CN109425686A - A kind of detection method of the cationic degree of drilling fluid synthetic polymer - Google Patents
A kind of detection method of the cationic degree of drilling fluid synthetic polymer Download PDFInfo
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Abstract
This application provides a kind of detection methods of the cationic degree of drilling fluid synthetic polymer, comprising: by cationic polymer sample with ethanol purified solution, then with sample after sodium-chloride water solution dissolution purification, obtains sample aqueous solution；Control apparent viscosity≤10mPas of sample aqueous solution described in 1wt%；Using tetraphenylboron sodium back titration, detection obtains the total content of quaternary ammonium salt cationic and potassium ion；It detects to obtain potassium content using ashing method, calculates the total content of the quaternary ammonium salt cationic and potassium ion and the difference of potassium content, obtain actual measurement cationic degree.Cause cationic degree accuracy of measurement not high or the defect of measurement difficulty for being influenced in prior art Sodium Tetraphenylborate Method by external interference, polymer molecular structure, the present invention improves the method for measurement synthetic polymer cationic degree, has higher accuracy and applicability after improvement.
Description
Technical field
The present invention relates to technical field of analytical chemistry more particularly to a kind of cationic degrees of drilling fluid synthetic polymer
Detection method.
Background technique
Compared to anionic additive for drilling fluid, the additive for drilling fluid of cation group (such as quaternary ammonium salt) is inhibiting
Shale Hydration, stabilizing borehole, protection oil-gas Layer, raising bit speed, reduction energy consumption and drilling well overall cost etc. are shown
Significant advantage becomes one of the research hotspot of oilfield chemistry worker concern.For synthetic cationic polymers inorganic agent,
Some cationic monomers being easily copolymerized with acrylic acid, acrylamide have been developed at present, such as 3- acrylamido n-propyl diformazan
Ammonium chloride, 2- acrylamidoethyl alkyl dimethyl ammonium chloride, trimethylallylammonium chloride etc..
Cationic degree typically refers to the mass fraction that cation group accounts for total material, is direct characterization cationic processing
The characteristic index and key index of agent, highly cationic are also its basic reason place with strong rejection capability, anti-collapse property.Sun from
The molecular size range of sub- polymer, cation group type are different with anions and canons group ratio difference generation molecular structure, lead
Cause the polymer cation degree otherness larger.Currently, the domestic inspection to Organic chemical products cations or cationic degree
Survey method groundwork is carried out around chemical analysis.
The manufacturer of cationic chemical products is often different according to the method for detection cationic degree and mixes corresponding
Introduced contaminants, mainly have inorganic potassium ion (K in KCl+), ammonium ion (NH4NH in Cl4 +) or Water soluble chloride ion, there are also close
At small cation monomer etc. remaining in the process.Therefore, although chemical analysis has strong operability, wants to laboratory equipment
Not high feature is sought, but the status causes each chemical analysis to have limitation, for example disturbing factor is more or interferes
Object difficulty is eliminated.
Document " tetraphenylboron sodium back titration measures quaternary ammonium salt research " (Xi'an Petroleum University's journal (natural science edition),
In July, 2009, the 4th phase of volume 24: 62-64, Li Yan etc.) in, describing Sodium Tetraphenylborate Method is existing as detection quaternary ammonium salt sun
Ion degree is maximally efficient, one of extensive method, and measuring principle is: tetraphenylboron sodium is anti-with quaternary ammonium salt to be measured in alkaline medium
White precipitate should be formed, excessive tetraphenylboron sodium can be titrated with cetyl trimethylammonium bromide, cetyl front three when terminal
Base ammonium bromide can form pink material with titan yellow, and the mass fraction of quaternary ammonium salt is calculated by titration results.
Fig. 1 is the flow diagram of conventional cationic degree measuring method, i.e. the above method first dissolves polymer with pure water,
Then quaternary ammonium salt cationic and potassium content are measured, then measures potassium content, last calculating difference obtains cationic degree.But
This method is easy by the external interferences such as inorganic potassium ion, ammonium ion and molecular structure itself (with anionic sulfonic groups and carboxylic
Based on acid groups) influence, cause the accuracy of cationic degree measurement result lower.
Summary of the invention
In view of this, the application provides a kind of detection method of the cationic degree of drilling fluid synthetic polymer, the present invention
The detection method of offer has higher accuracy.
The present invention provides a kind of detection method of the cationic degree of drilling fluid synthetic polymer, comprising:
By cationic polymer sample with ethanol purified solution, then with sample after sodium-chloride water solution dissolution purification, obtain
To sample aqueous solution；Sample aqueous solution described in 1wt% is controlled in 25 ± 3 DEG C of apparent viscosity≤10mPas；
Using tetraphenylboron sodium back titration, the sample aqueous solution of the apparent viscosity≤10mPas is detected, is obtained
To the total content of quaternary ammonium salt cationic and potassium ion；It detects to obtain potassium content using ashing method, calculates the quaternary ammonium salt sun
The difference of the total content and potassium content of ion and potassium ion obtains actual measurement cationic degree.
The present invention be based on conventional Sodium Tetraphenylborate Method shown in FIG. 1, in prior art Sodium Tetraphenylborate Method by
To external interference, polymer molecular structure influence and cause cationic degree accuracy of measurement not high or defect that measurement is difficult,
The method for giving improved measurement synthetic polymer cationic degree is proposed to it, and there is higher accuracy after improvement and is applicable in
Property.
Referring to fig. 2, Fig. 2 is the flow diagram of cationic degree detection method provided in an embodiment of the present invention.This method packet
Include pure, the salt water dissolution of sample alcohol elution, thermal-oxidative degradation, detection quaternary ammonium salt cationic and potassium ion total amount, potassium content measure,
The operating procedures such as modifying factor correction mainly exclude ion interference-modifying factor correction method, to improve measurement sun
Ion degree accuracy.
Cationic polymer sample with ethanol purified solution is removed small molecule ammonium ion and other water by the embodiment of the present invention
Solubility impurity, sample after being purified.Wherein, the cationic polymer is generally used as additive for drilling fluid, structure
In have anionic group such as the sulfonic group (- SO of quaternary ammonium salt cationic and variety classes, content3 2-), carboxyl (- COO-).The present invention
The cationic polymer includes but is not limited to acrylamidopropyl trimethyl ammonium chloride-acrylamide (AMPTA-AM) binary
Cationic polymer, dimethyl diallyl trimethyl ammonium chloride-acrylamide (DMD-AM) bipolymer, acrylamido
Hydroxypropyltrimonium chloride-acrylamide -2- acrylamide-2-methyl propane sulfonic (AMPTA-AM-AMPS) terpolymer, third
Acrylamide base hydroxypropyltrimonium chloride-acrylamide -2- acrylamide-2-methyl propane sulfonic-acrylic acid (AMPTA-AM-
AMPS-AA) quadripolymer.
Specific improvements of the invention include: the molecular size range according to synthetic polymer, and concentration generally can be used and be
90%~95% ethanol water washs polymer samples to be measured, remove the remaining cationic monomer that wherein contains and
Other water-solubility impurities such as inorganic ammonium salt, to exclude the interference of external substance.That is, the present invention is preferably by cationic polymer sample
Product carry out washing purification with the ethanol solution that volumetric concentration is 90%~95%.In some embodiments of the invention, if polymerization
25 DEG C of ± 3 DEG C of apparent viscosities of object 1wt% aqueous solution are greater than 10mPas, are purified using 90% ethanol solution；Of the invention another
In some embodiments, if 25 DEG C of ± 3 DEG C of apparent viscosities of polymer 1wt% aqueous solution are less than or equal to 10mPas, using 95% second
Alcoholic solution purification.
After the elution of sample alcohol is pure, the embodiment of the present invention sufficiently dissolves sample after purification with sodium-chloride water solution, obtains sample
Aqueous solution.Existing Sodium Tetraphenylborate Method generallys use pure water dissolution polymer, and this method is appropriate inorganic using addition in water
Salt (sodium chloride nacl) dissolves polymer, using common-ion effect and the flocculation of inorganic salts, a certain amount of inorganic salts in solvent
Electron screening is carried out to the anionic group on polymer molecular chain, removal or decrease anionic group are to tetraphenyl borate radical ion
Repulsive interaction, to be modified to tetraphenylboron sodium measuring method.
In an embodiment of the present invention, sulfonic group molar content is 0~25% in the cationic polymer, carboxyl mole
Content is 0~70%, is greater than sample after the 0 sodium-chloride water solution dissolution less than 10% purifies using mass fraction.Wherein, described
The mass fraction of sodium-chloride water solution is preferably 5%~8%.In addition, the other conditions that the present invention dissolves salt water are not special
Limitation.
When being dissolved in water due to high molecular polymer, an a kind of random ball of string is presented, a ball of string crimps and in a ball of string
Include many cationic units.In conventional determining method when cation synthesising copolymer encounters precipitating reagent tetraphenylboron sodium, largely
Polymer cation unit gets off with precipitating together coprecipitation coating, and the cationic unit wrapped up cannot occur with tetraphenylboron sodium
Abundant precipitation reaction keeps measurement result relatively low.However, the chemical means such as thermal-oxidative degradation is taken to reduce polymer molecule in the present invention
Quality makes it that complete precipitation reaction occur with small molecule state and tetraphenylboron sodium effect, measures polymer sun after degradation treatment again
Ion degree improves the accuracy of result.
Therefore, in some embodiments of the invention, after the purification sample aqueous solution in 25 ± 3 DEG C of apparent viscosity >
10mPas can carry out thermal-oxidative degradation to sample with oxidant while stirring, be cooled to room temperature after fully degraded, obtain apparent
Viscosity≤10mPas sample aqueous solution.Oxidant used in the sample thermal-oxidative degradation can be hydrogen peroxide, ozone, peroxide
Acetic acid or sodium hypochlorite, preferably hydrogen peroxide (hydrogen peroxide, H2O2).In a preferred embodiment of the invention, the oxidant is adopted
The hydrogen peroxide for being 30~40% with mass concentration, dosage are 0.25~2mL.Preferably, the sample thermal-oxidative degradation process
Specifically: hydrochloric acid and hydrogen peroxide is added in sample aqueous solution after the purification, is heated to 85~90 DEG C of 10~15min of constant temperature, obtains
To apparent viscosity≤10mPas sample aqueous solution.In other embodiments of the invention, the sample 1wt% aqueous solution
Apparent viscosity≤10mPas is not necessarily to degradation treatment.
Sample aqueous solution described in 1wt% is controlled after 25 ± 3 DEG C of apparent viscosity≤10mPas, the embodiment of the present invention
Quaternary ammonium salt cationic and potassium ion total content are measured by tetraphenylboron sodium back titration；With ash purification determining potassium content, as a result,
Calculate the actual measurement cationic degree A of synthesizing cationic quasi polymerIt is real.Shown in specific formula for calculation such as following formula (1):
In formula (1):
AIt is real--- synthetic polymer surveys cationic degree, and unit is mM every gram (mmol/g)；
c1--- tetraphenylboron sodium standard solution molar concentration, unit are mole every liter (mol/L)；
c2--- cetyl trimethylammonium bromide standard solution molar concentration, unit are mole every liter (mol/L)；
V1--- the tetraphenylboron sodium standard solution volume pipetted when measurement total amount, unit are milliliter (mL)；
V2--- the volume of the tetraphenylboron sodium filtrate pipetted after filtering precipitating when measurement total amount, unit are milliliter (mL)；
V3--- cetyl trimethylammonium bromide standard solution volume used when measurement total amount, unit is milliliter
(mL)；
V4--- the tetraphenylboron sodium standard solution volume pipetted when measurement potassium content, unit are milliliter (mL)；
V5--- the volume of the tetraphenylboron sodium filtrate pipetted after filtering precipitating when measurement potassium content, unit is milliliter
(mL)；
V6--- cetyl trimethylammonium bromide standard solution volume used when measurement potassium content, unit are milli
It rises (mL)；
m1--- sample quality after weighed purification, unit are gram (g) when measurement total amount；
m2--- sample quality after weighed purification, unit are gram (g) when measurement potassium content.
The present invention is not particularly limited the tetraphenylboron sodium back titration and concrete operations of ashing method etc., according to ability
Technology contents known to field technique personnel are implemented.According to respectively obtaining the total of quaternary ammonium salt cationic and potassium ion in formula (1)
Content, potassium content calculate the difference of the two to get actual measurement cationic degree.
Compared with prior art, the present invention have the advantage that (1) by way of purification, remove inorganic potassium ion, ammonium from
The interference that son and remaining small cation monomer measure Sodium Tetraphenylborate Method, improves the accuracy of measurement result.(2) one is used
Quantitative chemical inorganic agent (salt) in polymer molecular structure anionic group carry out electron screening, removal or weaken yin from
Subbase group generates biggish measurement deviation to the repulsive interaction of tetraphenyl borate radical ion, i.e., appropriate inorganic using addition in water
Salt (NaCl) dissolution polymer is modified tetraphenylboron sodium measuring method using common-ion effect and the flocculation of inorganic salts.
(3) it takes the chemical means such as thermal-oxidative degradation that the long chain of synthetic polymer is fractured into small molecule location mode, reduces molecule
Amount not only makes cationic unit (quaternary ammonium salt group) and precipitating reagent tetraphenylboron sodium in molecular structure that precipitating more sufficiently occur anti-
It answers, it is relatively low to avoid measurement result；The anionic group after degrading on each structural unit can also be weakened significantly to tetraphenyl borate
Root generates to obtain ion pair repulsive interaction, to reduce the measurement deviation of cationic degree, improves the accuracy of measurement result.
In addition, the cationic degree of actual measurement is final result by conventional Sodium Tetraphenylborate Method.And in fact, due in polymer
A large amount of anionic group can generate repulsive interaction to tetraphenylboron acid group, and measurement result cannot really reflect cationic degree.
Content of cationic monomer variation calculates polymer cation theoretical value before and after the method for the present invention further passes through measurement polymerization reaction,
And the accuracy and reliability of cationic degree theoretical value is verified by elemental microanalysis method.The invention also includes: cationic degree is surveyed
Definite value calculates cationic degree measurement deviation compared with theoretical value, investigates out different anions group in polymer molecular structure
The influence that type and quantity measure cationic degree using mathematics Datafit software and MATLAB software, and uses index coordinates
Axis, initiative proposition simultaneously establish modifying factor template, are modified to the measured value of cationic degree, substantially increase cationic degree
The accuracy of measurement result.
In an embodiment of the present invention, anionic group molar content is in different ranges in polymer, corresponding sun
Ion degree modifying factor is not identical.The embodiment of the present invention is by investigating indoor synthesis cationic polymer-SO3 2-Group mole contains
Amount is 0~25% (considering Product Cost Control) ,-COO-When group molar content is 0~70%, using mass percent 8%
NaCl aqueous dissolution polymer, measurement has cationic degree of the different anions containing weight polymers, to calculate corresponding
Cationic degree measurement deviation and modifying factor.It the results are shown in Table 1:
1 different anions content of table and polymer cation degree modifying factor relationship
Table 2 reflects the case where modifying factor in anionic part content range is zero.In order to simply and intuitively search
Remaining modifying factor being not zero handles the test data in subordinate list 1 using mathematics Datafit software.Modifying factor is made
For-SO3 2-Group molar content and-COO-The function of group molar content fits nonlinear multivariable equation, provides in software
Nearly 300 groups of equations in preferably go out that related coefficient is good, and the relatively simple equation of expression formula is as fit equation.
By fit equation, by MATLAB software, using index coordinates axis, the modifying factor subgraph under different condition is drawn,
It is that the cationic degree that polymer sulfonic acid base molar content is 16%~21% in the embodiment of the present invention is repaired referring to Fig. 3 and Fig. 4, Fig. 3
Positive divisor figure, Fig. 4 are the cationic degree modifying factor that polymer sulfonic acid base molar content is 22%~25% in the embodiment of the present invention
Subgraph.In Fig. 3 and 4, the sulfonic group molar content that each curve represents is respectively as follows: 1-16%, 2-17%, 3-18%, 4-
19%, 5-20%, 6-21%, 7-22%, 8-23%, 9-24%, 10-25%.
The relationship of table 2 polymer different anions molar content and cationic degree modifying factor
| Sulfonic group molar content/% | Carboxyl molar content/% | Modifying factor t |
| <15 | <70 | 0 |
| 16~18 | <30 | 0 |
| 19~21 | <20 | 0 |
| 22~23 | <15 | 0 |
| 24~25 | <7 | 0 |
Wherein, the method for measurement sulfonic acid group content: the sample solution after purification is provided according to SY/T5242-1991,
After cation exchange resin column, sodium carbonate base is fully converted into sulfonic group, is then titrated with standard solution of sodium hydroxide.Root
According to the variation of conductivity, so that it is determined that the standard solution of sodium hydroxide volume consumed when conductivity minimum, is calculated sulfonic acid
Group content.
The method of carboxylic acid group content is provided according to the mensuration program of degree of hydrolysis in GB/T13940: using normal hydrochloric acid
Solution titration, selection methyl orange-sodium indigotindisulfonate are indicator.Examination is calculated according to the volume of consumed hydrochloric acid standard solution
The degree of hydrolysis of sample, to obtain the carboxyl-content in sample molecule structure.The embodiment of the present invention determines polymer samples as a result,
Anionic group type and content in structure, the cationic degree modifying factor chart gone out according to above-mentioned experimental summary is (see 3 He of attached drawing
4, table 1 and 2), so that it is determined that the modifying factor t of cationic degree.
In an embodiment of the present invention, the cationic degree true value AVeryAre as follows: actual measurement cationic degree AIt is real× (1+ modifying factor
It is sub- t), referring to formula (2):
AVery=AIt is real(1+t) formula (2)；
In formula (2):
AIt is real--- synthetic polymer surveys cationic degree, and unit is mM every gram (mmol/g)；
T --- the modifying factor of synthetic polymer cationic degree；0≤t < 1.
The embodiment of the present invention can calculate polymer cation by content of cationic monomer variation before and after measurement polymerization reaction
It is inclined to be calculated cationic degree measurement by theoretical value compared with theoretical value for the cationic degree measured value that Sodium Tetraphenylborate Method after improvement obtains
Difference investigates out the influence that the type and quantity of different anions group in polymer molecular structure measure cationic degree, utilizes
Mathematics Datafit software and MATLAB software, and index coordinates axis is used, initiative proposition simultaneously establishes modifying factor template, right
The measured value of cationic degree is modified, and substantially increases the accuracy of cationic degree measurement result.
Detailed description of the invention
Fig. 1 is the flow diagram of conventional cationic degree measuring method；
Fig. 2 is the flow diagram of cationic degree detection method provided in an embodiment of the present invention；
Fig. 3 is the cationic degree modifying factor that polymer sulfonic acid base molar content is 16%~21% in the embodiment of the present invention
Figure；
Fig. 4 is the cationic degree modifying factor that polymer sulfonic acid base molar content is 22%~25% in the embodiment of the present invention
Figure.
Specific embodiment
The following is a clear and complete description of the technical scheme in the embodiments of the invention, it is clear that described embodiment
Only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, the common skill in this field
Art personnel every other embodiment obtained without making creative work belongs to the model that the present invention protects
It encloses.
For a further understanding of the application, below with reference to embodiment to drilling fluid synthetic polymer provided by the present application
The detection method of cationic degree is specifically described.
Since the method for the present invention introduces modifying factor, the measurement sample in embodiment is the theoretical value of known cationic degree
Indoor synthesis polymer.
Embodiment 1
(1) it is poly- to weigh 1.00g acrylamidopropyl trimethyl ammonium chloride-acrylamide (AMPTA-AM) binary cation
Object sample is closed, through 90% alcohol solution dipping 2h of 100mL, washing removes small molecule ammonium ion and other water-solubility impurities, with one
Layer middling speed qualitative filter paper filters, and washs the sample of surface in three times with 90% ethyl alcohol 30mL, removes the residual of sample surfaces
Remaining impurity dries 2h at 105 ± 3 DEG C, after being cooled to room temperature, for use.
(2) sample m after purifying is weighed1=0.2000g (is accurate to 0.0001g), and 8.0g sodium chloride is added and distilled water fills
Divide dissolution.
1mL hydrogen peroxide and 2-3 drop dilute hydrochloric acid (volume ratio 1:1) are added, in 80 DEG C of heating 10min, to fully degraded
After be cooled to room temperature, then is adjusted with the NaAc_HAc buffer solution that pH value is 3.6 and controls pH value to 3.0~4.0, then standard
Really move into excessive tetraphenylboron sodium standard solution V1=25mL makes it generate precipitating, and constant volume is in 100mL volumetric flask.Room temperature is quiet
After setting 30min, with the quantitative slow filter paper filtering precipitating of bilayer, the filtrate V of a certain amount of volume is accurately pipetted2=25mL, uses hydrogen-oxygen
Change sodium solution and adjust pH value to 7.0~8.0, bromophenol blue indicator is added, with cetyl trimethylammonium bromide standard solution into
Row titration, when solution colour becomes light blue from bluish violet, as titration end-point.According to cetyl trimethylammonium bromide standard
The consumption V of solution3, calculate quaternary ammonium salt cationic and potassium ion total content in sample.
(3) quality m is weighed2Acrylamidopropyl trimethyl ammonium chloride-after=0.2g (being accurate to 0.0001g) purification
Acrylamide (AMPTA-AM) binary cationic polymer sample, it is molten with 2mL 2mol/L hydrochloric acid solution after 800 DEG C are high temperature ashing
Ash content is solved, then accurately moves into excessive sodium tetraphenylborate (STPB) standard solution V4=25mL, make its generate precipitating, constant volume in
In 100mL volumetric flask.After being stored at room temperature 30min, with the quantitative slow filter paper filtering precipitating of bilayer, obtain containing excessive tetraphenylboron
The clear filtrate of sodium accurately pipettes the filtrate V of a certain amount of volume5=25mL, with sodium hydroxide solution adjust pH value to 7.0~
8.0, bromophenol blue indicator is added, is titrated with cetyl trimethylammonium bromide standard solution, when solution colour is by royal purple
Discoloration is light blue, as titration end-point.According to the consumption V of cetyl trimethylammonium bromide standard solution6, calculate sample
Potassium content in product.
Both (4) difference be two Yuanyang of acrylamidopropyl trimethyl ammonium chloride-acrylamide (AMPTA-AM) from
The actual measurement cationic degree A of sub- polymerIt is real, calculation formula is as follows:
Wherein, C1=0.02293mol/L；C2=0.005994mol/L；V1=V4=25mL；V2=V5=25mL；V3=
16.1mL；m1=0.2g, m2=0.2g.
Since there is no potassium ion interference for indoor synthesis polymer, and bipolymer does not have anionic group to generate
Measurement deviation, then modifying factor t=0, therefore survey cationic degree AIt is realCalculating process it is as follows:
Embodiment 2~4
Measurement sample object in embodiment 1 is changed to the bipolymer of different cationic monomers and contains anion
The ternary and quadripolymer of group, it is constant to control other experimental conditions, measurement result such as the following table 3.
According to above test method, a series of polymerizations containing different anions group content will be synthesized in laboratory
The theoretical cationic degree and actual measurement cationic degree of object compare, and go out looking into for the modifying factor of cationic degree by data analysis and summary
Ask chart.
The cationic degree measurement result of the different cationic polymer of table 3
Note: DMD-AM is dimethyl diallyl trimethyl ammonium chloride-acrylamide bipolymer；AMPTA-AM-
AMPS is acrylamidopropyl trimethyl ammonium chloride-acrylamide -2- acrylamide-2-methyl propane sulfonic terpolymer；
AMPTA-AM-AMPS-AA is acrylamidopropyl trimethyl ammonium chloride-acrylamide -2- acrylamide -2- methyl-prop sulphur
Acid-acrylic acid quadripolymer.
Comparative example 1
This comparative example is that (sulfonic group molar content 30%, AS are propylene to argentometry measurement terpolymer AMPTA-AM-AS
Sodium sulfonate) cationic degree, concrete operation step are as follows:
Sample 0.2g (being accurate to 0.0001g) after purifying is weighed, is placed in the beaker of dried and clean.50mL distillation is added
Water stirs sufficiently dissolution.It needs to be added 30% hydrogen peroxide of 1mL and 2-3 drop dust technology (1:1), is heated at 70 DEG C~80 DEG C
10min is cooled to room temperature after fully degraded, is adjusted pH value to neutral or alkalescent, dilution with sodium hydroxide solution and is settled to
100mL accurately pipettes 25mL solution, the potassium chromate solution of~10 drop 50g/L of 8 drop is added, under abundant shake, with nitric acid silver label
Quasi- solution is titrated, and solution is become just occurring brick-red, as terminal from glassy yellow, while doing blank test.Cationic degree
It is calculated as follows:
In formula (4):
AIt is real--- the actual measurement cationic degree of synthetic polymer, unit are mM every gram (mmol/g)；
M(Cl-)——Cl-Content, unit is mM every gram (mmol/g)；
M --- sample mass is weighed, unit is gram (g)；
The concentration of C --- silver nitrate standard solution, unit are mole every liter (moL/L)；
V1--- the volume of consumption silver nitrate standard solution, unit are milliliter (mL)；
V0--- blank test consumes the volume of silver nitrate standard solution, and unit is milliliter (mL).
Comparative example 2
This comparative example is the sun of colloid titration terpolymer AMPTA-AM-AS (sulfonic group molar content 30%)
Ion degree, concrete operation step are as follows:
Accurately weighing 0.01g, (cationic polymer after claiming the quasi- purification to 0.0001g), is added the dissolution of 50mL distilled water
4h with 50mL distilled water flushing, and is transferred in 250mL conical flask, and being adjusted to pH value with 0.5mol/L hydrochloric acid solution is 3.0,
2~3 drop TBO indicator are added dropwise, then titrate (rate of titration 2mL/ with 0.0025mol/L potassium polyvinyl sulfate (PVSK) solution
Min), when solution colour becomes darkviolet from blue and keeps 10 seconds constant, as terminals；Liquid is titrated consumed by record
Product, while doing blank test.
Actual measurement cationic degree is calculated as follows:
In formula (5):
AIt is real--- the actual measurement cationic degree of synthetic polymer, unit are mM every gram (mmol/g)；
C --- PVSK concentration of standard solution, unit are mole every liter (moL/L)；
V1--- PVSK standard solution volume consumed by titration sample, unit are milliliter (mL)；
V2--- PVSK standard solution volume consumed by titration blank sample, unit are milliliter (mL).
M --- the sample quality after purification, unit are gram (g).
Comparative example 3
This comparative example be phosphotungstic acid method measure terpolymer AMPTA-AM-AS (sulfonic group molar content 30%) sun from
Sub- degree, concrete operation step are as follows:
Sample 0.2g (being accurate to 0.0001g) after weighing purification, is placed in the beaker of dried and clean.50mL distillation is added
Water, stirring are completely dissolved.Need to be added 30% hydrogen peroxide of 1mL and 2-3 drop dilute hydrochloric acid (1:1), in 80 DEG C of heating 10min, wait fill
It is cooled to room temperature, is transferred in 250mL conical flask, and with 50mL distilled water flushing 2-3 times, flushing liquor pours into taper after dividing degradation
In bottle.PH to 3-4 is adjusted with 5mol/L hydrochloric acid solution ,~8 Congo red indicator of drop of 6 drop is added dropwise, is dripped with phosphotungstic acid standard solution
It is fixed, it generates after precipitating (no precipitating generates, and illustrates sample no cationic), is slowly titrated to red and completely disappears, solution is ethereal blue
Color is terminal.Actual measurement cationic degree is calculated as follows:
In formula (6):
AIt is real--- the actual measurement cationic degree of synthetic polymer, unit are mM every gram (mmol/g)；
C --- phosphotungstic acid molar concentration, unit are mole every liter (mol/L)；
V --- consumption phosphotungstic acid volume, unit are milliliter (mL)；
M --- the sample quality after purification, unit are gram (g).
By the improved Sodium Tetraphenylborate Method of the application and comparative example 1, comparative example 2 and comparative example 3 to the sun of terpolymer from
Sub- degree measured value and measurement deviation are compared.By table 4 the results show that for terpolymer, the silver content of the use of comparative example 1
The cationic degree measurement deviation for the phosphotungstic acid method that the colloid titration method and comparative example 3 that method, comparative example 2 use use is above this Shen
It please improve the measurement deviation of Sodium Tetraphenylborate Method.It can be seen that standard of the improved Sodium Tetraphenylborate Method of the application than other several methods
True property is higher.
The comparative situation of 4 several cation degree measuring method of table
Note: polymer is all made of pure water and sufficiently dissolves in four kinds of measuring methods.
5 molecular structure of embodiment tests the influence that cationic degree measures
Amphoteric ion polymer contains a certain number of anion-SO simultaneously3 2-Group and-COO-When group, with polymerization
There is relatively large deviation in the increase of anionic group molar content in object, tetraphenylboron sodium measuring method, as polymer-SO3 2-Group mole
Content is 20% ,-COO-When group molar content is 20%, Sodium Tetraphenylborate Method measurement deviation is up to 93%, it can be seen that, it uses
Sodium Tetraphenylborate Method has shown biggish inadaptability.For this purpose, the application using a certain amount of chemical treatments (salt) to yin from
Subbase group carries out electron screening, the repulsive interaction of removal or decrease anionic group to tetraphenyl borate radical ion, i.e., using in water
The middle appropriate inorganic salts (NaCl) of addition dissolve polymer, using common-ion effect and the flocculation of inorganic salts, to tetraphenylboron sodium
Measuring method is modified, to greatly reduce measurement deviation.Comparing result such as the following table 5:
The influence that 5 difference dosage NaCl of table measures quadripolymer cationic degree
By upper 5 data of table as it can be seen that using salt water dissolution polymer measurement gained cationic degree deviation (modifying factor) with nothing
The increase of machine salt dosage and the trend of being substantially reduced is presented, or even in polymer-SO3 2-Group molar content (5%) is lower, inorganic
When salt NaCl dosage is 10%, there is measurement overgauge, the impurity K that overgauge contains in analysis level NaCl+, thus select
When selecting inorganic salts NaCl dosage, as polymer-SO3 2-Group molar content is lower, overgauge does not occur with cationic degree measured value
It is preferred, as polymer-SO3 2-When group molar content is higher, cationic degree measurement deviation is the smaller the better, therefore inorganic salts NaCl
Recommended density is 8%.
6 molecular weight of embodiment tests the influence that cationic degree measures
For AMPTA-AM binary cationic polymer, the hydrogen peroxide of not thermal-oxidative degradation mode and different dosages is respectively adopted
Thermal-oxidative degradation mode constantly reduces the molecular weight of polymer, and it is identical to control other experimental conditions, carries out cationic degree measurement.Knot
Fruit such as following table.
Cationic degree measured value compares under 6 degradation condition of table
As seen from the above table, in a certain range as hydrogen peroxide dosage increases, polymer solution apparent viscosity, which is presented, to be reduced
After tend towards stability trend, the presentation of polymer cation degree measured value is increased to the state of tending towards stability.Work as H2O2When dosage is 0mL, gather
Adduct molecule chain is crimped in a random ball of string, and interior includes many cationic units as precipitating together coprecipitation coating is got off, and is not sent out
Raw abundant precipitation reaction, causes measurement result relatively low.Work as H2O2When dosage is 1.0mL, polymer solution apparent viscosity is down to substantially
Minimum, polymer cation degree measured value is maximum, illustrates that polymer is degradable at this time, polymer cation degree measurement knot
Fruit is also tended towards stability substantially, and cationic degree theoretical value comparative measurements deviation is less than 5%.It can be seen that taking thermal-oxidative degradation
Chemical means reduce polymer molecule quality, effectively increase the accuracy of measurement polymer cation degree.
7 elemental microanalysis method of embodiment verifies cationic degree theoretical value
For four kinds of cationic polymer samples of laboratory synthesis, the sun of sample is obtained by elemental analysis test method
Ion angle value, so that the cationic degree theoretical value with the calculating method that feeds intake is compared, the measured value size of the two is coincide substantially, because
The calculation method of this polymer cation topology degree value is accurate and reliable.Comparison result is as follows:
The calculating method that feeds intake of table 7 is compared with elemental microanalysis method experimental result
The test of 8 Accuracy Verification of embodiment
In chemical analysis processes, the accuracy of measurement is measured using measurement sample recovery of standard addition.Recovery of standard addition
Formula it is as follows: recovery of standard addition=(standardized sample measured value-Specimen Determination value) ÷ scalar quantity × 100%, test result are shown in
Following table.
The recovery of standard addition of 8 synthetic polymer cationic degree of table
By table 8 as it can be seen that with terpolymer AMPTA-AM-AA (AA molar content 30%) and (AS moles of AMPTA-AM-AS
Content 10%) it is research object, cetyl trimethylammonium bromide QAS is added, recovery of standard addition respectively reaches 92% He
Within the scope of 94.4%, the recovery of standard addition index 90%-110% for having reached analysis test request.
In conclusion technical solution of the present invention has the advantage that the present invention first to drilling fluid synthesizing cationic
Polymer carries out alcohol and elutes pure, exclusion external interference factor, then using salt water dissolution, hydrogen peroxide thermal-oxidative degradation means, Yi Jichuan
The property made proposes and establishes modifying factor template, ensure that tetraphenylboron sodium back titration has higher accuracy, is widely applicable in
Property, stronger operability can promote and apply in conventional detection laboratory.
The above is only a preferred embodiment of the present invention, it is noted that for making the professional technique of the art
Personnel are that by various modifications to these embodiments without departing from the technical principles of the invention, and these
Modification also should be regarded as the range that the present invention should protect.
Claims (9)
1. a kind of detection method of the cationic degree of drilling fluid synthetic polymer, comprising the following steps:
By cationic polymer sample with ethanol purified solution, then with sample after sodium-chloride water solution dissolution purification, sample is obtained
Product aqueous solution；Sample aqueous solution described in 1wt% is controlled in 25 ± 3 DEG C of apparent viscosity≤10mPas；
Using tetraphenylboron sodium back titration, the sample aqueous solution of the apparent viscosity≤10mPas is detected, season is obtained
The total content of ammonium salt cation and potassium ion；It detects to obtain potassium content using ashing method, calculates the quaternary ammonium salt cationic
With the total content of potassium ion and the difference of potassium content, actual measurement cationic degree is obtained.
2. detection method according to claim 1, which is characterized in that by cationic polymer sample concentration be 90%~
95% ethanol solution carries out washing purification.
3. detection method according to claim 1, which is characterized in that sulfonic group molar content in the cationic polymer
It is 0~25%, carboxyl molar content is 0~70%, is greater than the 0 sodium-chloride water solution dissolution less than 10% using mass fraction and mentions
Sample after pure.
4. detection method according to claim 3, which is characterized in that further include: by actual measurement cationic degree and theoretical value ratio
Compared with calculating, cationic degree measurement deviation is obtained；According to different anions base in cationic degree measurement deviation and cationic polymer
The relationship of mass contg using mathematics Datafit software and MATLAB software, and uses index coordinates axis, polynary non-by being fitted
Linear equation establishes modifying factor template, is modified to actual measurement cationic degree, obtains cationic degree true value.
5. detection method according to claim 4, which is characterized in that the cationic degree true value AVery=actual measurement cation
Spend AIt is real× (1+ modifying factor t), 0≤t < 1.
6. described in any item detection methods according to claim 1~5, which is characterized in that after the purification sample aqueous solution in
25 ± 3 DEG C of apparent viscosity > 10mPas carries out thermal-oxidative degradation to sample with oxidant, obtains apparent viscosity≤10mPas
Sample aqueous solution.
7. detection method according to claim 6, which is characterized in that oxidant used in the sample thermal-oxidative degradation was
Hydrogen oxide, ozone, Peracetic acid or sodium hypochlorite.
8. detection method according to claim 7, which is characterized in that the oxidant uses mass concentration for 30~40%
Hydrogen peroxide, dosage be 0.25~2mL.
9. detection method according to claim 8, which is characterized in that the sample thermal-oxidative degradation process specifically: mentioning
Hydrochloric acid and hydrogen peroxide is added after pure in sample aqueous solution, is heated to 85~90 DEG C of 10~15min of constant temperature, obtain apparent viscosity≤
The sample aqueous solution of 10mPas.
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| CN111812088A (en) * | 2020-07-14 | 2020-10-23 | 杭州格林达电子材料股份有限公司 | Method for accurately detecting content of quaternary ammonium salt cations in alkaline wastewater |
| CN114113460A (en) * | 2021-11-05 | 2022-03-01 | 南京大学 | Detection method for density of quaternary ammonium group on outer surface of quaternary ammonium resin |
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| CN111812088A (en) * | 2020-07-14 | 2020-10-23 | 杭州格林达电子材料股份有限公司 | Method for accurately detecting content of quaternary ammonium salt cations in alkaline wastewater |
| CN114113460A (en) * | 2021-11-05 | 2022-03-01 | 南京大学 | Detection method for density of quaternary ammonium group on outer surface of quaternary ammonium resin |
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