述溶液5ml至30ml西林瓶中，加入1.25mol/L氯化羟胺溶液1ml，平行制备7份样品，分别加入3.5mol/L氢氧化钠溶液1ml，2.5mol/L盐酸溶液2ml，三氯化铁溶液1ml，摇匀，按表9放置不同时间。Sample preparation: Weigh about 56mg of polyvinyl alcohol (batch number: 465190628), put it in a 100ml measuring bottle, add water to dissolve it completely, and dilute to the mark; take 5ml of the above solution into a 30ml vial, add 1.25mol/L chloride Prepare 7 samples in parallel with 1ml of hydroxylamine solution, add 1ml of 3.5mol/L sodium hydroxide solution, 2ml of 2.5mol/L hydrochloric acid solution, and 1ml of ferric chloride solution, shake well, and place for different times according to Table 9.
检测：分别取上述溶液适量，置于紫外-可见分光光度仪中检测其吸光度，波长为500nm。实验结果：结果如表9及图4所示Detection: Take an appropriate amount of the above solutions respectively, and place them in an ultraviolet-visible spectrophotometer to detect their absorbance at a wavelength of 500 nm. Experimental results: the results are shown in Table 9 and Figure 4
表9Table 9
| 络合时间complexation time | 吸光度Absorbance |
| 5min5min | 0.38460.3846 |
| 7min7min | 0.47620.4762 |
| 10min10min | 0.51090.5109 |
| 20min20min | 0.51260.5126 |
| 30min30min | 0.51320.5132 |
| 60min60min | 0.51240.5124 |
结论：结果显示，当络合时间大于等于10min时，氯乙烯醇溶液吸光度基本不变，说明络合反应已完全。Conclusion: The results show that when the complexation time is greater than or equal to 10min, the absorbance of the vinyl chloride alcohol solution basically does not change, indicating that the complexation reaction has been completed.
7.4络合温度对聚乙烯醇溶液吸光度的影响7.4 The effect of complexation temperature on the absorbance of polyvinyl alcohol solution
样品制备：称取聚乙烯醇(批号：465190628)约56mg，置100ml量瓶中，加水使其完全溶解后，稀释至刻度；取上述溶液5ml至30ml西林瓶中，加入1.25mol/L氯化羟胺溶液1ml，平行制备7份样品，分别加入3.5mol/L氢氧化钠溶液1ml，2.5mol/L盐酸溶液2ml，三氯化铁溶液1ml，摇匀，按表10所述温度下放置10min。Sample preparation: Weigh about 56mg of polyvinyl alcohol (batch number: 465190628), put it in a 100ml measuring bottle, add water to dissolve it completely, and dilute to the mark; take 5ml of the above solution into a 30ml vial, add 1.25mol/L chloride Prepare 7 samples in parallel with 1ml of hydroxylamine solution, add 1ml of 3.5mol/L sodium hydroxide solution, 2ml of 2.5mol/L hydrochloric acid solution, and 1ml of ferric chloride solution, shake well, and place at the temperature described in Table 10 for 10min.
检测：分别取上述溶液适量，置于紫外-可见分光光度仪中检测其吸光度，波长为500nm。Detection: Take an appropriate amount of the above solutions respectively, and place them in an ultraviolet-visible spectrophotometer to detect their absorbance at a wavelength of 500 nm.
实验结果：结果如表10及图5所示Experimental results: the results are shown in Table 10 and Figure 5
表10Table 10
|
络合温度 | 吸光度Absorbance | |
| 0℃0°C | 0.20320.2032 | |
| 10℃10°C | 0.38360.3836 | |
| 20℃20°C | 0.47360.4736 | |
| 25℃25°C | 0.50990.5099 | |
| 30℃30℃ | 0.51240.5124 | |
| 40℃40℃ | 0.51080.5108 | |
| 50℃50℃ | 0.45320.4532 |
结论：结果显示，络合反应完全之后，溶液放置的温度过高或过低均将影响聚乙烯醇溶液的吸光度，最佳的放置温度为25-40℃。Conclusion: The results show that after the complexation reaction is complete, the temperature of the solution placed too high or too low will affect the absorbance of the polyvinyl alcohol solution, and the best storage temperature is 25-40°C.
Claims (20)
- 一种分光光度法检测聚乙烯醇含量的方法，其特征在于，所述方法包括采用氯化羟胺或氯化羟胺衍生物和金属离子为显色剂，所述氯化羟胺衍生物为甲基氯化羟胺、乙基氯化羟胺或异丙基氯化羟胺。A method for spectrophotometric detection of polyvinyl alcohol content, characterized in that the method comprises the use of hydroxylamine chloride or hydroxylamine chloride derivatives and metal ions as color reagents, and the hydroxylamine chloride derivatives are methyl chloride Hydroxylamine, Ethylhydroxylamine Chloride, or Isopropyl Hydroxylamine Chloride.
- 根据权利要求1所述的方法，其特征在于，所述方法还包括对照品溶液的制备：称取聚乙烯醇对照品，加水使其完全溶解，然后加入碱性的氯化羟胺或氯化羟胺衍生物溶液及酸性的金属离子溶液，即得对照品溶液。The method according to claim 1, characterized in that, the method also includes the preparation of the reference substance solution: take the polyvinyl alcohol reference substance, add water to make it dissolve completely, and then add alkaline hydroxylamine chloride or hydroxylamine chloride The derivative solution and the acidic metal ion solution are the reference substance solution.
- 根据权利要求1所述的方法，其特征在于，所述方法还包括供试品溶液的制备：将聚乙烯醇供试品，加水使其完全溶解，然后加入碱性的氯化羟胺或氯化羟胺衍生物溶液及酸性的金属离子溶液，即得供试品溶液。The method according to claim 1, characterized in that, the method also includes the preparation of the test solution: polyvinyl alcohol for the test, add water to make it completely dissolved, then add alkaline hydroxylamine chloride or chlorinated Hydroxylamine derivative solution and acidic metal ion solution, that is, the test solution.
- 根据权利要求2所述的方法，其特征在于，所述方法还包括：The method according to claim 2, further comprising:对照品的溶液配制：称取聚乙烯醇对照品，置于量瓶中，加水使其完全溶解后，取上述溶液至西林瓶中，加入氯化羟胺或氯化羟胺衍生物溶液、碱性溶液，摇匀，再加入酸性溶液及金属离子溶液，用水稀释至刻度，摇匀，备用。Solution preparation of the reference substance: Weigh the polyvinyl alcohol reference substance, place it in a measuring bottle, add water to dissolve it completely, take the above solution into a vial, add hydroxylamine chloride or hydroxylamine chloride derivative solution, alkaline solution , shake well, then add acidic solution and metal ion solution, dilute with water to the mark, shake well, set aside.
- 根据权利要求3所述的方法，其特征在于，所述方法还包括：The method according to claim 3, further comprising:供试品的溶液配制：称取聚乙烯醇供试品，置于量瓶中，加水使其完全溶解后，取上述溶液至西林瓶中，加入氯化羟胺或氯化羟胺衍生物溶液、碱性溶液，摇匀，再加入酸性溶液及金属离子溶液，用水稀释至刻度，摇匀，备用。Preparation of the solution of the test product: Weigh the test product of polyvinyl alcohol, place it in a measuring bottle, add water to dissolve it completely, then take the above solution into a vial, add hydroxylamine chloride or hydroxylamine chloride derivative solution, alkali Add neutral solution, shake well, then add acidic solution and metal ion solution, dilute with water to the mark, shake well, set aside.
- 根据权利要求1所述的方法，其特征在于，所述金属离子为Fe 3+、Fe 2+、Mn 2+、Cd 2+、Cr 3+、Cu 2+或Pt 2+。 The method according to claim 1, wherein the metal ion is Fe 3+ , Fe 2+ , Mn 2+ , Cd 2+ , Cr 3+ , Cu 2+ or Pt 2+ .
- 根据权利要求6所述的方法，其特征在于，所述金属离子化合物为三氯化铁、氯化亚铁、氯化锰、硝酸铬、氯化铬、硫酸铜或氯铂酸钠。The method according to claim 6, wherein the metal ion compound is ferric chloride, ferrous chloride, manganese chloride, chromium nitrate, chromium chloride, copper sulfate or sodium chloroplatinate.
- 根据权利要求3所述的方法，其特征在于，所述碱性的氯化羟胺或氯化羟胺衍生物溶液中所用的碱为氢氧化钠、氢氧化钾、碳酸钠、碳 酸钾、碳酸氢钠、碳酸氢钾、三乙胺或N,N-二异丙基乙胺。The method according to claim 3, wherein the alkali used in the alkaline hydroxylamine chloride or hydroxylamine chloride derivative solution is sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate , potassium bicarbonate, triethylamine or N,N-diisopropylethylamine.
- 根据权利要求3所述的方法，其特征在于，所述碱性的氯化羟胺或氯化羟胺衍生物溶液的pH值为7～8。The method according to claim 3, characterized in that the pH value of the alkaline hydroxylamine chloride or hydroxylamine chloride derivative solution is 7-8.
- 根据权利要求3所述的方法，其特征在于，所述酸性的金属离子溶液中所用的酸为盐酸、磷酸、硫酸、三氟乙酸或甲磺酸。The method according to claim 3, characterized in that, the acid used in the acidic metal ion solution is hydrochloric acid, phosphoric acid, sulfuric acid, trifluoroacetic acid or methanesulfonic acid.
- 根据权利要求3所述的方法，其特征在于，所述酸性的金属离子溶液的pH值为4～5。The method according to claim 3, characterized in that the pH value of the acidic metal ion solution is 4-5.
- 根据权利要求1所述的方法，其特征在于，所述方法还包括：用紫外可见分光光度计，在498-502nm处测定吸收度A。The method according to claim 1, characterized in that the method further comprises: measuring the absorbance A at 498-502nm with a UV-Vis spectrophotometer.
- 根据权利要求1所述的方法，其特征在于，所述方法还包括：用紫外可见分光光度计，在500nm处测定吸收度A。The method according to claim 1, further comprising: measuring the absorbance A at 500 nm with an ultraviolet-visible spectrophotometer.
- 根据权利要求1所述的方法，其特征在于，所述方法还包括：按以下公式计算聚乙烯醇(C 2H 4O)n的含量： method according to claim 1, is characterized in that, described method also comprises: calculate the content of polyvinyl alcohol (C 2 H 4 O) n by following formula:RF＝(Cs×Ws)/AsRF=(Cs×Ws)/As
公式中：formula:A S：对照品溶液的吸光度； A S : the absorbance of the reference solution;A u：供试品溶液的吸光度； A u : the absorbance of the test solution;C S：对照品溶液的浓度，mg/ml； C S : the concentration of the reference substance solution, mg/ml;C u：供试品溶液的浓度，mg/ml； C u : the concentration of the test solution, mg/ml;W S：对照品的含量，％； WS : content of reference substance, %;RF：对照品溶液浓度校正因子；RF: correction factor for the concentration of the reference substance solution;对照品溶液测定结果对应的RF值的平均值。
The average value of RF values corresponding to the measurement results of the reference solution. - 根据权利要求1～14任一所述的方法，其特征在于，所述方法还包括：The method according to any one of claims 1-14, characterized in that the method further comprises:对照品的溶液配制：称取聚乙烯醇对照品，置于量瓶中，加水使其完全溶解后，取上述溶液适量至西林瓶中，加入适量氯化羟胺或氯化羟胺衍生物溶液、碱性溶液，摇匀，再加入适量酸性溶液及三氯化铁溶液，用水稀释至刻度，摇匀，用紫外可见分光光度计，在500nm处测定吸光度As；Solution preparation of the reference substance: Weigh the polyvinyl alcohol reference substance, place it in a measuring bottle, add water to dissolve it completely, take an appropriate amount of the above solution into a vial, add an appropriate amount of hydroxylamine chloride or hydroxylamine chloride derivative solution, alkali neutral solution, shake well, then add an appropriate amount of acidic solution and ferric chloride solution, dilute to the mark with water, shake well, and measure the absorbance As at 500nm with a UV-visible spectrophotometer;供试品的溶液配制：称取聚乙烯醇供试品置于量瓶中，加水使其完全溶解后，取上述溶液适量至西林瓶中，加入适量氯化羟胺或氯化羟胺衍生物溶液、碱性溶液，摇匀，再加入适量酸性溶液及三氯化铁溶液，用水稀释至刻度，摇匀，用紫外可见分光光度计，在500nm处测定吸收度A u； Preparation of the solution of the test product: Weigh the test product of polyvinyl alcohol and place it in a measuring bottle, add water to make it completely dissolved, then take an appropriate amount of the above solution into a vial, add an appropriate amount of hydroxylamine chloride or hydroxylamine chloride derivative solution, Alkaline solution, shake well, then add an appropriate amount of acidic solution and ferric chloride solution, dilute to the mark with water, shake well, and measure the absorbance Au at 500nm with an ultraviolet - visible spectrophotometer;按以下公式计算聚乙烯醇(C 2H 4O)n的含量： Calculate the content of polyvinyl alcohol ( C2H4O )n according to the following formula:RF＝(Cs×Ws)/AsRF=(Cs×Ws)/As
公式中：formula:A S：对照品溶液的吸光度； A S : the absorbance of the reference solution;A u：供试品溶液的吸光度； A u : the absorbance of the test solution;C S：对照品溶液的浓度，mg/ml； C S : the concentration of the reference substance solution, mg/ml;C u：供试品溶液的浓度，mg/ml； C u : the concentration of the test solution, mg/ml;W S：对照品的含量，％； WS : content of reference substance, %;RF：对照品溶液浓度校正因子；RF: correction factor for the concentration of the reference substance solution;对照品溶液测定结果对应的RF值的平均值；
The average value of the RF value corresponding to the reference substance solution measurement result;所述氯化羟胺衍生物为甲基氯化羟胺、乙基氯化羟胺或异丙基氯化羟胺。The hydroxylamine chloride derivatives are methyl hydroxylamine chloride, ethyl hydroxylamine chloride or isopropyl hydroxylamine chloride. - 根据权利要求15所述的方法，其特征在于，所述方法中包括加入氯化羟胺或氯化羟胺衍生物的量为1ml或以上。The method according to claim 15, characterized in that the method includes adding hydroxylamine chloride or hydroxylamine chloride derivatives in an amount of 1 ml or more.
- 根据权利要求15所述的方法，其特征在于，所述方法中包括加入三氯化铁的量为1ml或以上。The method according to claim 15, characterized in that the method includes adding ferric chloride in an amount of 1ml or more.
- 根据权利要求15所述的方法，其特征在于，所述方法中包括络合时间为10min或以上。The method according to claim 15, characterized in that the complexation time included in the method is 10min or more.
- 根据权利要求15所述的方法，其特征在于，所述方法中包括络合后进行检测温度为25～40℃。The method according to claim 15, characterized in that, the method includes performing detection after complexation at a temperature of 25-40°C.
- 根据权利要求15所述的方法，其特征在于，所述方法还包括：The method according to claim 15, further comprising:所述对照品的溶液配制：称取聚乙烯醇对照品56mg，置于量瓶中，加水使其完全溶解后，取上述溶液5ml至西林瓶中，精密量取1.25mol/L 氯化羟胺溶液1ml，3.5mol/L氢氧化钠溶液1ml，再精密量取2.5mol/L盐酸溶液2ml，三氯化铁溶液1ml，摇匀，放置10min，备用；Solution preparation of the reference substance: Weigh 56 mg of polyvinyl alcohol reference substance, place it in a measuring bottle, add water to dissolve it completely, then take 5 ml of the above solution into a vial, and accurately measure 1.25 mol/L hydroxylamine chloride solution 1ml, 1ml of 3.5mol/L sodium hydroxide solution, then precisely measure 2ml of 2.5mol/L hydrochloric acid solution, 1ml of ferric chloride solution, shake well, place for 10min, and set aside;供试品的溶液配制：称取聚乙烯醇供试品56mg，置于100ml量瓶中，加水使其完全溶解后，取上述溶液5ml至西林瓶中，精密量取1.25mol/L氯化羟胺溶液1ml，3.5mol/L氢氧化钠溶液1ml，再精密量取2.5mol/L盐酸溶液2ml，三氯化铁溶液1ml，摇匀，放置10min，备用。Preparation of the solution of the test product: Weigh 56 mg of the test product of polyvinyl alcohol, place it in a 100 ml measuring bottle, add water to make it completely dissolved, then take 5 ml of the above solution into a vial, and accurately measure 1.25 mol/L hydroxylamine chloride Solution 1ml, 3.5mol/L sodium hydroxide solution 1ml, and then accurately measure 2.5mol/L hydrochloric acid solution 2ml, ferric chloride solution 1ml, shake well, stand for 10min, and set aside.
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| CN110296990B (en) * | 2019-07-08 | 2021-07-13 | 浙江圣兆药物科技股份有限公司 | Device and method for detecting content of polyvinyl alcohol in microsphere preparation |
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2021
- 2021-07-16 CN CN202110803825.7A patent/CN113504196A/en active Pending
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2022
- 2022-03-15 WO PCT/CN2022/080812 patent/WO2023279760A1/en active Application Filing
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117470792A (en) * | 2023-12-22 | 2024-01-30 | 华通福源生物技术(北京)股份有限公司 | Analysis method for detecting polysorbate 80 content in protein freeze-dried preparation |
| CN117470792B (en) * | 2023-12-22 | 2024-05-24 | 华通福源生物技术(北京)股份有限公司 | Analysis method for detecting polysorbate 80 content in protein freeze-dried preparation |
| CN118190853A (en) * | 2024-01-17 | 2024-06-14 | 翎耀生物科技(上海)有限公司 | Method for rapidly and quantitatively detecting adsorption force of medicinal carbon or activated carbon |
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