CN103837507A - Method for testing influences of different pH values on intensity ratio of spectral vibration peak - Google Patents
Method for testing influences of different pH values on intensity ratio of spectral vibration peak Download PDFInfo
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- CN103837507A CN103837507A CN201210481863.6A CN201210481863A CN103837507A CN 103837507 A CN103837507 A CN 103837507A CN 201210481863 A CN201210481863 A CN 201210481863A CN 103837507 A CN103837507 A CN 103837507A
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Abstract
The invention discloses a method for testing the influences of different pH values on the intensity ratio of a spectral vibration peak. The method comprises the following steps: 1, preparing a hydrophobic associating polymer sample for later use; 2, preparing a methanol solution of pyrene; 3, sucking the methanol solution of pyrene, transferring the methanol solution of pyrene to clean experiment containers, introducing nitrogen to blow away methanol and dry pyrene, and spreading pyrene on the walls of volumetric flasks; 4, weighing the hydrophobic associating polymer, putting the hydrophobic associating polymer in the volumetric flasks, adding a quantitative amount of distilled water to prepare a same concentration of hydrophobic associating polymer solutions, adjusting the solutions to different pH values, putting the obtained solutions in constant temperature water-bath oscillators, and carrying out constant temperature oscillation to uniformity; and 5, introducing nitrogen, allowing the solutions obtained in step 4 to stand at normal temperature, carrying out fluorescent spectroscopy of the hydrophobic associating polymer solutions, and analyzing results to obtain the influences of different pH values on the intensity ratio of a spectral vibration peak. The method enables the influences of different pH values on the intensity ratio of a spectral vibration peak to be successfully tested, and has the advantages of accurate test result, simple test steps, and substantial reduction of the test cost.
Description
Technical field
The present invention relates to the method for testing of a kind of different pH value on the impact of spectrum vibration peak strength ratio.
Background technology
Hydrophobic associated polymer, refers to the water-soluble polymers with a small amount of hydrophobic grouping on polymer hydrophilicity macromolecular chain.On water-soluble macromolecule chain, introducing a small amount of hydrophobic grouping makes its aqueous solution show unique rheological property.On certain polymer concentration, hydrophobic part associates and forms dynamic three-dimensional net structure, thereby forms very large supermolecule chain aggregation body, increases the hydrodynamic volume of polymkeric substance, improves significantly the viscosity of solution.The electrolytical polarity that can increase solvent that adds of little molecule, strengthens hydrophobic association effect, produces obvious salt-resistance.Under high shear forces, the dynamic physical cross-linked network structure that hydrophobic association forms is destroyed, solution viscosity declines, shear action reduction or the physical crosslinking of eliminating between rear macromolecular chain form again, viscosity will be recovered again, the irreversible machinery degraded of the polymkeric substance that general high molecular do not occur under high-rate of shear.Just because of its unique SOLUTION PROPERTIES, it may be applied in a lot of fields, as tertiary oil recovery, pharmacy, sun power conversion, cosmetics, coating, water treatment and drag reducer etc.Its correlative study in recent years receives much attention.
Hydrophobic close ester phenomenon is very general, below critical association concentration, mainly forms in molecule and associates, and consequently makes a ball of string shrink, and hydrodynamic volume reduces; More than CAC, main formation take Interpolymer Association as main supramolecular structure has good tackifying.By Interpolymer Association, on the macro property of solution, show the feature that tackifying is strong, have certain temperature resistance, anti-salt and anti-shear ability.These special performances of hydrophobic associated polymer make it in many industrial technologies, all show huge application potential, and have great importance for the solution behavior that imitates the amphiphilic class material in life entity, thereby the exploration of hydrophobic associated water-soluble polymer is become to recent two decades carry out one of problem the most interesting in water-soluble polymers research field, and become the focus that industry and academia are studied.
Should trace back to the fifties initial stage to the research of amphiphilic base polymer, Strauss and assistant thereof have synthesized the solution behavior of a series of polysoaps in order to mimic protein for this reason, first Kauzmann has proposed the concept of " hydrophobic interaction ", and describes XC polymer as a series of phenomenons relevant to life science such as the formation of film in the constraint to enzyme of the conformation transition of protein, matrix, biosome with it.In the later stage in the sixties, Strauss group has synthesized again a series of hydrophobic super coil polymkeric substance that have.Contemporaneity, hydrophobically modified urea alkane (HEUR) comes out and is very fast for improving the rheological of water-based latex coating.Until today, researchist, still in effort, attempts that HEUR is made further improvements or find new material and replaces HEUR.
Last century the eighties, the SOLUTION PROPERTIES of hydrophobic associated polymer uniqueness and huge application potential thereof have attracted a large amount of researchists.Landoll is considered to study the real beginning of hydrophobic associated water-soluble polymer about the research of hydroxyethyl cellulose (HEC) hydrophobically modified.The people such as Emmons have delivered the patent with chain alkyl N-substituted acrylamide (CnAM) copolymerization cooperation water-based paint with acrylamide (AM).Before and after 1984, the researchist of Exxon research and engineering corporation starts to inquire into hydrophobic associated polymer the feasibility for oil-gas mining, and this is carried out to lasting and deep research, develop various hydrophobic monomer, and invent the novel polymeric method that solves hydrophilic monomer and the inconsistent problem of hydrophobic monomer in hydrophobic associated polymer polymerization process, it is micellar free radical copolymerization method, be called for short micellar copolymerization, the method is still the best approach in all polymerizations of hydrophobic associated polymer up to now.
Hydrophobic associated water-soluble polymer is by the atom difference that forms main chain, can be divided into carbochain and heteroatoms molecular backbone polymkeric substance, the former is mainly the multipolymer being obtained by the alkene monomer polymer of hydrophilic radical and hydrophobic grouping, what hydrophilic monomer was conventional mainly contains acrylamide and acrylic acid etc., and hydrophobic monomer mainly contains acrylamide derivative, long-chain acrylate etc.; The latter mainly passes through water-soluble high-molecular compound modification through macromolecular reaction, introduces hydrophobic functional group.Macromolecular reaction method advantage is directly to make initiation material with commercial polymer, and the product relative molecular mass obtaining is high, and its shortcoming is that reaction is carried out in full-bodied polymer solution, and reactant is not easy to mix.Hydroxyethyl cellulose (HEC) can be reacted with the hydrophobic compound with reactive group in this way, these hydrophobic compounds can be with the epoxy compound of chain alkyl, halogenated hydrocarbons, carboxylic acid halides, isocyanates etc., also can be at polyglycol (PEG) two termination hydrophobic groupings, but the amount of the general hydrophobic grouping of introducing is all little, because the high dissolubility that can significantly reduce water soluble polymer of content of hydrophobic monomers, and heteroatoms trunk polymer is compared with carbochain polymer, thermal stability is poor.Because when the carbon atom in macromolecular chain is replaced by heteroatomss such as oxygen, sulphur, nitrogen, the bond energy of C-O, C-S, C-N key is lower than C-C key, and polymer thermostable reduces.Therefore be, mainly the multipolymer being obtained by the vinyl monomer polymerization of hydrophilic radical and hydrophobic grouping for the hydrophobic associated water-soluble polymer of tertiary oil production in oil field at present.The conventional hydrophilic monomer of hydrophobic associated polymer that utilizes process for copolymerization to prepare is acrylamide (AM), because acrylamide is suitable for preparing the water-soluble polymers of high molecular, reasonable price.In addition, in order to increase the dissolubility of multipolymer, the anionic monomer that also can add other as acrylic acid (methacrylic acid), vinylsulfonate, 2-methyl-2-acrylamido propane sulfonic acid (AMPS) etc. with cationic monomer as β-dimethyl-aminoethylmethacrylate base trimethyl ammonium chloride, 2-acrylimide base-2-trimethoxysilyl propyl methacrylate ammonium chloride (AMPTAC), diallyldimethylammonium chloride etc.
The architectural feature of hydrophobic associated water-soluble polymer is on the strand of polymkeric substance, to introduce a small amount of hydrophobic grouping.The polar group of hydrophilic segment can form hydrogen bond and show very strong affinity with hydrone.What form hydrophobic associated polymer molecule hydrophobic part is non-polar group, between they and hydrone, only has Van der Waals force, this acting force a little less than than the interaction hydrogen bond between hydrone many, thereby can not effectively replace with hydrone with interaction of hydrogen bond.The hydrophobic grouping of this type of solute molecule in dissolved state is present in water environment, and the approach that hydrophobic group is fled from water environment is that hydrophobic associated polymer molecule associates and forms aggregation together with hydrophobic group at the inner association body that forms of solution.Hydrophobic grouping, due to water insoluble, is close together under the driving of hydrone, also can be understood as conversely the effect that hydrophobic grouping is subject to association force and flocks together.
Hydrophobic associated water-soluble polymer refers to the water-soluble polymers with a small amount of hydrophobic grouping (mole fraction≤5%) on polymer hydrophilicity macromolecular chain.In aqueous medium, the hydrophobic grouping generation hydrophobic interaction of hydrophobic associated water-soluble polymer, assemble and form hydrophobic microcell, cause macromolecular chain to produce in molecule or intermolecular association, form the micelle nano structure of various different shapes---Supramolecular Network structure, make its aqueous solution show unique rheological property.Survey the technology of macroscopical SOLUTION PROPERTIES, as viscosimetric analysis, fluid mechanics research, the research of hydrophobic associated water-soluble polymer molecular aggregates behavior is had to certain directive significance, but almost there is no the analytical approach from the interphase interaction of molecular level molecular detection.
Summary of the invention
The object of the invention is to overcome the shortcoming and defect of above-mentioned prior art, the method of testing of a kind of different pH value on the impact of spectrum vibration peak strength ratio is provided, this method of testing can successfully test out the impact of different pH values on spectrum vibration peak strength ratio, and test result is accurate, testing procedure is simple, greatly reduces testing cost.
Object of the present invention is achieved through the following technical solutions: the method for testing of a kind of different pH values on the impact of spectrum vibration peak strength ratio, comprises the following steps:
(a) first, prepare hydrophobic associated polymer sample for subsequent use;
(b) then, prepare the methanol solution of pyrene;
(c) methanol solution of drawing above-mentioned pyrene with microsyringe is in clean experiment container, and after passing into nitrogen methyl alcohol is dried up under shake, pyrene will spread on volumetric flask wall;
(d) take appropriate hydrophobic associated polymer in this volumetric flask, add again quantitative distilled water to be mixed with the hydrophobic association polymer solution of same concentrations, regulator solution is different pH values, puts into the vibration of water bath with thermostatic control oscillator isothermal evenly, makes pyrene disperse completely, dissolve;
(e) lead to nitrogen again, drive the oxygen in solution, solution normal temperature is transferred postpone, then carries out the fluorescent spectroscopy of hydrophobic association polymer solution, by analysis result, thereby draws the impact of different pH values on spectrum vibration peak strength ratio.
Described experiment container is 50mL volumetric flask.
The concrete steps of described step (b) are: accurately take pyrene 10.1mg, be dissolved in after methyl alcohol, transfer in 50mL volumetric flask, be diluted to scale, be 1 × 10
-3the methanol solution of the pyrene of mol/L.
In described step (e), the time of logical nitrogen is 30min, and be 48h standing time.
Described pH value is respectively 4,5,6,7,8,9,10.
In sum, the invention has the beneficial effects as follows: can successfully test out the impact of different pH values on spectrum vibration peak strength ratio, and test result is accurate, testing procedure is simple, greatly reduces testing cost.
Accompanying drawing explanation
?fig. 1 is the schematic diagram of different pH values on the impact of spectrum vibration peak strength ratio.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited only to this.
Embodiment:
The method of testing of a kind of different pH values that the present invention relates on the impact of spectrum vibration peak strength ratio, comprises the following steps:
(a) first, prepare hydrophobic associated polymer sample for subsequent use;
(b) then, prepare the methanol solution of pyrene;
(c) methanol solution of drawing above-mentioned pyrene with microsyringe is in clean experiment container, and after passing into nitrogen methyl alcohol is dried up under shake, pyrene will spread on volumetric flask wall;
(d) take appropriate hydrophobic associated polymer in this volumetric flask, add again quantitative distilled water to be mixed with the hydrophobic association polymer solution of same concentrations, regulator solution is different pH values, puts into the vibration of water bath with thermostatic control oscillator isothermal evenly, makes pyrene disperse completely, dissolve;
(e) lead to nitrogen again, drive the oxygen in solution, solution normal temperature is transferred postpone, then carries out the fluorescent spectroscopy of hydrophobic association polymer solution, by analysis result, thereby draws the impact of different pH values on spectrum vibration peak strength ratio.
Described experiment container is 50mL volumetric flask.
The concrete steps of described step (b) are: accurately take pyrene 10.1mg, be dissolved in after methyl alcohol, transfer in 50mL volumetric flask, be diluted to scale, be 1 × 10
-3the methanol solution of the pyrene of mol/L.
In described step (e), the time of logical nitrogen is 30min, and be 48h standing time.
Described pH value is respectively 4,5,6,7,8,9,10.
The result being recorded by said method as shown in Figure 1, in figure, I1/I3 refers to the intensity ratio of intensity and the 3rd vibration peak of the first vibration peak, as shown in Figure 1: in the time of pH < 8, along with the increase of pH value, I1/I3 value keeps certain value after first increasing gradually, when after pH > 8, I1/I3 value increases and reduces gradually with pH value.This phenomenon may be interpreted as: when low pH value, carboxyl keeps carboxylic acid state, and the large intermolecular hydrophobic effect of hydrophobic associated polymer and hydrogen bond action cause macromolecular chain mutually overlapping, and now pyrene molecule is enriched in hydrophobic microcell, with the minimizing that contacts of hydrone, therefore I1/I3 value is less; Along with the increase of pH value, hydroxy-acid group is progressively dissociated into the group of bear electricity, electrostatic repulsion between bear electric group and volume excluding effect make macromolecular chain expansion, chain amount of crimp variation, a small amount of hydrone permeable enter in hydrophobic microcell, pyrene molecule microenvironment polarity of living in increases, therefore in the time that pH is increased to 5～6, I1/I3 value sharply raises; Increase pH value, the hydrophobic effect between electrostatic repulsion and hydrophobic grouping between bear electric group and the hydrogen bond action between polar group reach balance again, and the residing hydrophobic domain structure of pyrene molecule tends towards stability, and I1/I3 value changes little; PH value further increases, and in solution, Na+ and OH-increase medium ionic strength, shielded carboxylate radical negative charge on hydrophobic associated polymer strand, thereby electrostatic repulsion is weakened, and Interpolymer Association effect strengthens, therefore I1/I3 value reduces.
The above, be only preferred embodiment of the present invention, not the present invention done to any pro forma restriction, every foundation technical spirit of the present invention, and any simple modification, equivalent variations that above embodiment is done, within all falling into protection scope of the present invention.
Claims (5)
1. the method for testing of different pH values on the impact of spectrum vibration peak strength ratio, is characterized in that, comprises the following steps:
(a) first, prepare hydrophobic associated polymer sample for subsequent use;
(b) then, prepare the methanol solution of pyrene;
(c) methanol solution of drawing above-mentioned pyrene with microsyringe is in clean experiment container, and after passing into nitrogen methyl alcohol is dried up under shake, pyrene will spread on volumetric flask wall;
(d) take appropriate hydrophobic associated polymer in this volumetric flask, add again quantitative distilled water to be mixed with the hydrophobic association polymer solution of same concentrations, regulator solution is different pH values, puts into the vibration of water bath with thermostatic control oscillator isothermal evenly, makes pyrene disperse completely, dissolve;
(e) lead to nitrogen again, drive the oxygen in solution, solution normal temperature is transferred postpone, then carries out the fluorescent spectroscopy of hydrophobic association polymer solution, by analysis result, thereby draws the impact of different pH values on spectrum vibration peak strength ratio.
2. the method for testing of different pH value according to claim 1 on the impact of spectrum vibration peak strength ratio, is characterized in that, described experiment container is 50mL volumetric flask.
3. the method for testing of different pH value according to claim 1 on the impact of spectrum vibration peak strength ratio, is characterized in that, the concrete steps of described step (b) are: accurately take pyrene 10.1mg, be dissolved in after methyl alcohol, transfer in 50mL volumetric flask, be diluted to scale, be 1 × 10
-3the methanol solution of the pyrene of mol/L.
4. the method for testing of different pH value according to claim 1 on the impact of spectrum vibration peak strength ratio, is characterized in that, in described step (e), the time of logical nitrogen is 30min, and be 48h standing time.
5. the method for testing of different pH value according to claim 1 on the impact of spectrum vibration peak strength ratio, is characterized in that, described pH value is respectively 4,5,6,7,8,9,10.
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Application publication date: 20140604 |