CN113866246A - Determination method of trace acid value of photoacid generator - Google Patents
Determination method of trace acid value of photoacid generator Download PDFInfo
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- CN113866246A CN113866246A CN202111084391.6A CN202111084391A CN113866246A CN 113866246 A CN113866246 A CN 113866246A CN 202111084391 A CN202111084391 A CN 202111084391A CN 113866246 A CN113866246 A CN 113866246A
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- 239000002253 acid Substances 0.000 title claims abstract description 103
- 238000000034 method Methods 0.000 title claims abstract description 36
- 239000002904 solvent Substances 0.000 claims abstract description 22
- 238000003918 potentiometric titration Methods 0.000 claims abstract description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 71
- 239000000523 sample Substances 0.000 claims description 43
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 24
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- 238000005303 weighing Methods 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical class CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 12
- -1 nitro, hydroxy, carboxyl Chemical group 0.000 claims description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 150000002431 hydrogen Chemical class 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 239000012488 sample solution Substances 0.000 claims description 8
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical class CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical class C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- LWNGJAHMBMVCJR-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenoxy)boronic acid Chemical compound OB(O)OC1=C(F)C(F)=C(F)C(F)=C1F LWNGJAHMBMVCJR-UHFFFAOYSA-N 0.000 claims description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Chemical class CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 125000005119 alkyl cycloalkyl group Chemical group 0.000 claims description 2
- 150000005215 alkyl ethers Chemical class 0.000 claims description 2
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 239000008346 aqueous phase Substances 0.000 claims description 2
- 150000001555 benzenes Chemical class 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- 150000008282 halocarbons Chemical class 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical class CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Chemical class C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims 2
- MBAKFIZHTUAVJN-UHFFFAOYSA-I hexafluoroantimony(1-);hydron Chemical compound F.F[Sb](F)(F)(F)F MBAKFIZHTUAVJN-UHFFFAOYSA-I 0.000 claims 1
- PNGLEYLFMHGIQO-UHFFFAOYSA-M sodium;3-(n-ethyl-3-methoxyanilino)-2-hydroxypropane-1-sulfonate;dihydrate Chemical compound O.O.[Na+].[O-]S(=O)(=O)CC(O)CN(CC)C1=CC=CC(OC)=C1 PNGLEYLFMHGIQO-UHFFFAOYSA-M 0.000 claims 1
- 238000001514 detection method Methods 0.000 abstract description 13
- 238000004448 titration Methods 0.000 abstract description 11
- 238000012360 testing method Methods 0.000 abstract description 2
- 150000007513 acids Chemical class 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 18
- 239000000243 solution Substances 0.000 description 17
- 239000012046 mixed solvent Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 7
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 6
- 239000012086 standard solution Substances 0.000 description 5
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 5
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000008231 carbon dioxide-free water Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical group CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- JGTNAGYHADQMCM-UHFFFAOYSA-N perfluorobutanesulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F JGTNAGYHADQMCM-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- DTQVDTLACAAQTR-UHFFFAOYSA-M Trifluoroacetate Chemical compound [O-]C(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-M 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- CASUWPDYGGAUQV-UHFFFAOYSA-M potassium;methanol;hydroxide Chemical compound [OH-].[K+].OC CASUWPDYGGAUQV-UHFFFAOYSA-M 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- PRZSXZWFJHEZBJ-UHFFFAOYSA-N thymol blue Chemical compound C1=C(O)C(C(C)C)=CC(C2(C3=CC=CC=C3S(=O)(=O)O2)C=2C(=CC(O)=C(C(C)C)C=2)C)=C1C PRZSXZWFJHEZBJ-UHFFFAOYSA-N 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/416—Systems
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
- G01N31/16—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using titration
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- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
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- Physics & Mathematics (AREA)
- Analytical Chemistry (AREA)
- Molecular Biology (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Abstract
本发明属于痕量酸值检测技术领域，具体为一种光致产酸剂痕量酸值测定方法。该方法对酸值含量低的检测更精准，结合标准加入法和电位滴定法，步骤包括在避光条件下，配制滴定液和测试用溶剂，先测定空白酸值，在定量的空白中加入不同浓度的对应酸，根据滴定值采用标准加入法方式计算空白中的游离酸的量；再测定空白加样品中酸值，称定量的样品加入定量的溶剂溶解，分别加入不同浓度的对应酸，根据滴定值采用标准加入法方式计算空白+样品中的酸值，再通过计算得样品的酸值。
The invention belongs to the technical field of trace acid value detection, in particular to a method for measuring the trace acid value of a photoacid generator. This method is more accurate for the detection of low acid value content. It combines standard addition method and potentiometric titration method. The steps include preparing titrant and test solvent under dark conditions, first measuring the blank acid value, and adding different amounts to the quantitative blank. Concentration of the corresponding acid, according to the titration value, use the standard addition method to calculate the amount of free acid in the blank; then measure the acid value in the blank plus sample, weigh the quantitative sample and add the quantitative solvent to dissolve, add corresponding acids of different concentrations respectively, according to The titration value is calculated by the standard addition method to calculate the acid value in the blank + sample, and then calculate the acid value of the sample.
Description
Technical Field
The invention belongs to the technical field of trace acid value detection, relates to trace acid value detection, and particularly relates to a method for determining a trace acid value of a photoacid generator.
Background
The photoacid generator is widely applied to the field of photocuring, and a product is decomposed under the irradiation of ultraviolet light to generate acid, and the generated acid enables a monomer to be polymerized or enables a polymer to be decomposed; accurate photoacid generator acid value determination is particularly important because the free acid in the product must be tightly controlled in order to prevent polymerization of the monomer or decomposition of the polymer prior to exposure of the product.
GB/T264-83 has product acid value detection, the reagent is 0.05N potassium hydroxide, 95% ethanol, alkaline blue 6B, the detection index is to titrate until blue becomes light red; detecting the acid value of GB/T12-8.5-2010 polyether polyol, wherein the reagent is isopropanol, phenolphthalein and potassium hydroxide methanol solution, and the detection standard is titration to light pink; CN102495059A acid value detection of an unsaturated polyester resin, compared with GB2895-82, the solubility is improved by replacing toluene with acetone, and observation is facilitated by replacing thymol blue with phenolphthalein.
Because the amount of free acid in the photoacid generator is low, the free acid in the product is difficult to accurately quantify, and some photoacid generators react with alkali for titration, so that an indicator cannot be used for indicating a terminal point; the above conventional detection method cannot be used for acid value detection of photoacid generators.
Disclosure of Invention
In order to solve the problems, the invention provides a method for measuring the trace acid value of a photoacid generator. The method comprises the following steps:
(1) preparing 0.005-0.01mol/L NaOH or KOH solution;
(2) accurately measuring or preparing the same solvent with the same volume according to the set parts;
(3) blank determination: weighing 5-10 free acid standard samples, wherein the weight range of the free acid standard samples is 1.000-10.000g, and then preparing a free acid solution corresponding to the parts of the free acid standard samples by using the solvent in the step (2); carrying out potentiometric titration on the free acid solution by using NaOH or KOH titrant prepared in the step (1) respectively to obtain a curve, and calculating the amount of acid in the blank according to the curve;
(4) and (3) sample determination: accurately weighing 5.000-10g of photoacid generator sample, weighing a free acid standard sample according to the method in the step (3), adding the photoacid generator sample into the solvent in the step (2), and uniformly dispersing to obtain a photoacid generator sample solution, wherein the weight ratio of the photoacid generator sample to the solvent is 1: 10-200 parts of the photoacid generator sample solution are the same as the free acid standard samples, the free acid standard samples are correspondingly added into the photoacid generator sample solution one by one, then the NaOH or KOH titrant prepared in the step (1) is respectively used for carrying out potentiometric titration, a curve is obtained, and the total acid amount in the photoacid generator sample solution when the free acid standard samples are not added is calculated according to the curve;
(5) and (3) calculating: and calculating the acid value in the sample according to the formula and the amount of the sample.
The formula is: acid (A1-A2) M/M,
in the formula, Acid- - -calculating to obtain the Acid value, mol/kg, in the photoacid generator sample;
a1- -calculating the total acid amount, g, in step (4) using standard addition methods
A2- -calculating the amount of acid in the blank in step (3), g, using standard addition methods
m- -mass of the photoacid generator sample referred to in step (4), g
M- -the molar concentration of the free acid standard added in step (3), mol/kg.
Specifically, the photoacid generator in step (4) comprises any one of the substances described by the following general formula:
further, R in the general formula1、R2、R3、R4Independently represent hydrogen, C1-C20Straight or branched alkyl of (2), C3-C20Cycloalkyl of, C4-C20Cycloalkylalkyl or C4-C20Alkyl cycloalkyl or C6-C20Or C wherein one or more hydrogens of the group are substituted by one or more groups selected from halogen, nitro, hydroxy, carboxyl, sulfonic acid, cyano or alkoxy1-C20Straight chain alkyl group of (1), C3-C20Cycloalkyl of, C4-C20Cycloalkylalkyl of (C)4-C20Alkyl cycloalkyl or C7-C20Any one of the aryl groups of (1).
Further, in the general formula, X is null or C1-C5An alkylene group of (a); y is O, S, N-R4Or C-R4Wherein R is4Is hydrogen, C1-C20Straight chain alkyl group of (1), C3-C20Cycloalkyl of, C4-C20Cycloalkylalkyl or C4-C20Any one of the alkyl cycloalkyl groups of (a).
Further, in the formula, Z is trifluoroacetate, tetrafluoroborate, hexafluorophosphate, hexafluoroantimonate, tetrakis (pentafluorophenyl) borate or
Any one of plasma anions, wherein R3Is hydrogen, C1-C20Straight or branched alkyl of (2), C3-C20Cycloalkyl of, C4-C20Cycloalkylalkyl or C4-C20Alkyl cycloalkyl or C6-C20Or C wherein one or more hydrogens of the group are substituted by one or more groups selected from halogen, nitro, hydroxy, carboxyl, sulfonic acid, cyano or alkoxy1-C20Straight chain alkyl group of (1), C3-C20Cycloalkyl of, C4-C20Cycloalkylalkyl of (C)4-C20Alkyl cycloalkyl or C7-C20Any one of the aryl groups of (a);
further, the free acid in the step (3) is
Wherein R is3Is hydrogen, C1-C20Straight or branched alkyl of (2), C3-C20Cycloalkyl of, C4-C20Cycloalkylalkyl of (5)Or C4-C20Alkyl cycloalkyl or C6-C20Or C wherein one or more hydrogens of the group are substituted by one or more groups selected from halogen, nitro, hydroxy, carboxyl, sulfonic acid, cyano or alkoxy1-C20Straight chain alkyl group of (1), C3-C20Cycloalkyl of, C4-C20Cycloalkylalkyl of (C)4-C20Alkyl cycloalkyl or C7-C20Any one of the aryl groups of (a);
further, the concentration of the free acid is 0.001-0.005 mol/kg;
further, the solvent used in the step (2) is an organic solvent which is liquid at normal temperature and normal pressure, and the organic solvent does not react with the free acid and the photoacid generator; for example, it may be any one or more of acetonitrile, halogenated hydrocarbon, benzene, substituted benzene, tetrahydrofuran, acetone, alkane, ethyl acetate, butyl acetate, or alkyl ether.
Further, a standard addition method and a potentiometric titration method are combined for use, and the electrode is a non-aqueous phase composite acid-base intelligent pH electrode.
Compared with the prior art, the invention achieves the following technical effects: 1) by using a potentiometric titration method and a standard addition method, detection interference is eliminated; 2) the proper detection reagent and conditions are matched and selected, so that the measurement result of the trace acid value is more accurate and reliable; 3) meets the acid value detection requirement of the photoacid generator which is decomposed by alkali.
Drawings
FIG. 1 is a graph obtained in step (3) in example 1 of the present invention;
FIG. 2 is a graph obtained in step (4) in example 1 of the present invention;
FIG. 3 is a graph obtained in step (3) in example 2 of the present invention;
FIG. 4 is a graph obtained in step (4) in example 2 of the present invention;
FIG. 5 is a graph obtained in step (3) in example 3 of the present invention;
FIG. 6 is a graph obtained in step (4) in example 3 of the present invention.
Note that the abscissa in the figure represents the mass (g) of the free acid standard added and the ordinate represents the amount (ml) of standard titration lye consumed.
Detailed Description
The present invention is not limited to the following embodiments, and those skilled in the art can implement the present invention in other embodiments according to the disclosure of the present invention, or make simple changes or modifications on the design structure and idea of the present invention, and fall into the protection scope of the present invention. It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
Firstly, the method of the invention is verified:
5 parts of the same solvent (50ml of dichloromethane and 50ml of acetonitrile) with the same volume are prepared, stirred uniformly, accurately weighed standard solutions (calculated according to actual concentration) of 0.002mol/kg of trifluoromethanesulfonic acid (2.000 g, 4.000g, 5.000g, 8.000g and 10.000 g) are added respectively, and then titrated with a standard solution of 0.005mol/L NaOH in sequence, and the amount of acid in the blank solvent is determined according to a standard addition method.
The same solvent (50ml dichloromethane and 50ml acetonitrile) with the same volume is prepared by 5 parts, stirred evenly, added with accurately weighed standard solution (calculated according to actual concentration) of 0.002mol/kg trifluoromethanesulfonic acid of 2.000g, 4.000g, 5.000g, 8.000g and 10.000g respectively, titrated by 0.005mol/L NaOH standard solution in sequence, and the acid amount in the blank solvent is measured according to the standard addition method.
The experimental results are as follows:
in the table, the recovery rate of acid value is (total acid amount-blank acid amount) × 100%/the amount of the standard sample, the standard sample means the mass of the added 0.002mol/kg of the standard solution of trifluoromethanesulfonic acid, and the amount of the sample means the mass of the added photoacid generator.
From the results, the results of the method after the sample is continuously used for 5 times and adjusted are all between 80% and 120%, and the range of the parallel sample is within 5%, so that the test requirements are met.
The invention is described in more detail below with reference to the following examples:
the calculation of the acid number in the samples in the following examples is as follows:
Acid＝(A1-A2)*M/m
acid- - -calculating the Acid value of the sample, mol/kg;
A1-calculating the total acid content, g, in the sample and solvent by standard addition;
A2-calculating the acid content of the solvent, g, by standard addition;
m-the mass of the sample, g;
m- -the molar concentration of the added standard acid, mol/kg;
example 1:
(1) weighing 0.2g of NaOH, putting the NaOH into a polyethylene container, adding 1000mL of carbon dioxide-free water, shaking up to clarify the solution, and preparing 0.005mol/L of NaOH solution;
(2) 50ml of acetonitrile and 50ml of dichloromethane are accurately measured and fully shaken to prepare a mixture of 1: 1, and preparing 10 parts of the mixed solvent for later use;
(3) blank determination: weighing 1.000g, 2.000g, 5.000g, 8.000g and 10.000g of p-toluenesulfonic acid standard sample of 0.002mol/kg, and respectively adding the p-toluenesulfonic acid standard sample into the mixed solvent prepared in the step (2); carrying out potentiometric titration by using NaOH titration solutions respectively to obtain curves (see figure 1), and calculating 0.6043g of acid in the blank according to the curves;
(4) and (3) sample determination: accurately weighing 5 parts of 5.000g photoacid generator
Respectively adding the mixture into the mixed solvent of 50ml acetonitrile and 50ml dichloromethane prepared in the step (2), and respectively adding the mixture into the mixed solvent0.002mol/kg p-toluenesulfonic acid standard 1.000g, 2.000g, 5.000g, 8.000g and 10.000g, respectively carrying out potentiometric titration by using NaOH titration solution, obtaining a curve (see figure 2), and calculating the total acid amount of 1.5848g according to the curve;
(5) and (3) calculating: calculating the acid value of 0.39 x 10 in the sample according to the formula and the amount of the sample-3mol/kg。
Specifically, the method comprises the following steps: taking the value of x as the amount of acid in the solvent when the standard curve y is 0, and A11.5848g (total acid amount in sample and solvent); a. the20.6043g (solvent blank, i.e. the amount of acid in the solvent); m is 0.002 mol/kg; m is 5.0002g, and the acid content in the sample is calculated to be 0.39 x 10-3mol/kg; examples 2 and 3 were the same, and the final data was entered and exited because the amount of sample weighed and the concentration of the standard acid were different.
Example 2
(1) Weighing 0.2g of NaOH, putting the NaOH into a polyethylene container, adding 1000mL of carbon dioxide-free water, shaking up to clarify the solution, and preparing 0.005mol/L of NaOH solution;
(2) 50ml of acetonitrile and 50ml of dichloroethane are accurately measured and fully shaken to prepare a mixture of 1: 1, and preparing 10 parts of the mixed solvent for later use;
(3) blank determination: weighing 1.000g, 2.000g, 5.000g, 8.000g and 10.000g of trifluoromethanesulfonic acid standard sample of 0.002mol/kg, and respectively adding the standard sample into the mixed solvent prepared in the step (2); carrying out potentiometric titration by using NaOH titration solutions respectively to obtain curves (see figure 3), and calculating 0.9592g of acid in the blank according to the curves;
(4) and (3) sample determination: accurately weighing 5 parts of 5.000g photoacid generator
Respectively adding the mixture into a mixed solvent of 50ml of acetonitrile and 50ml of dichloroethane prepared in the step (2), respectively adding 1.000g, 2.000g, 5.000g, 8.000g and 10.000g of 0.002mol/kg of trifluoromethanesulfonic acid standard sample, respectively carrying out potentiometric titration by using NaOH titration solution to obtain a curve (see figure 4), and calculating 2.0673g of total acid amount according to the curve;
(5) and (3) calculating: calculating the acid value of the sample according to the formula and the amount of the sampleIs 0.83 x 10-3mol/kg。
Example 3
(1) Weighing 0.2g of NaOH, putting the NaOH into a polyethylene container, adding 1000mL of carbon dioxide-free water, shaking up to clarify the solution, and preparing 0.005mol/L of NaOH solution;
(2) 50ml of acetone and 50ml of dichloromethane are precisely measured and thoroughly shaken to prepare a mixture of 1: 1, and preparing 10 parts of the mixed solvent for later use;
(3) blank determination: weighing 1.000g, 2.000g, 5.000g, 8.000g and 10.000g of perfluorobutyl sulfonic acid standard sample of 0.002mol/kg, and respectively adding the weighed materials into the mixed solvent prepared in the step (2); carrying out potentiometric titration by using NaOH titration solutions respectively to obtain curves (see figure 5), and calculating 1.0492g of acid in the blank according to the curves;
(4) and (3) sample determination: accurately weighing 5 parts of 5.000g photoacid generator
Respectively adding the mixture into a mixed solvent of 50ml of acetone and 50ml of dichloromethane prepared in the step (2), respectively adding 1.000g, 2.000g, 5.000g, 8.000g and 10.000g of perfluorobutyl sulfonic acid standard sample of 0.002mol/kg, respectively carrying out potentiometric titration by using NaOH titration solution to obtain a curve (see figure 6), and calculating 3.1461g of total acid according to the curve;
(5) and (3) calculating: calculating the acid value of 0.84 x 10 in the sample according to the formula and the amount of the sample-3mol/kg。
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and their concepts should be equivalent or changed within the technical scope of the present invention.
Claims (9)
1. A method for measuring the acid value of a photoacid generator trace is characterized in that: the method comprises the following steps:
(1) preparing 0.005-0.01mol/L NaOH or KOH solution;
(2) accurately measuring or preparing the same solvent with the same volume according to the set parts;
(3) blank determination: weighing 5-10 free acid standard samples, wherein the weight range of the free acid standard samples is 1.000-10.000g, and then preparing a free acid solution corresponding to the parts of the free acid standard samples by using the solvent in the step (2); carrying out potentiometric titration on the free acid solution by using NaOH or KOH titrant prepared in the step (1) respectively to obtain a curve, and calculating the amount of acid in the blank according to the curve;
(4) and (3) sample determination: accurately weighing 5.000-10g of photoacid generator sample, weighing a free acid standard sample according to the method in the step (3), adding the photoacid generator sample into the solvent in the step (2), and uniformly dispersing to obtain a photoacid generator sample solution, wherein the weight ratio of the photoacid generator sample to the solvent is 1: 10-200 parts of the photoacid generator sample solution are the same as the free acid standard samples, the free acid standard samples are correspondingly added into the photoacid generator sample solution one by one, then the NaOH or KOH titrant prepared in the step (1) is respectively used for carrying out potentiometric titration, a curve is obtained, and the total acid amount in the photoacid generator sample solution when the free acid standard samples are not added is calculated according to the curve;
(5) and (3) calculating: calculating according to a formula and the amount of the sample to obtain the acid value in the sample;
the formula is: acid (A1-A2) M/M,
in the formula, Acid- - -calculating to obtain the Acid value, mol/kg, in the photoacid generator sample;
a1-calculating the total acid content, g, in step (4) by standard addition method;
a2-measuring and calculating the amount of acid in the blank in the step (3), g, by adopting a standard addition method;
m-mass of the photoacid generator sample referred to in step (4), g;
m- -the molar concentration of the free acid standard added in step (3), mol/kg.
2. The method for determining the acid value of the photoacid generator trace according to claim 1, wherein: the photoacid generator is any one of the following general formulas:
3. the method for determining the acid value of the photoacid generator trace according to claim 2, characterized in that: in the general formula R1、R2、R3、R4Independently represent hydrogen, C1-C20Straight or branched alkyl of (2), C3-C20Cycloalkyl of, C4-C20Cycloalkylalkyl or C4-C20Alkyl cycloalkyl or C6-C20Or C wherein one or more hydrogens of the group are substituted by one or more groups selected from halogen, nitro, hydroxy, carboxyl, sulfonic acid, cyano or alkoxy1-C20Straight chain alkyl group of (1), C3-C20Cycloalkyl of, C4-C20Cycloalkylalkyl of (C)4-C20Alkyl cycloalkyl or C7-C20Any one of the aryl groups of (1).
4. The method for determining the acid value of the photoacid generator trace according to claim 2, characterized in that: in the general formula, X is null or C1-C5An alkylene group of (a); y is O, S, N-R4Or C-R4Wherein R is4Is hydrogen, C1-C20Straight chain alkyl group of (1), C3-C20Cycloalkyl of, C4-C20Cycloalkylalkyl or C4-C20Any one of the alkyl cycloalkyl groups of (a).
5. The method for determining the acid value of the photoacid generator trace according to claim 2, characterized in that: in the general formula, Z is trifluoroacetic acid, tetrafluoroboric acid, hexafluorophosphoric acid, hexafluoroantimonic acid, tetrakis (pentafluorophenyl) borate or
Wherein R is3Is hydrogen, C1-C20Straight or branched alkyl of (2), C3-C20Cycloalkyl of, C4-C20Cycloalkylalkyl or C4-C20Alkyl cycloalkyl or C6-C20Or C wherein one or more hydrogens of the group are substituted by one or more groups selected from halogen, nitro, hydroxy, carboxyl, sulfonic acid, cyano or alkoxy1-C20Straight chain alkyl group of (1), C3-C20Cycloalkyl of, C4-C20Cycloalkylalkyl of (C)4-C20Alkyl cycloalkyl or C7-C20Any one of the aryl groups of (1).
6. The method for determining the acid value of the photoacid generator trace according to claim 1, wherein: the solvent in the step (2) is one or more of acetonitrile, halogenated hydrocarbon, benzene, substituted benzene, tetrahydrofuran, acetone, alkane, ethyl acetate, butyl acetate and alkyl ether.
7. The method for determining the acid value of the photoacid generator trace according to claim 1, wherein: the free acid added is
Wherein R is3Is hydrogen, C1-C20Straight or branched alkyl of (2), C3-C20Cycloalkyl of, C4-C20Cycloalkylalkyl or C4-C20Alkyl cycloalkyl or C6-C20Or C wherein one or more hydrogens of the group are substituted by one or more groups selected from halogen, nitro, hydroxy, carboxyl, sulfonic acid, cyano or alkoxy1-C20Straight chain alkyl group of (1), C3-C20Cycloalkyl of, C4-C20Cycloalkylalkyl of (C)4-C20Alkyl cycloalkyl or C7-C20Any one of the aryl groups of (1).
8. The method for determining the acid value of the photoacid generator trace according to claim 1, wherein:
the concentration of the free acid standard sample weighed in the step (3) is 0.001-0.005 mol/kg.
9. The method for determining the acid value of the photoacid generator trace according to claim 1, wherein: the electrode used for potentiometric titration is a non-aqueous phase composite acid-base intelligent PH electrode.
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