CN110346330A - A kind of pH value detection method based on responsiveness thin-film material - Google Patents
A kind of pH value detection method based on responsiveness thin-film material Download PDFInfo
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- CN110346330A CN110346330A CN201910601342.1A CN201910601342A CN110346330A CN 110346330 A CN110346330 A CN 110346330A CN 201910601342 A CN201910601342 A CN 201910601342A CN 110346330 A CN110346330 A CN 110346330A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
- C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/55—Specular reflectivity
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2438/00—Living radical polymerisation
- C08F2438/03—Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]
Abstract
The invention discloses a kind of pH value detection method based on responsiveness thin-film material, the pH value of buffer solution is adjusted first, with responsiveness thin-film material element in response, is soaked responsiveness thin-film material with different pH value；Then the reflectance spectrum for acquiring wetted areas, it is long to obtain reflectance signature spike；The matched curve of origin software is finally applied, pH value calculation formula is obtained, for calculating the pH value of solution to be measured.Material preparation process of the invention uses emulsion polymerization, and preparation process is simple, energy conservation and environmental protection；Detection method susceptibility is high simultaneously, speed is fast, precision is high, responsive materials are reusable, and testing result is not affected by environment to have huge application prospect.
Description
Technical field
The invention belongs to high molecular material application field more particularly to a kind of pH value detections based on responsiveness thin-film material
Method.
Background technique
Photonic crystal is a kind of medium by different refractivity periodic arrangement and micro-nano structure for being formed in space.Root
According to bragg's formula, photonic crystal reflectance signature spike is long directly proportional to average refraction index and lattice constant.Need to only it pass through
The refraction index or lattice constant for changing photon crystal material are that can reach the purpose of regulation photonic crystal structure color.In recent years
Photon crystal material receives extensive research, has delivered the tens of thousands of pieces of correlative theses at present.There is research by photon crystal material and sound
Answering property functional group combines, and realizes the preparation of photonic crystal sensors material, is that detection becomes with the color of photon crystal material
Amount, can be used for chemical substance detection field.In view of different degrees of ionization can be presented in carboxyl under different pH environments, by it
It is combined with photon crystal material, new application space may be brought in responsiveness detection field for photon crystal material.
Currently used pH value detection method is pH test paper or pH meter.However pH test paper is that disposably, can not repeat to make
With.Judgement pH value is compared to color by naked eye in pH test paper detection mode, determines that the examined personnel's subjective factor of result is dry
It disturbs, and is not particularly suited for the personnel such as anomalous trichromatism, colour blindness.In addition, pH test paper dips the color presented after liquid and uneven, usually it is in
The selection of the deeper phenomenon in the existing shallower intermediate region of fringe region, region will be impacted to result is determined.Meanwhile pH test paper
The color of presentation also suffers from temperature influence.Therefore, for the testing result of pH test paper vulnerable to interference, error is larger.PH meter measurement knot
Fruit is more accurate, but it is larger compared to pH test paper volume and weight, and using preceding need by deionized water clean, Duo Zhongbiao
Many more manipulations, the data such as the correction of quasi- pH value buffer solution are not easy to stablize, using the electrode of complex steps, and pH meter usually require into
The long-term maintenance of row carries out having certain limitation when the quick detection of a small amount of sample.Therefore how to be facilitated by routine use fast
Prompt, repeatable mode realizes that the detection of pH value is extremely important.
Summary of the invention
In view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to provide a kind of pH value inspection based on responsiveness thin-film material
Survey method.
The purpose of the present invention is achieved through the following technical solutions: a kind of pH value inspection based on responsiveness thin-film material
Survey method, comprising the following steps:
(1) pH value for adjusting buffer solution, obtains multiple and different pH value solution.
(2) with responsiveness thin-film material, element, the different pH value obtained with step (1) are thin by responsiveness in response
Membrane material soaks, and obtain corresponding to different pH value soaks film；
(3) wetted areas for soaking film for the different pH value of correspondence that acquisition step (2) obtains is in 300~1000nm wave band
Reflectance spectrum in range, the reflectance signature spike for obtaining corresponding to different pH value is long, fitting reflectance signature spike is long and pH value it
Between relation curve, obtain pH value calculation formula.
(4) responsiveness thin-film material is soaked with solution to be measured, the wetted areas for soaking film for acquiring solution to be measured exists
Reflectance spectrum in 300~1000nm wavelength band, it is long to obtain the corresponding reflectance signature spike of solution to be measured, passes through step (3)
In pH value calculation formula, the pH value of solution to be measured is calculated.
Responsiveness thin-film material in the step (2) is by Nanosize particle latex and carbon black particle containing carboxyl
And it removes water and is dried to obtain after silicon dioxide granule mixing；
The polymer nanocomposite core-shell particles latex is three-decker, and specially one layer of reversible addition of amphiphilic macromolecular is disconnected
Split the structure that chain transfer agents wrap up two layers of segmented copolymer latex；The polymer nanocomposite core-shell particles latex contains carboxyl,
It is prepared by adding amphiphilic macromolecular Reversible Addition Fragmentation Chain Transfer reagent technique after segmented copolymer latex；Wherein gather
The equal diameter of body for closing object nano core-shell particle is 100~350nm；
The segmented structure expression formula of the segmented copolymer latex are as follows: R-AAn1-b-Stn2-b-Xn3-b-Yn4-Z；Wherein, R
For isopropyl acidic group, acetate, 2- itrile group acetate or 2- glycine base；AAn1In, AA is methacrylic acid monomer units or third
Acrylic monomer unit, n1 are the average degree of polymerization of AA, n1=10~60；Stn2In, St is styrenic monomer units, and n2 is St's
Average degree of polymerization, n2=3~10；Xn3In, X is styrenic monomer units, methyl methacrylate monomer unit, methyl acrylate
Monomeric unit, acrylonitrile monomer unit or vinylnaphthalene monomers unit, n3 are the average degree of polymerization of X, n3=1000~10000；
Yn4In, Y is methyl acrylate monomer units, ethyl acrylate monomer units, n-butyl acrylate monomer unit, i-butyl
Ester monomer unit, tert-butyl acrylate monomeric unit or Isooctyl acrylate monomer monomeric unit, n4 are the average degree of polymerization of Y, n4=
1500-15000；Z is alkyl dithioesters, three monothioester of phenyl dithioesters, benzyl dithioesters or alkyl.
Further, the buffer solution in the step (1) is tris-HCI buffer, citric acid-
Sodium citrate buffer solution, phosphate buffer, acetic acid-sodium acetate buffer solution or borax-hydrochloride buffer.
Further, the responsiveness thin-film material in the step (2) is prepared by the following method to obtain:
(3.1) by the carbon black particle water dispersion of the Nanosize particle latex of 1~100 parts by weight and 0~10 parts by weight
The mixing of the silica aqueous dispersion of liquid and 0~100 parts by weight, stir process 1~60 minute, obtains mixture water dispersion
Liquid；
(3.2) the mixture aqueous dispersions water removal that step (3.1) obtains is dried to obtain responsiveness thin-film material.
Further, the silica aqueous dispersion solid content in the step (3.1) is 10~70%, wherein titanium dioxide
Silicon particle diameter is 10~350nm；Carbon black particle aqueous dispersions solid content in the step (3.1) is 0.01~10%,
Middle carbon black particle diameter is 5~100nm.
Further, the Nanosize particle latex is prepared by the following method to obtain:
(5.1) it takes the amphiphilic macromolecular Reversible Addition Fragmentation Chain Transfer reagent of 1~10 parts by weight to stir and is dissolved in 1~100
Macromolecular agent aqueous dispersions are formed in the water of parts by weight；
(5.2) the macromolecular agent aqueous dispersions and 10~10000 weight that the step of taking 1~100 parts by weight (5.1) obtains
The segmented copolymer latex of part and the X of 0~100 parts by weight are poured into reactor together；Reactor is warming up to 60~80 DEG C,
It is kept stirring, continues letting nitrogen in and deoxidizing 5 minutes or more；Then the water soluble starter of 0~0.1 parts by weight is added, causes polymerization 15
Nanosize particle latex is obtained after~120 minutes.
Further, the water soluble starter in the step (5.2) is azodiisobutyronitrile, azobisisoheptonitrile, mistake
Aoxidize dibenzoyl, tert-butyl hydroperoxide, potassium peroxydisulfate or ammonium persulfate.
Further, the segmented copolymer latex is prepared by the following method to obtain:
(7.1) stirring of the amphiphilic macromolecular Reversible Addition Fragmentation Chain Transfer reagents of 1~10 parts by weight is dissolved in 100~
Water phase is formed in the water of 10000 parts by weight, then is mutually poured into reactor and stirred together with the oil being made of 10~1000 parts by weight X
Mixing；Temperature of reactor is risen to 60~80 DEG C, is kept stirring, letting nitrogen in and deoxidizing 5 minutes or more, 0.01~0.2 parts by weight are added
Water soluble starter, reaction 1~20 hour after, obtain R-AAn1-b-Stn2-b-Xn3- Z polymer emulsion；
(7.2) Y of 10~1000 parts by weight is added in the polymer emulsion that step (7.1) obtains, reacts 1~20 hour
Afterwards, it adds the Y of 10~1000 parts by weight and the crosslinking agent of 0~30 parts by weight obtains R- after the reaction was continued 1~20 hour
AAn1-b-Stn2-b-Xn3-b-Yn4- Z segmented copolymer latex.
Further, the water soluble starter in the step (7.1) is azodiisobutyronitrile, azobisisoheptonitrile, mistake
Aoxidize dibenzoyl, tert-butyl hydroperoxide, potassium peroxydisulfate or ammonium persulfate；Crosslinking agent in the step (7.2) is diethyl
Alkenyl benzene, 1,4-butanediol diacrylate, dipropylene glycol diacrylate, ethylene glycol diacrylate, 1,6- hexylene glycol two
Acrylate, diethylene glycol diacrylate, tripropylene glycol diacrylate, tri (propylene glycol) diacrylate or dimethyl
Acrylic acid glycol ester.
Further, the general formula of the chemical structure of the amphiphilic macromolecular Reversible Addition Fragmentation Chain Transfer reagent are as follows:
Wherein, Z is carbon atom number two alkylthio group, alkyl, phenyl or benzyl from four to ten；In Stn2, St is styrene
Monomeric unit, n2 are the average degree of polymerization of St, n2=3~10；In AAn1, AA be methacrylic acid or acrylic monomer units,
N1 is the average degree of polymerization of AA, n1=10~60；R is isopropyl acidic group, acetate, 2- itrile group acetate or 2- glycine base.
Further, the amphiphilic macromolecular Reversible Addition Fragmentation Chain Transfer reagent be the following chemical structure formula (I),
One of (II):
The beneficial effects of the present invention are:
1, the present invention has the characteristics that fast and easy, high-precision, and without artificial comparison colour atla, testing result is not by temperature etc.
Such environmental effects have great application value.
2, the responsiveness thin-film material in the present invention is substantially photon crystal material, the reflectance signature of photon crystal material
Spike is long to be positively correlated with lattice constant, while the material internal contains carboxyl, can absorb moisture, internal carboxyl is with pH value liter
Height generation ionization, which forms osmotic pressure, causes material to absorb water, and pH value is bigger, and the bigger water absorption of carboxyl degree of ionization is more, photonic crystal
Material lattice constant is bigger, and reflectance signature spike length is also bigger, therefore is fitted the long relationship between pH value of reflectance signature spike
Curve simultaneously show that pH value calculation formula can be used in detecting pH value；The material internal carboxyl-content is low (< 5wt%), therefore detects
Required amount of solution to be measured is few, and cleaned after the materials'use with clear water dry save it is reusable, it is easy to use, be easy to protect
It deposits.
3, the preparation method of polymer nano-particle selects reversible addition fracture in the responsiveness thin-film material in the present invention
Chain tra nsfer emulsion polymerization, this method energy conservation and environmental protection, simple process, suitable monomers are wide, are conducive to be widely applied, and be prepared
Latex particle size uniformity, stable structure.
Detailed description of the invention
Fig. 1 is the R-AA that the embodiment of the present invention 1 obtainsn1-b-Stn2-b-Stn3-nBAn4- b-Z segmented copolymer latex
GPC curve synoptic diagram；
Fig. 2 is that the transmission electron microscope photo for the three one polymer nano core-shell particles that the embodiment of the present invention 1 obtains is shown
It is intended to；
Fig. 3 is visible reflectance spectrum of the obtained thin-film material of the embodiment of the present invention 1 in different pH value buffer solutions
Variation diagram；
Fig. 4 be reflectance signature spike of the obtained thin-film material of the embodiment of the present invention 1 in different pH value buffer solutions it is long-
PH value standard curve；
Fig. 5 is the reflection spectrum curve when thin-film material that the embodiment of the present invention 1 obtains detects unknown solution pH value；
Fig. 6 is the obtained thin-film material elongation at break of the embodiment of the present invention 2 with polyacrylic acid in polymer nano-particle
The curve graph of N-butyl changes of contents.
Specific embodiment
A kind of pH value detection method based on responsiveness thin-film material of the present invention, comprising the following steps:
(1) with responsiveness thin-film material element in response, the pH value of buffer solution is adjusted, with buffer solution by responsiveness
Thin-film material soaks；The buffer solution is trishydroxymethylaminomethane-hydrochloric acid (Tris-HCl) buffer, citric acid-lemon
Lemon acid sodium buffer, phosphate buffer, acetic acid-sodium acetate buffer solution or borax-hydrochloride buffer.
The responsiveness thin-film material is by the polymer nano-particle containing carboxyl and carbon black particle and silica
Particle is removed water after being blended and is dried to obtain.The polymer nano-particle contains carboxyl, by adding two after segmented copolymer latex
Parent's property macromolecular Reversible Addition Fragmentation Chain Transfer reagent technique is prepared, which forms latex in water,
Particle is averaged the equal diameter of body as 100~350nm.The wherein segmented structure expression formula of segmented copolymer latex are as follows: R-AAn1-b-
Stn2-b-Xn3-b-Yn4-Z；Wherein, R is isopropyl acidic group, acetate, 2- itrile group acetate or 2- glycine base；AAn1In, AA
For methacrylic acid monomer units or acrylic monomer units, n1 is the average degree of polymerization of AA, n1=10~60；Stn2In, St is
Styrenic monomer units, n2 are the average degree of polymerization of St, n2=3~10；Xn3In, X is styrenic monomer units, methacrylic acid
Methylmethacrylate monomer unit, methyl acrylate monomer units, acrylonitrile monomer unit or vinylnaphthalene monomers unit, n3 are being averaged for X
The degree of polymerization, n3=1000~10000；Yn4In, Y be methyl acrylate monomer units, ethyl acrylate monomer units, acrylic acid just
Butyl ester monomeric unit, isobutyl acrylate monomeric unit, tert-butyl acrylate monomeric unit or Isooctyl acrylate monomer monomeric unit,
N4 is the average degree of polymerization of Y, n4=1500-15000；Z be alkyl dithioesters, phenyl dithioesters, benzyl dithioesters or
Three monothioester of alkyl；
Segmented copolymer latex is synthesized using reversible addition fragmentation chain emulsion polymerization method, is included the following steps:
(1.1) stirring of the amphiphilic macromolecular Reversible Addition Fragmentation Chain Transfer reagents of 1~10 parts by weight is dissolved in 100~
Water phase is formed in the water of 10000 parts by weight, then is mutually poured into reactor and stirred together with the oil being made of 10~1000 parts by weight X
Mixing.Temperature of reactor is risen to 60~80 DEG C, is kept stirring, letting nitrogen in and deoxidizing 5 minutes or more, 0.01~0.2 parts by weight are added
Water soluble starter, reaction 1~20 hour after, obtain R-AAn1-b-Stn2-b-Xn3- Z polymer emulsion；
The general formula of the chemical structure of amphiphilic macromolecular Reversible Addition Fragmentation Chain Transfer reagent in above-mentioned steps (1.1) are as follows:
Wherein, St is styrenic monomer units, and AA is methacrylic acid or acrylic monomer units, Z be carbon atom number from
Four to ten two alkylthio group, alkyl, phenyl or benzyl, R are isopropyl acidic group, acetate, 2- itrile group acetate or 2- glycine
Base；N1 is the average degree of polymerization of AA, n1=10~60；N2 is the average degree of polymerization of St, n2=3~10.
Water soluble starter in above-mentioned steps (1.1) includes but is not limited to azodiisobutyronitrile, azobisisoheptonitrile, mistake
Aoxidize dibenzoyl, tert-butyl hydroperoxide, potassium peroxydisulfate, ammonium persulfate.
(1.2) Y of 10~1000 parts by weight is added in the latex that step (1.1) obtains, after reaction 1~20 hour, then
The crosslinking agent of Y and 0~30 parts by weight that 10~1000 parts by weight are added obtain R-AA after the reaction was continued 1~20 hourn1-b-
Stn2-b-Xn3-b-Yn4- Z segmented copolymer latex.
Crosslinking agent in above-mentioned steps (1.2) includes but is not limited to divinylbenzene, 1,4 butanediol diacrylate, two
Propylene glycol diacrylate, ethylene glycol diacrylate, 1,6- hexanediyl ester, diethylene glycol diacrylate, three
Propylene glycol diacrylate, tri (propylene glycol) diacrylate, ethylene glycol dimethacrylate.
It is prepared by adding amphiphilic macromolecular Reversible Addition Fragmentation Chain Transfer reagent technique after segmented copolymer latex
The step of to polymer nano-particle, is as follows:
(1.3) it takes the amphiphilic macromolecular Reversible Addition Fragmentation Chain Transfer reagent of 1~10 parts by weight to stir and is dissolved in 1~100
Macromolecular agent aqueous dispersions are formed in the water of parts by weight；
The general formula of the chemical structure of amphiphilic macromolecular Reversible Addition Fragmentation Chain Transfer reagent in above-mentioned steps (1.3) are as follows:
Wherein, St is styrenic monomer units, and AA is methacrylic acid or acrylic monomer units, Z be carbon atom number from
Four to ten two alkylthio group, alkyl, phenyl or benzyl, R are isopropyl acidic group, acetate, 2- itrile group acetate or 2- glycine
Base；N1 is the average degree of polymerization of AA, n1=10~60；N2 is the average degree of polymerization of St, n2=3~10.
The chemical structural formula of amphiphilic macromolecular Reversible Addition Fragmentation Chain Transfer reagent used in the embodiment of the present invention are as follows:
(1.4) the macromolecular agent aqueous dispersions and 10~10000 weight that the step of taking 1~100 parts by weight (1.3) obtains
The segmented copolymer latex of part and the X of 0~100 parts by weight are poured into reactor together；Reactor is warming up to 60~80 DEG C,
It is kept stirring, continues letting nitrogen in and deoxidizing 5 minutes or more；Then the water soluble starter of 0~0.1 parts by weight is added, causes polymerization 15
Polymer nano-particle is obtained after~120 minutes.
Water soluble starter in above-mentioned steps (1.4) includes but is not limited to azodiisobutyronitrile, azobisisoheptonitrile, mistake
Aoxidize dibenzoyl, tert-butyl hydroperoxide, potassium peroxydisulfate, ammonium persulfate.
Responsiveness thin-film material is total to by the polymer nano-particle containing carboxyl with carbon black particle and silicon dioxide granule
It removes water and is dried to obtain after mixed, step are as follows:
(1.5) by the Nanosize particle latex of 1~100 parts by weight and 0~10 parts by weight of carbon black per particle water dispersion liquid
And 0~100 parts by weight silica aqueous dispersion mixing, stir process 1~60 minute, obtain mixture aqueous dispersions；
(1.6) the mixture aqueous dispersions water removal that step (1.5) obtains is dried to obtain responsiveness thin-film material.
The silica aqueous dispersion solid content be 10~70%, wherein silicon dioxide granule diameter be 10~
350nm。
The carbon black particle aqueous dispersions solid content is 0.01~10%, and wherein carbon black particle diameter is 5~100nm.
(2) detect responsiveness thin-film material wetted areas in the case of different pH value in 300~1000nm wavelength band
Reflectance spectrum, be fitted reflectance signature spike length-pH value standard curve and pH value calculation formula using origin software；Response
Property thin-film material using it is rear with clear water clean dry save it is reusable；
(3) responsiveness thin-film material is soaked with unknown pH value solution, detects the anti-of responsiveness thin-film material wetted areas
Penetrate reflectance spectrum.It is compared by the long standard curve with (2) of reflectance signature spike and substitutes into pH value calculation formula, you can learn that not
Know the pH value of solution；
The monomer conversion respectively walked is measured by gravimetric method.
Design molecular weight is calculated by following formula:
Wherein, Mn,thRefer to the design value of polymer molecular weight at the end of each step is reacted, m is walked thus reacts the total of added monomer
Quality, x are conversion ratio, and [RAFT] is the substance of amphipathic Reversible Addition Fragmentation Chain Transfer reagent added before reaction starts
Amount, Mn,RAFTFor the molecular weight of amphipathic Reversible Addition Fragmentation Chain Transfer reagent.
The microstructure of thin-film material is characterized by Hitachi's SU-8010 scanning electron microscope.
The reflection spectrum curve of thin-film material is by Shimadzu (SHIMADZU) UV-2450 and Olympus (OLYMPUS)
USPM-RU spectrophotometer measurement obtains.
The mechanical stretch performance of thin-film material is tested by Zi Weike (Zwick/Roell) Z020 universal testing machine
It arrives.
The molecular weight characterization of polymer carries out on water generation (Waters) 1525-2414-717 gel permeation chromatograph,
Eluent is tetrahydrofuran, is corrected with Narrow distribution polystyrene standard specimen.
The partial size and particle diameter distribution of latex particle are tested in Malvern (Malvern) ZETASIZER 3000HAS particle size analyzer
Upper progress.
Polyalcohol emulsion particle pattern is characterized using JOEL JEMACRO-123 transmission electron microscope, and test voltage is
80kV。
Embodiment 1:
Step 1: amphiphilic macromolecular Reversible Addition Fragmentation Chain Transfer reagent (I) stirring of 1 parts by weight is dissolved in 1450 weights
Water phase is formed in amount part water, then is mutually poured into reactor and be stirred together with the oil being made of 120 parts by weight of styrene.It will be anti-
It answers device temperature to rise to 70 DEG C, is kept stirring, the potassium peroxydisulfate of 0.07 parts by weight is added in logical nitrogen after 30 minutes, react 10 hours
Afterwards, R-AA is obtainedn1-b-Stn2-b-Xn3- Z polymer emulsion.
Step 2: the first step is after reaction, the n-butyl acrylate monomer of 100 parts by weight is added, reacts 4.5 hours
Afterwards, the n-butyl acrylate of 120 parts by weight and the 1,4-butanediol diacrylate of 0 parts by weight are added, it is 5 small that the reaction was continued
When after obtain R-AAn1-b-Stn2-b-Stn3-b-nBAn4- Z polymer emulsion.
Step 3: taking the amphiphilic macromolecular Reversible Addition Fragmentation Chain Transfer reagent (I) of 1 parts by weight to stir is dissolved in 14 weight
Macromolecular agent aqueous dispersions are formed in the water of part.
Step 4: the macromolecular agent aqueous dispersions for taking the third step of 6 parts by weight to be prepared, second with 35 parts by weight
Walk the R-AA being preparedn1-b-Stn2-b-Stn3-b-nBAn4- Z polymer emulsion and the mixing of the styrene of 0.4 parts by weight add
Enter in reactor and is stirred.Temperature of reactor is risen to 70 DEG C, is kept stirring, 0.005 weight is added after 30 minutes in logical nitrogen
The potassium peroxydisulfate of part, reaction obtained polymer nano-particle after 1 hour.
Step 5: the carbon black grain for being 0.1% by the Nanosize particle latex of 10 parts by weight and the solid content of 4 parts by weight
The silica aqueous dispersion that sub- aqueous dispersions and the solid content of 0.6 parts by weight are 30% mixes, and stir process 10 minutes, obtains
To mixture aqueous dispersions；
Step 6: moisture is evaporated by the mixture aqueous dispersions that the 5th step obtains under the conditions of 30 DEG C, film material is obtained
Material.
Step 7: film is soaked by different pH value buffer solutions respectively, detection thin-film material wetted areas 300~
Reflectance spectrum in 1000nm wavelength band is fitted reflectance signature peak wavelength X-pH value standard curve using origin software, and
PH value calculation formula: pH=0.1256 λ -66.7 is obtained by origin software automatic Fitting
Step 8: the thin-film material is contacted with unknown pH value solution, the reflected light of the thin-film material wetted areas is detected
Spectrum, characteristic peak wavelength, which is compared substitution pH value calculation formula to standard curve, can obtain corresponding solution ph.
Test verifying: the pH meter for being PHS-3C with thunder magnetic company model carries out pH value detection to five kinds of solution to be measured, by pH
Meter testing result is compared with the pH value that the pH value calculation formula that the present invention is obtained by the 7th step calculates, as a result such as 1 institute of table
Show:
Table 1:pH value testing result
As it can be seen from table 1 the present invention is based on the testing result error of the pH value detection method of responsiveness thin-film material compared with
It is small；The present invention is convenient and efficient compared with pH meter, high compared with the accuracy of pH test paper.
As shown in Figure 1, the molecular weight of the first step and each block of second step polymerization process gradually increases, it was demonstrated that obtained block
Copolymer.
As shown in Fig. 2, the polymer nanocomposite core-shell particles that the 4th step obtains are with the formal distribution of micelle, average grain diameter exists
230 rans, particle morphology is good, and apparent nucleocapsid separated structure is presented in particle.Wherein the particle is dyed by ruthenic acid, shallowly
Form and aspect are polyacrylic acid N-butyl kernel；Dark is mutually polystyrene shell；Particle external surface should there are also third layer, by adsorbing
It is constituted in the amphiphilic macromolecular Reversible Addition Fragmentation Chain Transfer reagent of particle surface, containing carboxyl, but too due to carboxyl-content
Low (< 5wt%), therefore, it is difficult to observe directly third layer structure.However, being tried by macromolecular Reversible Addition Fragmentation Chain Transfer
Agent it is amphiphilic, it is possible to determine that after the reagent added can be adsorbed on segmented copolymer latex particle surface and form very thin carboxyl
Layer.It does not absorb water after segmented copolymer latex particle simple simultaneously is dry, thus according to the suction of the photon crystal material in Fig. 3
Water-responsive characteristic can illustrate that the material also contains one layer of carboxyl layer, it was demonstrated that segmented copolymer latex particle surface, which exists, contains carboxylic
The third layer structure of base.
As shown in figure 3, there are apparent reflectance signature peaks for the thin-film material, it is photonic crystal character.With solution ph by
2.3 increase to 12.7, and obvious red shift occurs for the visible reflectance spectrum characteristic peak of the thin-film material, and wavelength is moved to by 560nm
640nm can be determined that material internal contains carboxyl by thin-film material absorbent solution, and as pH value increases electricity occurs for internal carboxyl
Material is caused to absorb water from osmotic pressure is formed, pH value is bigger, and water absorption is more, and photon crystal material lattice constant is bigger, therefore reflects
Characteristic peak wavelength is also bigger.
As shown in figure 4, the thin-film material reflectance signature spike is long, there are quantitative correlations with solution ph, with solution ph
Increase, characteristic peak wavelength increases, which can be used as standard curve, the pH value calculation formula being fitted: pH value=0.1256
× wavelength -66.7.
As shown in figure 5, the thin-film material and unknown pH value solution wetted areas characteristic peak wavelength are 609nm, pH value is substituted into
Calculation formula show that solution ph is 9.8.
Embodiment 2:
Step 1: amphiphilic macromolecular Reversible Addition Fragmentation Chain Transfer reagent (I) stirring of 2 parts by weight is dissolved in 5000 weights
It measures and forms water phase in the water of part, then mutually pour into reactor and be stirred together with the oil being made of 500 parts by weight of styrene.It will
Temperature of reactor rises to 70 DEG C, is kept stirring, and the potassium peroxydisulfate of 0.15 parts by weight is added in logical nitrogen after 30 minutes, and reaction 9.5 is small
Shi Hou obtains R-AAn1-b-Stn2-b-Xn3- Z polymer emulsion.
Step 2: the first step is after reaction, the n-butyl acrylate monomer of 340 parts by weight is added, reacts 5.5 hours
Afterwards, the n-butyl acrylate of 430 parts by weight and the 1,4-butanediol diacrylate of 10 parts by weight are added, the reaction was continued 6
R-AA is obtained after hourn1-b-Stn2-b-Stn3-b-nBAn4- Z polymer emulsion.
Step 3: taking the amphiphilic macromolecular Reversible Addition Fragmentation Chain Transfer reagent (I) of 2 parts by weight to stir is dissolved in 56 weight
Macromolecular agent aqueous dispersions are formed in the water of part.
Step 4: the macromolecular agent aqueous dispersions for taking the third step of 24 parts by weight to be prepared, with 75 parts by weight
The R-AA that two steps are preparedn1-b-Stn2-b-Stn3-b-nBAn4- Z polymer emulsion and the mixing of the styrene of 0.8 parts by weight
It is added in reactor and is stirred.Temperature of reactor is risen to 70 DEG C, is kept stirring, 0.01 weight is added after 30 minutes in logical nitrogen
The potassium peroxydisulfate of part, reaction obtained polymer nano-particle after 1.5 hours.
Step 5: the carbon black for being 0.04% by the Nanosize particle latex of 10 parts by weight and the solid content of 1 parts by weight
The silica aqueous dispersion that particle water dispersion liquid and the solid content of 1 parts by weight are 20% mixes, and stir process 20 minutes, obtains
To mixture aqueous dispersions；
Step 6: moisture is evaporated by the mixture aqueous dispersions that the 5th step obtains under the conditions of 35 DEG C, film material is obtained
Material.
Step 7: film is soaked by different pH value buffer solutions respectively, detection thin-film material wetted areas 300~
Reflectance spectrum in 1000nm wavelength band is fitted reflectance signature spike length-pH value standard curve using origin software, and logical
It crosses origin software automatic Fitting and obtains pH value calculation formula.
Step 8: the thin-film material is contacted with unknown pH value solution, the reflectance spectrum of the thin-film material is detected, will be reflected
Characteristic peak wavelength, which compares substitution pH value calculation formula to standard curve, can obtain corresponding solution ph.
As shown in fig. 6, the thin film material mechanics performance can be regulated and controled according to practical application, in polymer nano-particle
For polyacrylic acid N-butyl content by 52% to 68%, elongation at break can rise to 96% by 20%.
The molecular weight of the first step and each block of second step polymerization process gradually increases, it was demonstrated that has obtained block copolymer.
The polymer nanocomposite core-shell particles that 4th step obtains with the formal distribution of micelle, average grain diameter in 250 rans,
Particle morphology is good, and apparent nucleocapsid separated structure is presented in particle.Particle external surface should there are also third layer, by being adsorbed on particle
The amphiphilic macromolecular Reversible Addition Fragmentation Chain Transfer reagent on surface is constituted, containing carboxyl, but due to the too low (< of carboxyl-content
5wt%), therefore, it is difficult to observe directly third layer structure.However, passing through the double of macromolecular Reversible Addition Fragmentation Chain Transfer reagent
Parent's property, it is possible to determine that after the reagent added can be adsorbed on segmented copolymer latex particle surface and form very thin carboxyl layer.Together
It does not absorb water after the segmented copolymer latex particle of Shi Danchun is dry, thus the water suction response characteristic of the photon crystal material can
Illustrate that the material also contains one layer of carboxyl layer, it was demonstrated that segmented copolymer latex particle surface has the third layer knot containing carboxyl
Structure.
Embodiment 3:
Step 1: amphiphilic macromolecular Reversible Addition Fragmentation Chain Transfer reagent (I) stirring of 5 parts by weight is dissolved in 9000 weights
It measures and forms water phase in the water of part, then mutually pour into reactor and be stirred together with the oil being made of 1000 parts by weight of styrene.
Temperature of reactor is risen to 70 DEG C, is kept stirring, the potassium peroxydisulfate of 0.2 parts by weight is added in logical nitrogen after 30 minutes, reaction 9.5 is small
Shi Hou obtains R-AAn1-b-Stn2-b-Xn3- Z polymer emulsion.
Step 2: the first step is after reaction, the n-butyl acrylate monomer of 850 parts by weight is added, reacts 5.5 hours
Afterwards, the n-butyl acrylate of 1000 parts by weight and the 1,4-butanediol diacrylate of 30 parts by weight are added, the reaction was continued 7
R-AA is obtained after hourn1-b-Stn2-b-Stn3-b-nBAn4- Z polymer emulsion.
Step 3: taking the amphiphilic macromolecular Reversible Addition Fragmentation Chain Transfer reagent (II) of 10 parts by weight to stir is dissolved in 98 weights
It measures and forms macromolecular agent aqueous dispersions in the water of part.
Step 4: the macromolecular agent aqueous dispersions for taking the third step of 1 parts by weight to be prepared, second with 10 parts by weight
Walk the R-AA being preparedn1-b-Stn2-b-Stn3-b-nBAn4- Z polymer emulsion and the mixing of the styrene of 0 parts by weight are added
It is stirred in reactor.Temperature of reactor is risen to 70 DEG C, is kept stirring, the mistake of 0 parts by weight is added in logical nitrogen after 30 minutes
Potassium sulfate, reaction obtained polymer nano-particle after 1 hour.
Step 5: being 0.3% carbon black particle by the Nanosize particle latex of 90 parts by weight and the solid content of 3 parts by weight
The silica aqueous dispersion that aqueous dispersions and the solid content of 10 parts by weight are 70% mixes, and stir process 20 minutes, obtains
Mixture aqueous dispersions；
Step 6: moisture is evaporated by the mixture aqueous dispersions that the 5th step obtains under the conditions of 50 DEG C, film material is obtained
Material.
Step 7: film is soaked by different pH value buffer solutions respectively, detection thin-film material wetted areas 300~
Reflectance spectrum in 1000nm wavelength band is fitted reflectance signature spike length-pH value standard curve using origin software, and logical
It crosses origin software automatic Fitting and obtains pH value calculation formula.
Step 8: the thin-film material is contacted with unknown pH value solution, the reflectance spectrum of the thin-film material is detected, will be reflected
Characteristic peak wavelength, which compares substitution pH value calculation formula to standard curve, can obtain corresponding solution ph.
The molecular weight of the first step and each block of second step polymerization process gradually increases, it was demonstrated that has obtained block copolymer.
The polymer nanocomposite core-shell particles that 4th step obtains with the formal distribution of micelle, average grain diameter in 190 rans,
Particle morphology is good, and apparent nucleocapsid separated structure is presented in particle.Particle external surface should there are also third layer, by being adsorbed on particle
The amphiphilic macromolecular Reversible Addition Fragmentation Chain Transfer reagent on surface is constituted, containing carboxyl, but due to the too low (< of carboxyl-content
5wt%), therefore, it is difficult to observe directly third layer structure.However, passing through the double of macromolecular Reversible Addition Fragmentation Chain Transfer reagent
Parent's property, it is possible to determine that after the reagent added can be adsorbed on segmented copolymer latex particle surface and form very thin carboxyl layer.Together
It does not absorb water after the segmented copolymer latex particle of Shi Danchun is dry, thus the water suction response characteristic of the photon crystal material can
Illustrate that the material also contains one layer of carboxyl layer, it was demonstrated that segmented copolymer latex particle surface has the third layer knot containing carboxyl
Structure.
Embodiment 4:
Step 1: amphiphilic macromolecular Reversible Addition Fragmentation Chain Transfer reagent (I) stirring of 1 parts by weight is dissolved in 100 weights
It measures and forms water phase in the water of part, then mutually pour into reactor and be stirred together with the oil being made of 600 parts by weight of styrene.It will
Temperature of reactor rises to 70 DEG C, is kept stirring, and the potassium peroxydisulfate of 0.1 parts by weight is added in logical nitrogen after forty minutes, reacts 8 hours
Afterwards, R-AA is obtainedn1-b-Stn2-b-Xn3- Z polymer emulsion.
Step 2: the first step is after reaction, the n-butyl acrylate monomer of 10 parts by weight is added, after reaction 6.5 hours,
The n-butyl acrylate of 1000 parts by weight and the 1,4-butanediol diacrylate of 30 parts by weight are added, it is 7 small that the reaction was continued
When after obtain R-AAn1-b-Stn2-b-Stn3-b-nBAn4- Z polymer emulsion.
Step 3: taking the amphiphilic macromolecular Reversible Addition Fragmentation Chain Transfer reagent (I) of 10 parts by weight to stir is dissolved in 100 weights
It measures and forms macromolecular agent aqueous dispersions in the water of part.
Step 4: the macromolecular agent aqueous dispersions for taking the third step of 57 parts by weight to be prepared, with 350 parts by weight
The R-AA that two steps are preparedn1-b-Stn2-b-Stn3-b-nBAn4- Z polymer emulsion and the mixing of the styrene of 13 parts by weight add
Enter in reactor and is stirred.Temperature of reactor is risen to 70 DEG C, is kept stirring, 0.02 parts by weight are added after 30 minutes in logical nitrogen
Potassium peroxydisulfate, reaction 1.5 hours after obtain polymer nano-particle.
Step 5: the carbon black for being 10% by the Nanosize particle latex of 80 parts by weight and the solid content of 9.5 parts by weight
The silica aqueous dispersion that particle water dispersion liquid and the solid content of 0 parts by weight are 20% mixes, and stir process 20 minutes, obtains
To mixture aqueous dispersions；
Step 6: moisture is evaporated by the mixture aqueous dispersions that the 5th step obtains under the conditions of 40 DEG C, film material is obtained
Material.
Step 7: film is soaked by different pH value buffer solutions respectively, detection thin-film material wetted areas 300~
Reflectance spectrum in 1000nm wavelength band is fitted reflectance signature spike length-pH value standard curve using origin software, and logical
It crosses origin software automatic Fitting and obtains pH value calculation formula.
Step 8: the thin-film material is contacted with unknown pH value solution, the reflectance spectrum of the thin-film material is detected, will be reflected
Characteristic peak wavelength, which compares substitution pH value calculation formula to standard curve, can obtain corresponding solution ph.
The molecular weight of the first step and each block of second step polymerization process gradually increases, it was demonstrated that has obtained block copolymer.
The polymer nanocomposite core-shell particles that 4th step obtains with the formal distribution of micelle, average grain diameter in 270 rans,
Particle morphology is good, and apparent nucleocapsid separated structure is presented in particle.Particle external surface should there are also third layer, by being adsorbed on particle
The amphiphilic macromolecular Reversible Addition Fragmentation Chain Transfer reagent on surface is constituted, containing carboxyl, but due to the too low (< of carboxyl-content
5wt%), therefore, it is difficult to observe directly third layer structure.However, passing through the double of macromolecular Reversible Addition Fragmentation Chain Transfer reagent
Parent's property, it is possible to determine that after the reagent added can be adsorbed on segmented copolymer latex particle surface and form very thin carboxyl layer.Together
It does not absorb water after the segmented copolymer latex particle of Shi Danchun is dry, thus the water suction response characteristic of the photon crystal material can
Illustrate that the material also contains one layer of carboxyl layer, it was demonstrated that segmented copolymer latex particle surface has the third layer knot containing carboxyl
Structure.
Embodiment 5:
Step 1: amphiphilic macromolecular Reversible Addition Fragmentation Chain Transfer reagent (I) stirring of 3 parts by weight is dissolved in 6900 weights
It measures and forms water phase in the water of part, then mutually pour into reactor and be stirred together with the oil being made of 10 parts by weight of styrene.It will
Temperature of reactor rises to 70 DEG C, is kept stirring, and the potassium peroxydisulfate of 0.09 parts by weight is added in logical nitrogen after 30 minutes, and reaction 7.5 is small
Shi Hou obtains R-AAn1-b-Stn2-b-Xn3- Z polymer emulsion.
Step 2: the first step is after reaction, the n-butyl acrylate monomer of 1000 parts by weight is added, reacts 5.5 hours
Afterwards, the n-butyl acrylate of 10 parts by weight and the 1,4-butanediol diacrylate of 0 parts by weight are added, it is 6 small that the reaction was continued
When after obtain R-AAn1-b-Stn2-b-Stn3-b-nBAn4- Z polymer emulsion.
Step 3: taking the amphiphilic macromolecular Reversible Addition Fragmentation Chain Transfer reagent (I) of 3 parts by weight to stir is dissolved in 80 weight
Macromolecular agent aqueous dispersions are formed in the water of part.
Step 4: the macromolecular agent aqueous dispersions for taking the third step of 0 parts by weight to be prepared, with 160 parts by weight
The R-AA that two steps are preparedn1-b-Stn2-b-Stn3-b-nBAn4- Z polymer emulsion and the mixing of the styrene of 0.9 parts by weight
It is added in reactor and is stirred.Temperature of reactor is risen to 70 DEG C, is kept stirring, 0.01 weight is added after 30 minutes in logical nitrogen
The potassium peroxydisulfate of part, reaction obtained polymer nano-particle after 1 hour.
Step 5: being 0.8% carbon black particle by the Nanosize particle latex of 79 parts by weight and the solid content of 0 parts by weight
The silica aqueous dispersion that aqueous dispersions and the solid content of 100 parts by weight are 10% mixes, and stir process 30 minutes, obtains
Mixture aqueous dispersions；
Step 6: moisture is evaporated by the mixture aqueous dispersions that the 5th step obtains under the conditions of 55 DEG C, film material is obtained
Material.
Step 7: film is soaked by different pH value buffer solutions respectively, detection thin-film material wetted areas 300~
Reflectance spectrum in 1000nm wavelength band is fitted reflectance signature spike length-pH value standard curve using origin software, and logical
It crosses origin software automatic Fitting and obtains pH value calculation formula.
Step 8: the thin-film material is contacted with unknown pH value solution, the reflectance spectrum of the thin-film material is detected, will be reflected
Characteristic peak wavelength, which compares substitution pH value calculation formula to standard curve, can obtain corresponding solution ph.
The molecular weight of the first step and each block of second step polymerization process gradually increases, it was demonstrated that has obtained block copolymer.
The polymer nanocomposite core-shell particles that 4th step obtains with the formal distribution of micelle, average grain diameter in 180 rans,
Particle morphology is good, and apparent nucleocapsid separated structure is presented in particle.Particle external surface should there are also third layer, by being adsorbed on particle
The amphiphilic macromolecular Reversible Addition Fragmentation Chain Transfer reagent on surface is constituted, containing carboxyl, but due to the too low (< of carboxyl-content
5wt%), therefore, it is difficult to observe directly third layer structure.However, passing through the double of macromolecular Reversible Addition Fragmentation Chain Transfer reagent
Parent's property, it is possible to determine that after the reagent added can be adsorbed on segmented copolymer latex particle surface and form very thin carboxyl layer.Together
It does not absorb water after the segmented copolymer latex particle of Shi Danchun is dry, thus the water suction response characteristic of the photon crystal material can
Illustrate that the material also contains one layer of carboxyl layer, it was demonstrated that segmented copolymer latex particle surface has the third layer knot containing carboxyl
Structure.
The segmented structure expression formula of segmented copolymer latex in the embodiment of the present invention are as follows: R-AAn1-b-Stn2-b-Xn3-b-
Yn4-Z；Wherein, R is isopropyl acidic group, acetate, 2- itrile group acetate or 2- glycine base, and above-mentioned group property is similar, can
Play similar effects；In AAn1, AA is methacrylic acid monomer units or acrylic monomer units, and above-mentioned monomeric unit is parent
Aqueous monomer unit, property is similar, can play similar effects, and n1 is the average degree of polymerization of AA, n1=10~60；In Stn2, St is
Styrenic monomer units, n2 are the average degree of polymerization of St, n2=3~10；In Xn3, X is styrenic monomer units, metering system
Sour methylmethacrylate monomer unit, methyl acrylate monomer units, acrylonitrile monomer unit or vinylnaphthalene monomers unit, above-mentioned monomer list
First property is similar, can play similar effects, and n3 is the average degree of polymerization of X, n3=1000~10000；In Yn4, Y is acrylic acid first
Ester monomer unit, ethyl acrylate monomer units, n-butyl acrylate monomer unit, isobutyl acrylate monomeric unit, propylene
Tert-butyl acrylate monomeric unit or Isooctyl acrylate monomer monomeric unit, above-mentioned monomeric unit property is similar, can play similar effects, n4
For the average degree of polymerization of Y, n4=1500~15000；Z is alkyl dithioesters, phenyl dithioesters, benzyl dithioesters or alkane
Three monothioester of base, above-mentioned group property is similar, can play similar effects.
In the embodiment of the present invention water soluble starter used include but is not limited to azodiisobutyronitrile, azobisisoheptonitrile,
Dibenzoyl peroxide, tert-butyl hydroperoxide, potassium peroxydisulfate, ammonium persulfate, above compound property is similar, can play similar
Effect.
In the embodiment of the present invention crosslinking agent used include but is not limited to divinylbenzene, 1,4 butanediol diacrylate,
Dipropylene glycol diacrylate, ethylene glycol diacrylate, 1,6- hexanediyl ester, diethylene glycol diacrylate,
Tripropylene glycol diacrylate, tri (propylene glycol) diacrylate, ethylene glycol dimethacrylate, above compound property
It is similar, similar effects can be played.
Aqueous tenside used includes but is not limited to lauryl sodium sulfate, detergent alkylate in the embodiment of the present invention
Sodium sulfonate, polyethylene glycol, Tween 80, alkyl glycosides, lauric acid amide of ethanol, ethoxylated alkyl sulfate, lauramide
Propyl betaine, above compound property is similar, can play similar effects.
Buffer solution used is tris-HCI buffer, citric acid-citric acid in the embodiment of the present invention
Sodium buffer, phosphate buffer, acetic acid-sodium acetate buffer solution or borax-hydrochloride buffer, above-mentioned buffer property is similar, can
Play similar effects.
Claims (10)
1. a kind of pH value detection method based on responsiveness thin-film material, which comprises the following steps:
(1) pH value for adjusting buffer solution, obtains multiple and different pH value solution.
(2) with responsiveness thin-film material element in response, the different pH value that is obtained with step (1) is by responsiveness film material
Material soaks, and obtain corresponding to different pH value soaks film.
(3) wetted areas for soaking film for the different pH value of correspondence that acquisition step (2) obtains is in 300~1000nm wavelength band
Interior reflectance spectrum, the reflectance signature spike for obtaining corresponding to different pH value is long, and fitting reflectance signature spike is long between pH value
Relation curve obtains pH value calculation formula.
(4) responsiveness thin-film material is soaked with solution to be measured, acquire the wetted areas for soaking film of solution to be measured 300~
Reflectance spectrum in 1000nm wavelength band, it is long to obtain the corresponding reflectance signature spike of solution to be measured, passes through the pH in step (3)
It is worth calculation formula, the pH value of solution to be measured is calculated.
Responsiveness thin-film material in the step (2) by the Nanosize particle latex containing carboxyl and carbon black particle and
It removes water and is dried to obtain after silicon dioxide granule mixing；
The polymer nanocomposite core-shell particles latex is three-decker, and the reversible addition of specially one layer of amphiphilic macromolecular is broken chain
Transfering reagent wraps up the structure of two layers of segmented copolymer latex；The polymer nanocomposite core-shell particles latex contains carboxyl, passes through
Amphiphilic macromolecular Reversible Addition Fragmentation Chain Transfer reagent technique is added after segmented copolymer latex to be prepared；Wherein polymer
The equal diameter of the body of nano core-shell particle is 100~350nm；
The segmented structure expression formula of the segmented copolymer latex are as follows: R-AAn1-b-Stn2-b-Xn3-b-Yn4-Z；Wherein, R is different
Propionyloxy, acetate, 2- itrile group acetate or 2- glycine base；AAn1In, AA is methacrylic acid monomer units or acrylic acid
Monomeric unit, n1 are the average degree of polymerization of AA, n1=10~60；Stn2In, St is styrenic monomer units, and n2 is being averaged for St
The degree of polymerization, n2=3~10；Xn3In, X is styrenic monomer units, methyl methacrylate monomer unit, methacrylate monomer
Unit, acrylonitrile monomer unit or vinylnaphthalene monomers unit, n3 are the average degree of polymerization of X, n3=1000~10000；Yn4In,
Y is methyl acrylate monomer units, ethyl acrylate monomer units, n-butyl acrylate monomer unit, isobutyl acrylate list
Body unit, tert-butyl acrylate monomeric unit or Isooctyl acrylate monomer monomeric unit, n4 are the average degree of polymerization of Y, n4=1500-
15000；Z is alkyl dithioesters, three monothioester of phenyl dithioesters, benzyl dithioesters or alkyl.
2. the pH value detection method according to claim 1 based on responsiveness thin-film material, which is characterized in that the step
(1) buffer solution in is tris-HCI buffer, citric acid-sodium citrate buffer solution, phosphoric acid buffer
Liquid, acetic acid-sodium acetate buffer solution or borax-hydrochloride buffer.
3. the pH value detection method according to claim 1 based on responsiveness thin-film material, which is characterized in that the step
(2) the responsiveness thin-film material in is prepared by the following method to obtain:
(3.1) by the Nanosize particle latex of 1~100 parts by weight and the carbon black particle aqueous dispersions of 0~10 parts by weight with
And 0~100 parts by weight silica aqueous dispersion mixing, stir process 1~60 minute, obtain mixture aqueous dispersions；
(3.2) the mixture aqueous dispersions water removal that step (3.1) obtains is dried to obtain responsiveness thin-film material.
4. the pH value detection method according to claim 3 based on responsiveness thin-film material, which is characterized in that the step
(3.1) the silica aqueous dispersion solid content in is 10~70%, and wherein silicon dioxide granule diameter is 10~350nm；Institute
Stating the carbon black particle aqueous dispersions solid content in step (3.1) is 0.01~10%, and wherein carbon black particle diameter is 5~100nm.
5. the pH value detection method according to claim 1 based on responsiveness thin-film material, which is characterized in that the polymer
Nanoparticle latex is prepared by the following method to obtain:
(5.1) it takes the amphiphilic macromolecular Reversible Addition Fragmentation Chain Transfer reagent of 1~10 parts by weight to stir and is dissolved in 1~100 weight
Macromolecular agent aqueous dispersions are formed in the water of part；
(5.2) macromolecular agent aqueous dispersions that the step of taking 1~100 parts by weight (5.1) obtains and 10~10000 parts by weight
Segmented copolymer latex and the X of 0~100 parts by weight are poured into reactor together；Reactor is warming up to 60~80 DEG C, is kept
Stirring continues letting nitrogen in and deoxidizing 5 minutes or more；Then the water soluble starter of 0~0.1 parts by weight is added, causes polymerization 15~120
Nanosize particle latex is obtained after minute.
6. the pH value detection method according to claim 5 based on responsiveness thin-film material, which is characterized in that the step
(5.2) water soluble starter in is azodiisobutyronitrile, azobisisoheptonitrile, dibenzoyl peroxide, tert-butyl hydroperoxide
Hydrogen, potassium peroxydisulfate or ammonium persulfate.
7. the pH value detection method according to claim 1 based on responsiveness thin-film material, which is characterized in that the block is total
Polymers latex is prepared by the following method to obtain:
(7.1) the amphiphilic macromolecular Reversible Addition Fragmentation Chain Transfer reagent stirring of 1~10 parts by weight is dissolved in 100~10000
Water phase is formed in the water of parts by weight, then is mutually poured into reactor and be stirred together with the oil being made of 10~1000 parts by weight X；
Temperature of reactor is risen to 60~80 DEG C, is kept stirring, letting nitrogen in and deoxidizing 5 minutes or more, the water-soluble of 0.01~0.2 parts by weight is added
Property initiator, reaction 1~20 hour after, obtain R-AAn1-b-Stn2-b-Xn3- Z polymer emulsion；
(7.2) Y of 10~1000 parts by weight is added in the polymer emulsion that step (7.1) obtains, after reaction 1~20 hour,
It adds the Y of 10~1000 parts by weight and the crosslinking agent of 0~30 parts by weight obtains R-AA after the reaction was continued 1~20 hourn1-
b-Stn2-b-Xn3-b-Yn4- Z segmented copolymer latex.
8. the pH value detection method according to claim 7 based on responsiveness thin-film material, which is characterized in that the step
(7.1) water soluble starter in is azodiisobutyronitrile, azobisisoheptonitrile, dibenzoyl peroxide, tert-butyl hydroperoxide
Hydrogen, potassium peroxydisulfate or ammonium persulfate；Crosslinking agent in the step (7.2) is divinylbenzene, 1,4- butanediol diacrylate
Ester, dipropylene glycol diacrylate, ethylene glycol diacrylate, 1,6- hexanediyl ester, diethylene glycol diacrylate
Ester, tripropylene glycol diacrylate, tri (propylene glycol) diacrylate or ethylene glycol dimethacrylate.
9. the pH value detection method according to claim 1 based on responsiveness thin-film material, which is characterized in that described amphipathic
The general formula of the chemical structure of macromolecular Reversible Addition Fragmentation Chain Transfer reagent are as follows:
Wherein, Z is carbon atom number two alkylthio group, alkyl, phenyl or benzyl from four to ten；In Stn2, St is styrene monomer
Unit, n2 are the average degree of polymerization of St, n2=3~10；In AAn1, AA is methacrylic acid or acrylic monomer units, and n1 is
The average degree of polymerization of AA, n1=10~60；R is isopropyl acidic group, acetate, 2- itrile group acetate or 2- glycine base.
10. the pH value detection method according to claim 9 based on responsiveness thin-film material, which is characterized in that the amphiphilic
Property macromolecular Reversible Addition Fragmentation Chain Transfer reagent be one of the following chemical structure formula (I), (II):
。
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