CN112831007B - Self-repairing polyacrylate elastomer with multiphase structure and preparation method thereof - Google Patents
Self-repairing polyacrylate elastomer with multiphase structure and preparation method thereof Download PDFInfo
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- 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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- C—CHEMISTRY; METALLURGY
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C—CHEMISTRY; METALLURGY
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- 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 relates to a self-repairing polyacrylate elastomer with a multiphase structure and a preparation method thereof. The toughening of the polyacrylate elastomer can be realized by using a multiphase design with different carboxyl densities, and the self-repairing performance of the polyacrylate elastomer is not influenced. In addition, the resulting elastomer was transparent and strongly fluorescent under 365nm UV illumination and exhibited an Aggregate Enhanced Emission (AEE) profile.
Description
Technical Field
The invention belongs to the field of thermoplastic elastomers, and relates to a self-repairing polyacrylate elastomer with a multiphase structure and a preparation method thereof.
Background
Elastomers are used in a wide variety of applications in everyday products, medical and other engineering applications, and play an important role in various aspects of human life and production. However, they inevitably cause various damages and cracks during use, which form potential safety hazards and shorten the service life of the material to some extent. In the 80 s of the 19 th century, the concept of self-repairing was proposed, and since the basic performance of the material can be partially or completely recovered after mechanical damage, the self-repairing material becomes a novel intelligent material and is widely concerned. In the field of elastomers, elastomers having both self-healing capability and good mechanical properties have attracted great interest in both academic and industrial areas in order to meet the requirements of applications in various fields.
However, the self-repairing material generally utilizes the dynamic characteristics of low-bond-energy dynamic covalent bonds (Diels-Alder reaction, transesterification reaction, olefin metathesis, disulfide bond exchange, imine exchange, etc.) or some non-covalent bonds (such as hydrogen bonds, metal-ligand coordination, ion interaction, and pi-pi stacking) to realize self-repairing of the material, so the overall strength of the material is low. Therefore, for practical applications, there is a need to develop an elastomer having both excellent self-repairing ability and good mechanical properties.
Achieving reinforcement and toughening of elastomers generally requires a good crosslinking structure and a continuous energy absorption-dissipation mechanism in itself. According to the literature, microphase separation molecular structure design and reversible sacrificial bonds introduction are reported to be two effective methods for improving the strength and toughness of the elastomer, wherein the reversible sacrificial bonds can also endow the material with self-repairing capability. Gradient interaction commonly exists in natural biological materials such as spider silks, mussel feet and the like, and the materials are gradually dissociated in the forced deformation process to become sacrificial bonds, so that energy dissipation in the deformation process is allowed, and the overall mechanical performance of the materials is remarkably improved. Thus, the introduction of bio-inspired sacrificial bonds is a widely used strategy for elastomer toughening. The construction of the double-cross-linked network system proposed by Gong Jian Nu et al is also one of the most potential strategies in the aspect of polymer molecular structure design. One of the crosslinked networks maintains structural and shape stability while the other network dissipates energy. Furthermore, Naoko Yoshie et al propose a new design strategy to improve the toughness of elastomers by introducing physically cross-linked microphase-separated structures with different densities formed by the quadruple hydrogen bonding motifs 2-ureido-4 [1H ] -pyrimidinone (UPy). However, the poor solubility of UPy makes the whole preparation process more complicated, and greatly limits the practical application of the materials.
Disclosure of Invention
Technical problem to be solved
In order to avoid the defects of the prior art and combine the requirements of self-repairing materials on molecular composition, the invention provides a self-repairing polyacrylate elastomer with a multiphase structure and a preparation method thereof. The reinforcing and toughening of the self-repairing polyacrylate elastomer are realized by designing and preparing an ABA triblock copolymer, wherein blocks A at two ends of a molecular chain are poly (tert-butyl acrylate), a block B in the middle is a copolymer of n-butyl acrylate and tert-butyl acrylate, acid hydrolysis is carried out to convert tert-butyl ester groups into carboxyl groups, the interaction of hydrogen bonds formed by the carboxyl groups is used as a physical crosslinking point, the segmented design of the carboxyl groups leads the prepared polymer PAA-B-P (AA-r-nBA) -B-PAA to have different crosslinking densities along the molecular chain, the block A consisting of polyacrylic acid chain segments has high physical crosslinking density, can maintain the macroscopic shape of the material and obstruct the slippage of the molecular chain, and the block B has low crosslinking density and is mainly used for dissipating energy so as to realize the mechanical toughening of the material. High fracture toughness (77.06 MJ.m) was obtained-3) And high tensile strength (20.96 MPa). In addition, the invention uses common commercial monomers, thereby being more beneficial to practical application and popularization. The characteristics of transparent elastomer and fluorescence emission create the possibility for potential application in multiple fields.
Technical scheme
A self-repairing polyacrylate elastomer with a multiphase structure is characterized in that: the elastomer has a multiphase structure, the A blocks at two ends are polyacrylic acid, and the B block in the middle is a copolymer of n-butyl acrylate and acrylic acid; the elastomers exhibit fluorescent emission properties in solution and solid state when irradiated by an ultraviolet lamp, and enhance emission properties for aggregation in solution.
A method for preparing the self-repairing polyacrylate elastomer with the multiphase structure is characterized by comprising the following steps:
and 2, hydrolysis reaction of the copolymer: and (3) after purifying the purified copolymer obtained in the step (1), adding acid to react for 10-48 h, and precipitating the product by using deionized water.
The method for the controllable free radical polymerization comprises a nitrogen-oxygen stable free radical method, an atom transfer radical polymerization method ATRP or a reversible addition-fragmentation chain transfer method RAFT.
The inert gas is N2Or Ar.
The initiator is azobisisobutyronitrile AIBN, dibenzoyl peroxide BPO, azobisisoheptonitrile ABVN or dimethyl azobisisobutyrate AIBME.
The acid added in the step 2 is trifluoroacetic acid or hydrochloric acid.
The concentration range of the trifluoroacetic acid is 4.0-7.0 mol/L.
The concentration range of the hydrochloric acid is 0.7-1.5 mol/L.
Advantageous effects
The invention provides a self-repairing polyacrylate elastomer with a multiphase structure and a preparation method thereof.A ABA triblock butyl acrylate copolymer (copolymer P (tBA-r-nBA) with two end blocks of tert-butyl acrylate PtBA and a middle block of n-butyl acrylate (nBA) and tert-butyl acrylate (tBA)) is obtained through controllable free radical polymerization, acid hydrolysis is carried out to convert tert-butyl ester groups into carboxyl groups, and the interaction of hydrogen bonds formed by the carboxyl groups is used as a physical crosslinking point. The toughening of the polyacrylate elastomer can be realized by using a multiphase design with different carboxyl densities, and the self-repairing performance of the polyacrylate elastomer is not influenced. In addition, the resulting elastomer was transparent and strongly fluorescent under 365nm UV illumination and exhibited an Aggregate Enhanced Emission (AEE) profile.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention provides a self-repairing polyacrylate elastomer with a multiphase structure and a preparation method thereof, the design idea has better reference value in the reinforcing and toughening category of the acrylate thermoplastic elastomer, and the used raw materials are commercialized, cheap and easily available, and have the potential of large-scale production;
2. the overall performance of the elastomer material can be regulated and controlled by adjusting the length and the monomer composition ratio of a PAA-b-P (AA-r-nBA) -b-PAA triblock molecular chain: when the PAA chain segment length at the two ends of the molecular chain is increased in percentage of the whole molecular chain length or the acrylic acid content in the middle block is increased, the glass transition temperature of the polymer is increased, the tensile strength is increased, and the Young modulus is increased; on the contrary, when the PAA chain segment length at the two ends of the molecular chain is reduced in the whole molecular chain length percentage or the acrylic acid content in the middle block is reduced, the tensile strength of the polymer is reduced, the Young modulus is reduced, and the polymer is soft and easy to deform.
3. The elastomer prepared by the invention can be self-repaired at room temperature: after the sample is cut off in the gauge length, the section is contacted again and then placed at room temperature for 24 hours, and the tensile strength, the elongation at break and the toughness of the sample are respectively restored to 93 percent, 89 percent and 83 percent of the original values; has good mechanical properties: compared with a random copolymer P (AA-r-nBA) and a homoblock copolymer PAA-b-PnBA-b-PAA which do not have a phase-separation structure design, the PAA-b-P (AA-r-nBA) -b-PAA prepared by the invention has better mechanical properties (the tensile strength is 20.96MPa, and the toughness is 77.06 MJ.m.-3) Specifically, the fracture toughness of the PAA-b-P (AA-r-nBA) -b-PAA is improved by 16 percent compared with that of the P (AA-r-nBA); the fluorescent material has the property of fluorescence emission under the irradiation of an ultraviolet lamp, and has potential application prospect;
4. the self-repairing polyacrylate elastomer with the multiphase structure provided by the invention has abundant carboxyl groups and a large post-functionalization space, and provides a new idea for designing more high-performance polyacrylate elastomers with complex structures.
Drawings
FIG. 1: stress-strain curves for polyacrylate elastomers prepared with different block lengths/monomer charge ratios
FIG. 2: self-repairing test: (a) a tensile test photo of a polyacrylate elastomer Tri-ARA-1-4 sample strip after being cut in a gauge length and repaired for 24 hours at room temperature; (b) stress-strain curves of samples at different repair times at room temperature
FIG. 3: the photos of the solutions with different concentrations obtained by dissolving the polyacrylate elastomer in ethanol in the invention under sunlight and ultraviolet light
Detailed Description
The invention will now be further described with reference to the following examples and drawings:
the elastomer has a multiphase structure design, wherein the A blocks at two ends are polyacrylic acid, and the B block in the middle is a copolymer of n-butyl acrylate and acrylic acid. Because hydrogen bonds can be formed among carboxyl groups, the physical crosslinking densities of different blocks are different, the A block consisting of polyacrylic acid chain segments has high physical crosslinking density and can keep the macroscopic shape of the material and block the slippage of a molecular chain as a hard block, the B block has low crosslinking density and forms a soft matrix, and the loosely distributed hydrogen bonds mainly dissipate energy so as to realize the mechanical toughening of the material. The regulation and control of the mechanical property of the material can be realized by changing the length and the composition of the triblock molecular chain in the preparation process. The physical crosslinking formed by hydrogen bond interaction is distributed along the molecular chain of the polymer and has the characteristics of strong two ends and weak middle part.
Under the condition of no traditional chromophoric group, the elastomer shows stronger fluorescence emission property in both solution and solid states when irradiated by ultraviolet lamp. And exhibits an aggregation-enhanced emission effect in solution.
The preparation process of the self-repairing polyacrylate elastomer comprises the following steps: firstly, ABA triblock butyl acrylate copolymer PtBA-b-P (tBA-r-nBA) -b-tBA (two end blocks are poly tert-butyl acrylate, and a middle block is a copolymer of n-butyl acrylate and tert-butyl acrylate) is obtained through polymerization, and then acid hydrolysis reaction is carried out to convert tert-butyl ester group into carboxyl, thus obtaining PAA-b-P (AA-r-nBA) -b-PAA.
Example 1: preparation of self-repairing polyacrylate elastomer
Preparation of butyl acrylate copolymer using RAFT polymerisation: 0.1058g of the double headed RAFT reagent S, S ' -bis (. alpha.,. alpha. ' -dimethyl-. alpha. ' -acetic acid) trithiocarbonate (BDATC), 0.0308g of the initiator AIBN and 7.20g of tert-butyl acrylate tBA were first dissolved in 25mL of dioxane and transferred to an eggplant shaped flask equipped with a magnetic stirrer and an argon inlet. High purity argon was bubbled for 30 minutes after two freeze-thaw cycles on a high vacuum line. Polymerizing for 24 hours at 65 ℃, precipitating the poly (tert-butyl acrylate) macromolecular RAFT reagent, and drying for later use. Next, 0.4747g of the PtBA macroRAFT reagent prepared above was dissolved in 35mL of dioxane in a single-neck flask equipped with a magnetic stirrer and an argon inlet, and then 0.0039g of AIBN as an initiator, 12.63g of n-butyl acrylate nBA and 3.41g of tBA were added thereto, and after freezing and thawing twice, high-purity argon was bubbled into the reaction mixture at room temperature for 30 minutes, and after polymerization at 65 ℃ for 20 hours, the reaction was quenched to terminate, thereby obtaining a triblock copolymer PtBA-b-P (tBA-r-nBA) -b-PtBA. After polymerization, 11.65mL of concentrated hydrochloric acid was diluted with 85mL of dioxane and added to the polymerization system and refluxed at 90 ℃ overnight. Finally, the product was precipitated with deionized water. The elastomer obtained was dried in a forced air drying oven for 24 hours and then dried in a vacuum drying oven to a constant weight.
Example 2: preparation of self-repairing polyacrylate elastomer
Preparation of butyl acrylate copolymer using RAFT polymerisation: 0.1058g of the double headed RAFT reagent S, S ' -bis (. alpha.,. alpha. ' -dimethyl-. alpha. ' -acetic acid) trithiocarbonate (BDATC), 0.0308g of the initiator AIBN and 5.50g of tert-butyl acrylate tBA were first dissolved in 25mL of dioxane and transferred to an eggplant shaped flask equipped with a magnetic stirrer and an argon inlet. High purity argon was bubbled for 30 minutes after two freeze-thaw cycles on a high vacuum line. Polymerizing for 24 hours at 65 ℃, precipitating the poly (tert-butyl acrylate) macromolecular RAFT reagent, and drying for later use. Next, 0.4747g of the PtBA macroRAFT reagent prepared above was dissolved in 35mL of dioxane in a single-neck flask equipped with a magnetic stirrer and an argon inlet, and then 0.0038g of AIBN as an initiator, 10.01g of n-butyl acrylate nBA and 6.04g of tBA were added thereto, and after freezing and thawing twice, high-purity argon was bubbled into the reaction mixture at room temperature for 30 minutes, and after polymerization at 65 ℃ for 20 hours, the reaction was quenched to terminate, thereby obtaining a triblock copolymer PtBA-b-P (tBA-r-nBA) -b-PtBA. After polymerization, 9.75mL of concentrated hydrochloric acid was diluted with 65mL of dioxane and added to the polymerization system and refluxed at 90 ℃ overnight. Finally, the product was precipitated with deionized water. The elastomer obtained was dried in a forced air drying oven for 24 hours and then dried in a vacuum drying oven to a constant weight.
Example 3: preparation of self-repairing polyacrylate elastomer
Preparation of butyl acrylate copolymer using RAFT polymerisation: 0.1058g of the double headed RAFT reagent S, S ' -bis (. alpha.,. alpha. ' -dimethyl-. alpha. ' -acetic acid) trithiocarbonate (BDATC), 0.0308g of the initiator AIBN and 7.20g of tert-butyl acrylate tBA were first dissolved in 25mL of dioxane and transferred to an eggplant shaped flask equipped with a magnetic stirrer and an argon inlet. High purity argon was bubbled for 30 minutes after two freeze-thaw cycles on a high vacuum line. Polymerizing for 24 hours at 65 ℃, precipitating the poly (tert-butyl acrylate) macromolecular RAFT reagent, and drying for later use. Next, 0.4747g of the PtBA macroRAFT reagent prepared above was dissolved in 35mL of dioxane in a single-neck flask equipped with a magnetic stirrer and an argon inlet, and then 0.0039g of AIBN as an initiator, 12.63g of n-butyl acrylate nBA and 3.41g of tBA were added thereto, and after freezing and thawing twice, high-purity argon was bubbled into the reaction mixture at room temperature for 30 minutes, and after polymerization at 65 ℃ for 20 hours, the reaction was quenched to terminate, thereby obtaining a triblock copolymer PtBA-b-P (tBA-r-nBA) -b-PtBA. After the polymerization, the copolymer was precipitated, and a dioxane solution having a concentration of 6.5mol/L and containing 6.92g of trifluoroacetic acid as a solute was added thereto, and reacted at 30 ℃ for 48 hours. After the reaction is finished, the residual trifluoroacetic acid is dried in a spinning mode, and the product is precipitated by deionized water. The elastomer obtained was dried in a forced air drying oven for 24 hours and then dried in a vacuum drying oven to a constant weight.
Example 4: preparation of self-repairing polyacrylate elastomer
Preparation of butyl acrylate copolymer using RAFT polymerisation: 0.0529g of RAFT reagent 4-cyano-4- (thiobenzoylthio) pentanoic acid, 0.0308g of initiator AIBN and 3.60g of tert-butyl acrylate tBA were first dissolved in 50mL dioxane and transferred to an eggplant-shaped flask equipped with a magnetic stirrer and an argon inlet. High purity argon was bubbled for 30 minutes after two freeze-thaw cycles on a high vacuum line. Polymerizing for 24 hours at 65 ℃, precipitating the poly (tert-butyl acrylate) macromolecular RAFT reagent, and drying for later use. Then, 0.0039g of initiator AIBN, 12.03g of n-butyl acrylate nBA and 3.01g of tBA are added into the reaction bottle, high-purity argon is blown into the reaction mixture for 30 minutes at room temperature after two times of freezing and melting, and the reaction system is cooled to the room temperature after polymerization reaction for 24 hours at 65 ℃. And (3) adding 0.0035g of AIBN initiator and 3.60g of tBA into the reaction bottle, freezing and melting for two times, blowing high-purity argon gas into the reaction mixture for 30 minutes at room temperature, and carrying out polymerization reaction for 24 hours at 65 ℃ to obtain the triblock copolymer PtBA-b-P (tBA-r-nBA) -b-PtBA. After polymerization, 11.50mL of concentrated hydrochloric acid was diluted with 65mL of dioxane and added to the polymerization system and refluxed at 90 ℃ overnight. Finally, the product was precipitated with deionized water. The elastomer obtained was dried in a forced air drying oven for 24 hours and then dried in a vacuum drying oven to a constant weight.
Example 5: preparation of self-repairing polyacrylate elastomer
Preparation of butyl acrylate copolymer using the method of ATRP: first 42. mu.L of the initiator ethyl alpha-bromoisobutyrate, 0.0285g of cuprous chloride, 58. mu.L of the ligand Pentamethyldiethylenetriamine (PMDETA), 7.20g of tert-butyl acrylate tBA were dissolved in 25mL of dioxane and then transferred to a eggplant-shaped flask equipped with a magnetic stirrer. After three times of freeze-thaw cycle on a high vacuum line, polymerizing for 10 hours at 60 ℃, and precipitating out the tert-butyl polyacrylate macromolecular ATRP initiator to be dried for later use. Then, 4.47g of the prepared PtBA macromolecular ATRP initiator is taken and dissolved into 35mL of dioxane, 0.0542g of cuprous chloride, 110 mu L of PMDETA, 12.63g of n-butyl acrylate nBA and 3.41g of tBA are added into the initiator, and the initiator is polymerized for 10 hours at 60 ℃ after three times of freeze-thaw cycles, and then PtBA-b-P (tBA-r-nBA) is precipitated and dried for later use; subsequently, PtBA-b-P (tBA-r-nBA) obtained above, 0.0285g of cuprous chloride, 58. mu.L of ligand PMDETA and 7.20g of tert-butyl acrylate tBA were dissolved in 50mL of dioxane, and then transferred to a eggplant-shaped flask equipped with a magnetic stirrer. After three freeze-thaw cycles on a high vacuum line and 16 hours of polymerization at 60 ℃, a triblock copolymer PtBA-b-P (tBA-r-nBA) -b-PtBA is obtained. After polymerization, 12mL of concentrated hydrochloric acid was diluted with 80mL of dioxane and added to the polymerization system and refluxed at 90 ℃ overnight. Finally, the product was precipitated with deionized water. The elastomer obtained was dried in a forced air drying oven for 24 hours and then dried in a vacuum drying oven to a constant weight.
TABLE 1 formulation for the Synthesis of macromolecular PtBA raft reagents and tBA and nBA copolymers
a) S, S ' -Bis (alpha, alpha ' -dimethyl-alpha ' -acetic acid) trithiocarbonate (BDATC) used as a chain transfer agent; b) macro PtBA 1(Mn 11350) used as a chain transfer agent; c) macro PtBA 2(Mn ═ 14379) used as a chain transfer agent; d) number average molecular weight, weight average molecular weight and polydispersity index as determined by GPC; d) the nBA/tBA ratio was calculated using nuclear magnetic hydrogen spectroscopy.
Description of the drawings: M-T presented in the description is a macromolecular PtBA raft reagent, Tri-TRT represents PAA-b-P (AA-R-nBA) -b-PAA with a phase structure design, R represents one of the controls-P (AA-R-nBA) with a random copolymerization structure, and Tri-THT represents another chain structure-PAA-b-PnBA-b-PAA. And the Arabic numerals in the sample marks are used for distinguishing different monomer structural unit molar ratios and different molecular weights of the composition chain segments.
Claims (8)
1. A self-repairing polyacrylate elastomer with a multiphase structure is characterized in that: the elastomer has a multiphase structure, the A blocks at two ends are polyacrylic acid, and the B block in the middle is a copolymer of n-butyl acrylate and acrylic acid; the elastomers exhibit fluorescent emission properties in solution and solid state when irradiated by an ultraviolet lamp, and enhance emission properties for aggregation in solution.
2. A method of preparing the self-healing polyacrylate elastomer with multiphase structure of claim 1, characterized by the steps of:
step 1, controllable free radical polymerization is carried out to obtain a PtBA-b-P (tBA-r-nBA) -b-PtBA triblock copolymer: the method comprises the steps of taking n-butyl acrylate nBA and tert-butyl acrylate tBA as monomers by using a controllable free radical polymerization method, adding an initiator with the molar weight of 0.010-0.350 mol% relative to the monomers, and polymerizing at the temperature of 55-80 ℃ in an inert gas atmosphere;
and 2, hydrolysis reaction of the copolymer: and (3) after purifying the copolymer obtained in the step (1), adding acid to react for 10-48 h, and precipitating the product by using deionized water.
3. The method of claim 2, wherein: the method for the controllable free radical polymerization comprises a nitrogen-oxygen stable free radical method, an atom transfer radical polymerization method ATRP or a reversible addition-fragmentation chain transfer method RAFT.
4. The method of claim 2, wherein: the inert gas is N2Or Ar.
5. The method of claim 2, wherein: the initiator is azobisisobutyronitrile AIBN, dibenzoyl peroxide BPO, azobisisoheptonitrile ABVN or dimethyl azobisisobutyrate AIBME.
6. The method of claim 2, wherein: the acid added in the step 2 is trifluoroacetic acid or hydrochloric acid.
7. The method of claim 6, wherein: the concentration range of the trifluoroacetic acid is 4.0-7.0 mol/L.
8. The method of claim 6, wherein: the concentration range of the hydrochloric acid is 0.7-1.5 mol/L.
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