CN109696517A - In a kind of detection polymerization liquid in fluorine-containing alkylacrylate fluorine content method - Google Patents
In a kind of detection polymerization liquid in fluorine-containing alkylacrylate fluorine content method Download PDFInfo
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Abstract
The present invention relates to the methods of fluorine content in fluorine-containing alkylacrylate in a kind of detection polymerization liquid, comprising: prepares total ionic strength and adjusts buffer solution, measures the potential value of fluorine ion standard solution, establish working curve equation；Polymerization liquid is obtained precipitating containing fluoroalkyl using reverse-extraction method, the precipitating after drying is placed in burning in the oxygen bottle for be previously added water and obtains sample to be tested absorbing liquid；Finally using potential value in Fluoride ion selective electrode method Accurate Determining sample to be tested absorbing liquid, gained potential value substitution working curve equation is obtained into fluorinion concentration in sample to be tested absorbing liquid, finally calculates the method for the fluorine content in polymerization liquid.The method has the advantages that test is quick, accuracy is high, instrument cost is low etc..
Description
Technical field
The present invention relates to analytical chemistry field, relate more specifically in a kind of detection polymerization liquid containing perfluoroalkyl acrylic
The method of fluorine content in esters.
Background technique
Fluorine-contaninig polyacrylate in addition to the loose feature of good film-forming property, network structure for having acrylate polymer itself,
The characteristics of also showing fluoropolymer has the performances such as lower surface energy, hydrophobic, oleophobic, corrosion-resistant, heat-resisting, inoxidizability,
It is had been widely used in recent years in fine chemical fields.But it since its cementability is poor, at high cost, largely limits
Occupation rate, the appropriate dosage for reducing fluorine monomer are that reduction fluorine content is one of solution to this problem in the market for it,
Reduce it by product cost, therefore the survey to fluorinated acrylate fluorine content in polymerization liquid while retention property is constant
Examination and its result become particularly important to the process of process optimization.There are many methods for the detection of F ion content at present, most common
For a variety of detection methods such as the chromatography of ions, electrode method, spectrophotometry or ICP, requirement of the different methods for sample
With selective difference.Ion chromatography --- Vavle switching method, time-consuming for this method, at high cost, difficulty is big, high to analysis personnel requirement；
ICP method is at high cost, complex pretreatment；And electrochemical methods are only applicable to the survey of content of fluoride ion in Inorganic water-soluble sample
It is fixed, it is easy currently without one to the content of fluoride ion in fluorine-containing alkylacrylate water-insoluble sample, accurately survey
Method for testing.
CN106525906A discloses the detection method of fluorine ion in per-fluoroalkyl sulfonyl inferior amine salt.Per-fluoroalkyl sulfonyl is sub-
Amine salt is soluble easily in water, and this method prepares at least two different fluorine ion standard test solutions of fluorinion concentration first and measures electricity
Place value calculates electrode constant S according to Nernst equation；Total ionic strength is added into per-fluoroalkyl sulfonyl imines and adjusts buffering
Then solution is diluted with water, measure the potential value of sample solution after mixing；Fluorine ion standard is added into sample solution again
Stock solution is uniformly mixed and measures the potential value of mixed solution；Fluorine ion in sample solution is calculated according to Nernst equation
Concentration, finally calculate the concentration of fluorine ion in per-fluoroalkyl sulfonyl imines.This method energy Accurate Determining per-fluoroalkyl sulfonyl
Fluorine ion in inferior amine salt, since sample is water-soluble, therefore the survey for water-insoluble fluorine-containing alkylacrylate sample
Fixed, this method is infeasible.CN104614416A discloses the detection method of fluoride in solder(ing) paste, and this method utilizes Oxygen Bomb Combustion
Method and ionic association constant, which combine, to be detected, in oxygen bomb combustion by solder(ing) paste sample pass through acetone treatment, dissolution halogen from
Son obtains acetone halogen solutions, obtained solution evaporation is concentrated to get concentrate, concentrate is handled by oxygen bomb combustion
To the test sample solution of fluoride ion, test solution is analyzed by ionic association constant, in ion selectivity battery
In measuring circuit and test sample solution battery device, fluorine ion standard sample solution is added, to measure current potential, using Standard entertion
Method calculates fluorinion concentration.This method be test solder(ing) paste in fluorine content, the measurement for fluorine in acrylate containing fluorine,
Sample type is different, and the methods of sample pre-treatments is without reference function, and sample pre-treatments have used acetone extraction, oxygen bomb in document
Requirement of the combustion method to instrument is higher, such as pressure etc., and experimental provision and experimental procedure are more.
CN101078709A discloses the method that fluorine ion detects in glass, will be leached after glass melting with hot deionized water
Sample solution after melting, with the method for fluoride ion selective electrode test content of fluoride ion；CN101793857A discloses soil
The detection method of middle fluorine ion, the soil for being 1:5 with solid-to-liquid ratio: water concussion obtains sample solution after extracting, then is selected with fluorine ion
It selects electrode test and obtains content of fluoride ion；The detection method of fluorine ion in rare earth is disclosed in CN103792269B, it is molten with hydrochloric acid
After final proof product, then with fluoride ion selective electrode test fluorine content；CN104713909A discloses a kind of side of plant leaf blade survey fluorine
Method, this method is air-dried for sample, is crushed, is sieved, hydrochloric acid extraction pre-treatment obtains sample solution, then with fluoride ion selective electrode
Test fluorine content；CN105651851A- tetrafluoride Du surveys fluorine, and this method handles sample using microwave digestion method, uses aluminium element
Interference is tested after eliminating using fluoride electrode, with the content of fluorine in the sample of standard addition method survey；CN102539516B- is disclosed
The method of ICP surveys the metal cation in fluoropolymer, after this method is using propyl alcohol or high boiling solvent sample dissolution, uses
Metal cation in ICPMS test sample, this method is compared in the invention belongs to different detection techniques.
The content of fluoride ion in different samples can be effectively detected in approach described above, but it fails effectively accurately to determine
The method that amount detects fluorine content in fluorine-containing alkylacrylate in polymerization liquid.
In current fluorine ion analyzing detecting method, do not provide it is a kind of simplicity, accurately, reliably, can detect
In polymerization liquid in fluorine-containing alkylacrylate fluorine content method.Therefore it develops and a kind of can solve above technical problem
Analysis method is very significant and necessary.
Summary of the invention
The present invention provides a kind of analysis method for detecting fluorine content in fluorine-containing alkylacrylate in polymerization liquid, should
Method is easy, accurate and quick.
In order to solve the above technical problems, the present invention adopts the following technical scheme:
In a kind of detection polymerization liquid in fluorine-containing alkylacrylate fluorine content analysis method, including walk as follows
It is rapid:
(1) it prepares total ionic strength and adjusts buffer solution: preparing the mixed solution of sodium acetate and sodium citrate, and ice is added
Acetic acid adjusts pH=5.0~5.5；
(2) it measures the potential value of fluorine ion standard solution: first preparing at least two different fluorine ion marks of fluorinion concentration
Quasi- solution, then fluorine ion standard solution and total ionic strength adjusting buffer solution that volume ratio is about 1:1 are taken, it stirs evenly, so
Measure its current potential on potentiometric titrimeter with fluoride ion selective electrode afterwards；
(3) working curve equation is established: according to Nernst equation E=E0-S×lgCF, with step (2) resulting potential value
Line Chart is made to the logarithm of fluorinion concentration, obtains working curve equation, wherein
E is electrode test current potential, mv；
E0For standard electrode potential, mv；
S is the slope of standard curve, i.e. electrode constant；
CFFor the concentration of fluorine ion in test solution, mol/L；
(4) sample analysis
Step 1: preparation is precipitated containing fluoroalkyl
Polymerization liquid is taken, methanol or ethyl alcohol is added dropwise thereto until precipitating is not further added by, standing discards supernatant liquor,
Lower layer's turbid is placed in baking oven, at 100~120 DEG C dry 2~for 24 hours to get containing fluoroalkyl precipitating；
Step 2: the absorbing liquid of sample to be tested is prepared
Precipitating after taking drying containing fluoroalkyl, makes it burn in Molotov cocktail after accurately weighed, wherein in advance
Suitable quantity of water is added in Molotov cocktail, is passed through oxygen at least 1min, makes in Molotov cocktail full of oxygen；After all burnt, shaking makes to generate
Smog be fully entrained in absorbing liquid, i.e., non smoke is transparent above absorbing liquid, absorbing liquid is transferred in volumetric flask, constant volume
To scale to get the absorbing liquid of sample to be tested；
Step 3: measurement content of fluoride ion
The absorbing liquid and total ionic strength for taking the sample to be tested that volume ratio is about 1:1 adjust buffer solution, stir evenly, use
Fluoride ion selective electrode measures its current potential on potentiometric titrimeter, brings its potential value into step (3) resulting working curve side
To get fluorinion concentration C in the absorbing liquid of sample to be tested in journeyF, calculate further according to formula (I) containing fluorine in fluoroalkyl
Percentage composition；Formula (I) is as follows:
Wherein, WFFor containing fluorine content in fluoroalkyl, %；
CFFor fluorinion concentration in absorbing liquid, mol/L；
V is the volume of absorbing liquid volumetric flask, L；
MFFor the molal weight of fluorine atom, g/mol；
WSFor the quality containing fluoroalkyl after drying, g.
Preferably, the total ionic strength adjusts buffer solution: weighing 8.2g anhydrous sodium acetate and 0.3g sodium citrate is set
In 1000mL water, after ultrasonic dissolution, 1.5ml glacial acetic acid is added and adjusts pH=5.0~5.5；
Preferably, the concentration of the fluorine ion standard solution is 0.0005mol/L~0.05mol/L.
Specifically, the preparation method of the fluorine ion standard solution are as follows: optionally that sodium fluoride preparation is dry in 100~110 DEG C
Dry 2~6h, and be cooled to room temperature, then precision weighing sodium fluoride preparation 0.2100g, is configured to 100ml solution, obtains
The fluorine ion standard solution of 0.05mol/L, with deionized water be diluted to concentration be 0.01mol/L, 0.005mol/L,
The fluorine ion standard solution of 0.001mol/L or 0.0005mol/L.
In the present invention, the fluorine-containing alkylacrylate includes but is not limited to general formula shown in formula one:
In formula one, A is hydrogen or methyl；B is alkyl；RFFor containing fluoroalkyl, general formula CmF2m+1, m be 4~20 integer.
The invention has the following advantages over the prior art:
The present invention provides the methods of fluorine ion in fluorine-containing alkylacrylate in a kind of detection polymerization liquid, utilize
Stripping process and the method for Oxygen bottle combustion pre-treatment obtain the absorbing liquid of sample to be tested, fluoride ion selective electrode test, using mark
Directrix curve method measures fluorine content, with ion chromatography-valve switch method compared with, have it is at low cost, difficulty is small, and the requirement to analysis is low
Advantage；Simultaneously compared with the pre-treatment of Oxygen Bomb Combustion, this method has lower requirement of experiment, simplifies analytic process, reduces
Analysis difficulty and cost.
Term definition
In the present invention, unless otherwise stated, " % " refers both to mass percent.
In the present invention, unless otherwise stated, the aqueous solution of used water or meaning refers to that analysis field is usually used
Analysis water, including but not limited to purified water, ultrapure water, deionized water etc..
In the present invention, no matter whether have before specific value " about " indicate, all refer to the specific value can this
Field is fluctuated in the range of approving, specifically can be fluctuation in absolute value ± 10% of specific value.
In the present invention, R2For linearly dependent coefficient.
Detailed description of the invention
Fig. 1 shows the constant-current titration working curve diagram of fluorine ion.
Specific embodiment
In order to make those skilled in the art more fully understand technical solution of the present invention, disclose further below some non-
Limiting embodiment, the present invention is described in further detail.
Reagent used in the present invention is available on the market or can described method system through the invention
It is standby and obtain.
Analytical reagent used in following embodiment is analytical reagents, and analysis is purified water with water.
Method validation embodiment
(1) it prepares total ionic strength and adjusts buffer solution: weighing 8.2g anhydrous sodium acetate and 0.3g sodium citrate is placed in
In 1000mL water, after ultrasonic dissolution, 1.5ml glacial acetic acid is added and adjusts pH=5.0~5.5.
(2) potential value of fluorine ion standard solution is measured: first by sodium fluoride preparation in 100~110 DEG C of dry 2~6h, and
Be cooled to room temperature, then precision weighing sodium fluoride preparation 0.2100g, be configured to 100ml solution, obtain the fluorine of 0.05mol/L from
Substandard solution, diluted with deionized water up to concentration for 0.01mol/L, 0.005mol/L, 0.001mol/L or
The standard solution of 0.0005mol/L.
The fluorine ion standard solution and 25mL total ionic strength for taking the various concentration in 25mL step (2) respectively adjust buffering
Solution stirs evenly, and measures its current potential on potentiometric titrimeter with fluoride ion selective electrode, obtains the fluorine ion mark of various concentration
The potential value of quasi- solution.
(3) working curve equation is established: according to Nernst equation (Nernst equation) E=E0-S×lgCF, with step (2)
Gained potential value makees Line Chart to the logarithm of fluorinion concentration, as shown in Figure 1, obtaining working curve equation: y=-58.5857x-
136.5192, R2=1.0000.
(4) sample analysis
Sodium fluoride preparation 0.0421g is weighed, with deionized water dissolving, is transferred in 500ml volumetric flask, and be diluted to quarter
Degree, shake up to get.It takes 25mLNaF aqueous solution and 25mL total ionic strength to adjust buffer solution, stirs evenly, selected with fluorine ion
Selecting electrode and measuring solution potential is 21.8mV, is updated to the resulting working curve equation of step (3): y=-58.5857x-
In 136.5192, C is obtainedF=1.9845 × 10-3Mol/L, calculate in sodium fluoride the mass percentage of fluorine ion be
44.78%, test value is as a result substantially consistent with theoretical value than theoretical value 45.24% less than normal 0.46%.
Embodiment 1
(1) it prepares total ionic strength and adjusts buffer solution: with method validation embodiment.
(2) potential value of fluorine ion standard solution is measured: with method validation embodiment.
(3) working curve equation is established: with method validation embodiment.
(4) sample analysis
Step 1: preparation is precipitated containing fluoroalkyl
In the present embodiment, the fluorochemical monomer of polymerization liquid is perfluorooctylethyl group acrylate, and inventory is
5.52g, fluorochemical monomer inventory 6.48g, solvent are not ethyl acetate for other, aobvious through gas chromatographic detection after reaction 12 hours
After showing polymerization reaction, the polymerization liquid of 10~50ml is taken, proper amount of methanol or ethyl alcohol are added dropwise thereto, there have at this time to be a large amount of heavy
Form sediment and generate, continue to be added dropwise, until precipitating is not further added by, stands, discard supernatant liquor, by lower layer's turbid be placed in baking oven 100~
120 DEG C of dryings 2~precipitated for 24 hours to get containing fluoroalkyl.
Step 2: the absorbing liquid of sample to be tested is prepared
25.1mg is precipitated containing fluoroalkyl after taking drying, so that it is burnt in Molotov cocktail after accurately weighed,
In, suitable quantity of water is added in Molotov cocktail in advance, is passed through oxygen at least 1min, makes in Molotov cocktail full of oxygen；After all burnt, vibration
It shakes, is fully entrained the smog generated in absorbing liquid, i.e., non smoke is transparent above absorbing liquid, and absorbing liquid is transferred to
In 250ml volumetric flask, scale is settled to get the absorbing liquid of sample to be tested.
Step 3: measurement content of fluoride ion
The absorbing liquid 25mL and total ionic strength for taking sample to be tested respectively adjust buffer solution 25mL, stir evenly, use fluorine
It is 28.4mV that ion-selective electrode measures its current potential on potentiometric titrimeter, brings its potential value into step (3) resulting work
In curvilinear equation y=-58.5857x-136.5192, the concentration C of fluorine ion in sample absorbing liquid is acquiredF=1.5311 × 10- 3Mol/L is 28.98% according to the mass percentage that public formula (I) can must contain fluorine ion in fluoroalkyl, as a result base
This is consistent with theoretical value 28.68%.The calculation formula of theoretical fluorine content is as shown in Formula II in polymerization liquid:
Wherein, WF' is theoretical fluorine content in polymerization liquid；
mFFor the inventory of fluorochemical monomer, g；
M is polymerization reaction total amount of feeding, g；
ωFFor the percentage composition of fluorine atom in fluorochemical monomer, %.
Embodiment 2
(1) it prepares total ionic strength and adjusts buffer solution: with method validation embodiment.
(2) potential value of fluorine ion standard solution is measured: with method validation embodiment.
(3) working curve equation is established: with method validation embodiment.
(4) sample analysis
Step 1: preparation is precipitated containing fluoroalkyl
In the present embodiment, the fluorochemical monomer of polymerization reaction is perfluoro hexyl ethylmethyl acrylate, and inventory is
5.52g, fluorochemical monomer inventory is not 6.48g for other, and solvent is ethyl acetate, after reaction 12 hours, through gas chromatographic detection
After completion of the reaction, the polymerization liquid of 10~50ml is taken, sample treatment is the same as embodiment 1.
Step 2: the absorbing liquid of sample to be tested is prepared
25.1mg is precipitated containing fluoroalkyl after taking drying, so that it is burnt in Molotov cocktail after accurately weighed,
In, suitable quantity of water is added in Molotov cocktail in advance, is passed through oxygen at least 1min, is in Molotov cocktail full of oxygen；After all burnt, vibration
It shakes, is fully entrained the smog generated in absorbing liquid, i.e., non smoke is transparent above absorbing liquid, and absorbing liquid is transferred to
In 250ml volumetric flask, scale is settled to get the absorbing liquid of sample to be tested.
Step 3: measurement content of fluoride ion
Take 25mL sample to be tested absorbing liquid and 25mL total ionic strength adjust buffer solution, stir evenly, with fluorine from
Son selects electrode to measure its current potential on potentiometric titrimeter as 31.1mV.The potential value of solution to be measured is brought into step (3)
In working curve equation y=-58.5857x-136.5192, the concentration C of fluorine ion in sample absorbing liquid is acquiredF=1.3769 ×
10-3Mol/L is 26.05% according to the mass percentage that public formula (I) can must contain fluorine ion in fluoroalkyl, as a result
Substantially consistent with fluorine content 26.30% theoretical in polymerization liquid.
Embodiment 3
(1) it prepares total ionic strength and adjusts buffer solution: with method validation embodiment.
(2) potential value of fluorine ion standard solution is measured: with method validation embodiment.
(3) working curve equation is established: with method validation embodiment.
(4) sample analysis
Step 1: preparation is precipitated containing fluoroalkyl
In the present embodiment, the fluorochemical monomer of polymerization reaction is perfluoro butyl ethylmethyl acrylate, and inventory is
6.4g, fluorochemical monomer inventory is not 5.6g for other, and solvent is ethyl acetate, anti-through gas chromatographic detection after reaction 12 hours
After answering, the polymerization liquid of 10~50ml is taken, sample treatment is the same as embodiment 1.
Step 2: the absorbing liquid of sample to be tested is prepared
24.9mg is precipitated containing fluoroalkyl after taking drying, so that it is burnt in Molotov cocktail after accurately weighed,
In, suitable quantity of water is added in Molotov cocktail in advance, is passed through oxygen at least 1min, makes in Molotov cocktail full of oxygen；After all burnt, vibration
It shakes, is fully entrained the smog generated in absorbing liquid, i.e., non smoke is transparent above absorbing liquid, and absorbing liquid is transferred to
In 250ml volumetric flask, scale is settled to get the absorbing liquid of sample to be tested.
Step 3: measurement content of fluoride ion
The total ionic strength of the absorbing liquid and 25mL that take the sample to be tested of 25mL adjusts buffer solution, stirs evenly, uses fluorine
It is 29.9mV that ion-selective electrode measures its current potential on potentiometric titrimeter.Bring the potential value of solution to be measured into step (3) institute
In the working curve equation y=-58.5857x-136.5192 obtained, the concentration C of fluorine ion in sample absorbing liquid is acquiredF=
1.4434×10-3Mol/L is according to the mass percentage that public formula (I) can must contain fluorine ion in fluoroalkyl
27.53%, it is as a result substantially consistent with theoretical value 27.47%.
Embodiment 4
(1) it prepares total ionic strength and adjusts buffer solution: with method validation embodiment.
(2) potential value of fluorine ion standard solution is measured: with method validation embodiment.
(3) working curve equation is established: with method validation embodiment.
(4) sample analysis
Step 1: preparation is precipitated containing fluoroalkyl
In the present embodiment, the fluorochemical monomer of polymerization reaction is perfluoro butyl ethylmethyl acrylate, and inventory is
9.0g, fluorochemical monomer inventory is not 4.6g for other, and solvent is ethyl acetate, anti-through gas chromatographic detection after reaction 12 hours
After answering, the polymerization liquid of 10~50ml is taken, sample treatment is the same as embodiment 1.
Step 2: the absorbing liquid of sample to be tested is prepared
24.8mg is precipitated containing fluoroalkyl after taking drying, so that it is burnt in Molotov cocktail after accurately weighed,
In, suitable quantity of water is added in Molotov cocktail in advance, is passed through oxygen at least 1min, makes in Molotov cocktail full of oxygen；After all burnt, vibration
It shakes, is fully entrained the smog generated in absorbing liquid, i.e., non smoke is transparent above absorbing liquid, and absorbing liquid is transferred to
In 250mL volumetric flask, scale is settled to get the absorbing liquid of sample to be tested.
Step 3: measurement content of fluoride ion
The total ionic strength of the absorbing liquid and 25mL that take the sample to be tested of 25mL adjusts buffer solution, stirs evenly, uses fluorine
It is 25.0mV that ion-selective electrode measures its current potential on potentiometric titrimeter.The potential value of solution to be measured is substituted into step (3)
Working curve equation y=-58.5857x-136.5192 in, acquire the concentration C of fluorine ion in sample absorbing liquidF=1.7500
×10-3Mol/L is 33.51% according to the mass percentage that public formula (I) can must contain fluorine ion in fluoroalkyl, knot
Fruit is substantially consistent with theoretical value 34.08%.
Embodiment 5
(1) it prepares total ionic strength and adjusts buffer solution: with method validation embodiment.
(2) potential value of fluorine ion standard solution is measured: with method validation embodiment.
(3) working curve equation is established: with method validation embodiment.
(4) sample analysis
Step 1: preparation is precipitated containing fluoroalkyl
In the present embodiment, the fluorochemical monomer of polymerization reaction is perfluoro hexyl ethylmethyl acrylate, and inventory is
8.84g, fluorochemical monomer inventory is not 4.76g for other, and solvent is ethyl acetate, after reaction 12 hours, through gas chromatographic detection
After completion of the reaction, a certain amount of polymerization liquid is taken, sample treatment is the same as embodiment 1.
Step 2: the absorbing liquid of sample to be tested is prepared
24.8mg is precipitated containing fluoroalkyl after taking drying, so that it is burnt in Molotov cocktail after accurately weighed,
In, suitable quantity of water is added in Molotov cocktail in advance, is passed through oxygen at least 1min, makes in Molotov cocktail full of oxygen；After all burnt, vibration
It shakes, is fully entrained the smog generated in absorbing liquid, i.e., non smoke is transparent above absorbing liquid, and absorbing liquid is transferred to
In 250ml volumetric flask, scale is settled to get the absorbing liquid of sample to be tested.
Step 3: measurement content of fluoride ion
The absorbing liquid and 25mL total ionic strength for taking 25mL sample to be tested adjust buffer solution, stir evenly, use fluorine ion
Electrode is selected to measure its current potential on potentiometric titrimeter as 22.4mV.Bring the potential value of solution to be measured into step (3) gained
In working curve equation y=-58.5857x-136.5192, the concentration C of fluorine ion in sample absorbing liquid is acquiredF=1.9382 ×
10-3Mol/L is 37.12% according to the mass percentage that public formula (I) can must contain fluorine ion in fluoroalkyl, as a result
Substantially consistent with theoretical value 37.17%.
Embodiment 6
(1) it prepares total ionic strength and adjusts buffer solution: with method validation embodiment.
(2) potential value of fluorine ion standard solution is measured: with method validation embodiment.
(3) working curve equation is established: with method validation embodiment.
(4) sample analysis
Step 1: preparation is precipitated containing fluoroalkyl
In the present embodiment, the fluorochemical monomer of polymerization reaction be perfluorooctylethyl group acrylate, inventory 9.52g,
Other not fluorine-containing monomeric charge amounts are 4.08g, and solvent is ethyl acetate, after reaction 12 hours, are reacted through gas chromatographic detection
After, a certain amount of polymerization liquid is taken, sample treatment is the same as embodiment 1.
Step 2: the absorbing liquid of sample to be tested is prepared
24.9mg is precipitated containing fluoroalkyl after taking drying, so that it is burnt in Molotov cocktail after accurately weighed,
In, suitable quantity of water is added in Molotov cocktail in advance, is passed through oxygen at least 1min, makes in Molotov cocktail full of oxygen；After all burnt, vibration
It shakes, is fully entrained the smog generated in absorbing liquid, i.e., non smoke is transparent above absorbing liquid, and absorbing liquid is transferred to
In 250ml volumetric flask, scale is settled to get the absorbing liquid of sample to be tested.
Step 3: measurement content of fluoride ion
Take the sample to be tested of 25mL absorbing liquid and 25mL total ionic strength adjust buffer solution, stir evenly, with fluorine from
Son selects electrode to measure its current potential on potentiometric titrimeter as 18.3mV.The potential value of solution to be measured is brought into obtained by step (3)
Working curve equation y=-58.5857x-136.5192 in, acquire the concentration C of fluorine ion in sample absorbing liquidF=2.2771
×10-3Mol/L is 43.44% according to the mass percentage that public formula (I) can must contain fluorine ion in fluoroalkyl, knot
Fruit is substantially consistent with theoretical value 43.65%.
To sum up described in embodiment,
According to the experimental result of embodiment 1-6, it is seen that contain fluothane in a kind of detection polymerization liquid provided by the present invention
The method of fluorine content in base acrylate, this method is easy, accurate, reliable, is suitble to contain perfluoroalkyl acrylic in polymerization liquid
The Accurate Determining of fluorine content in ester.
Method of the invention is described by preferred embodiment, related personnel obviously can the content of present invention,
To method described herein and application is modified or appropriate changes and combinations in spirit and scope, carry out the implementation and application present invention
Technology.Those skilled in the art can use for reference present disclosure, be suitably modified realization of process parameters.In particular, it should be pointed out that institute
There are similar replacement and change apparent to those skilled in the art, they are considered as being included in the present invention
It is interior.
Claims (5)
1. a kind of method for detecting fluorine content in fluorine-containing alkylacrylate in polymerization liquid, it is characterised in that: including such as
Lower step:
(1) it prepares total ionic strength and adjusts buffer solution: preparing the mixed solution of sodium acetate and sodium citrate, and glacial acetic acid is added
Adjust pH=5.0~5.5；
(2) it measures the potential value of fluorine ion standard solution: it is molten first to prepare at least two different fluorine ion standards of fluorinion concentration
Liquid, then fluorine ion standard solution and total ionic strength adjusting buffer solution that volume ratio is about 1:1 are taken, it stirs evenly, then uses
Fluoride ion selective electrode measures its current potential on potentiometric titrimeter；
(3) working curve equation is established: according to Nernst equation E=E0-S×lgCF, with step (2) resulting potential value to fluorine
The logarithm of ion concentration makees Line Chart, obtains working curve equation, wherein
E is electrode test current potential, mv；
E0For standard electrode potential, mv；
S is the slope of standard curve, i.e. electrode constant；
CFFor the concentration of fluorine ion in test solution, mol/L；
(4) sample analysis
Step 1: preparation is precipitated containing fluoroalkyl
Take polymerization liquid, methanol or ethyl alcohol be added dropwise thereto until precipitating is not further added by, stands, discards supernatant liquor, will under
Layer turbid is placed in baking oven, at 100~120 DEG C dry 2~for 24 hours to get containing fluoroalkyl precipitating；
Step 2: the absorbing liquid of sample to be tested is prepared
Precipitating after taking drying containing fluoroalkyl, makes it burn in Molotov cocktail, wherein firing in advance after accurately weighed
Suitable quantity of water is added in flask, is passed through oxygen at least 1min, makes in Molotov cocktail full of oxygen；After all burnt, shaking makes the cigarette generated
Mist is fully entrained in absorbing liquid, i.e., non smoke is transparent above absorbing liquid, and absorbing liquid is transferred in volumetric flask, quarter is settled to
Spend the absorbing liquid to get sample to be tested；
Step 3: measurement content of fluoride ion
Take the sample to be tested that volume ratio is about 1:1 absorbing liquid and total ionic strength adjust buffer solution, stir evenly, with fluorine from
Son selection electrode measures its current potential on potentiometric titrimeter, its potential value is brought into the resulting working curve equation of step (3),
Up to fluorinion concentration C in absorbing liquidF, further according to formula (I) calculate in the percentage composition containing fluorine ion in fluoroalkyl,
Formula (I) is as follows:
Wherein, WFFor containing content of fluoride ion in fluoroalkyl, %；
CFFor fluorinion concentration in absorbing liquid, mol/L；
V is the volume of absorbing liquid volumetric flask, L；
MFFor the molal weight of fluorine atom, g/mol；
WSFor the quality containing fluoroalkyl after drying, g.
2. according to the method described in claim 1, the total ionic strength adjusts the preparation method of buffer solution are as follows: weigh 8.2g
Sodium acetate and 0.3g sodium citrate are placed in 1000mL water, after ultrasonic dissolution, addition 1.5ml glacial acetic acid adjusting pH=5.0~
5.5。
3. according to the method described in claim 1, the concentration of the fluorine ion standard solution be 0.0005mol/L~
0.05mol/L。
4. according to the method described in claim 1, the preparation method of the fluorine ion standard solution are as follows: precision weighing sodium fluoride
0.2100g is configured to 100ml solution, obtains the fluorine ion standard solution of 0.05mol/L, is diluted with deionized water to obtain the final product
Concentration is the standard solution of 0.01mol/L, 0.005mol/L, 0.001mol/L or 0.0005mol/L.
5. according to the method described in claim 1, the fluorine-containing alkylacrylate has general formula shown in formula one:
Wherein, A is hydrogen or methyl；B is alkyl；RFFor containing fluoroalkyl, general formula CmF2m+1, m be 4~20 integer.
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