CN102558434B - Associative polyacrylamide solution and preparation method and applications thereof - Google Patents
Associative polyacrylamide solution and preparation method and applications thereof Download PDFInfo
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Abstract
The invention discloses an associative polyacrylamide solution and a preparation method and applications thereof. The solution comprises associative polyacrylamide serving as a solute and a mixture of formamide and water serving as a solvent. According to the associative polyacrylamide solution and the preparation method and applications thereof, series hydrophobically associating water-soluble polymer (HAWSP) solutions in different hydrophobic association degrees can be obtained through changing the ratio of components in solvent compositions.
Description
Technical field
The present invention relates to a kind of association type polyacrylamide solution and preparation method thereof and application.
Background technology
Hydrophobic associated polymer (Hydrophobically Associating Water-Soluble Polymers is called for short HAWSP), refers to the water-soluble polymers with a small amount of hydrophobic grouping on polymer hydrophilicity macromolecular chain.In aqueous, when polymer concentration is higher than a certain threshold concentration (Critical Association Concentration, CAC) after, macromolecular chain is assembled by heat resistance and salt tolerance, form the supramolecular structure (dynamic physical cross-linked network) based on Interpolymer Association, hydrodynamic volume increases, soltion viscosity significantly raises (Alain Hill, Francoise Candau, Joseph Selb, Properties of Hydrophobically Associating Polyacrylamides:Influence of the Method of Synthesis, Macromolecules, 1993, 26 (17): 4521-4532).The supramolecular network structure formed due to HAWSP has the feature of reversible recovery, therefore in different solutions environment and under different shear rate, show the ability of good control working fluid rheological, in Oil-Gas Well Engineering and petroleum engineering field, particularly in drilling fluid and raising recovery ratio, there is huge application potential (Taylor K C, Nasr-El-Din H A, Water-Soluble Hydrophobically Associating Polymers for Improved OilRecovery:A Literature Review, Society of Petroleum Engineers, SPE29008, 675-690).Association type polyacrylamide is using acrylamide and vinylformic acid as a hydrophobically associating polymkeric substance of polymer molecule backbone, this base polymer is one of topmost type of hydrophobic associated polymer, and the application (Zhou Shouwei obtained in the actual production in oil field to a certain degree, Han Ming, Xiang Wentao, Zhang Jian etc., the technical study of Bohai Bay Oil enhancing oil recovery in polymer flooding and application, China's offshore oil and gas, 2006,18 (6): 386-389).
It is that this effect is exactly heat resistance and salt tolerance because hydrophobic grouping Specific Interactions in aqueous that the HAWSP aqueous solution has unique rheological.Heat resistance and salt tolerance refers to that hydrophobic grouping (non-polar molecule) can make the water molecules of surrounding be arranged in around it again, more in an orderly manner in aqueous, formed so-called " ice-like cage structure ", this is a kind of negentropy process, cause producing (the Lu Shouci chief editor that assembles or associate between hydrophobic grouping in aqueous, industry suspension-performance, modulation and processing [M], Beijing: Chemical Industry Press, in May, 2003; Hu Hongqi, Chen Mingcai, during journey Rong, the research of lyophobic association effect, Guangzhou chemistry, 2003,28 (1): 26-33), heat resistance and salt tolerance can be present in molecule with intermolecular.The theoretical model of system viscosity is set up according to the interaction between polymer molecular chain, polymer molecule bundle or polymer molecule group that utilizes that the sub-academician in Luoping proposes, Associating Polymer Solution is a kind of supramolecular system, be typical structural fluid, its apparent viscosity is made up of structural viscosity and non-structural viscosity; Structural viscosity determines primarily of intermolecular heat resistance and salt tolerance; After polymer concentration exceedes the overlapping concentration of chain, the structural viscosity that the viscosity of HAWSP solution produces primarily of intermolecular hydrophobic association forms (Asia, Luoping, the polymer class Oilfield Chemicals of Twenty-First Century, the public lecture of the Southwest Petroleum Institute anniversary of the founding of a school 40 anniversary academic paper, Sichuan Nanchong).Author have studied the relation of HAWSP solution structure viscosity and Interpolymer Association effect, and in non-entanglement semidilute district, the ratio shared by structural viscosity is greater than 80%; In entanglement semidilute district, structural viscosity proportion reached for more than 99% (Feng Rusen, the relation research of hydrophobic associated polymer molecular structure and solution structure and rheological characteristics, Southwest Petrol University's Ph D dissertation, Chengdu, Sichuan, in April, 2008).
Research about heat resistance and salt tolerance is the research emphasis in HAWSP field always, has more report abroad to the research of solvent property and heat resistance and salt tolerance relation in HAWSP solution system.Chang Y H etc. adopt methanol/water mixed solvent to eliminate heat resistance and salt tolerance, but this solvent condition thoroughly cannot destroy association (Chang Y H, Mccormick C L, Water-Soluble Copolymers.49.Effect of the Distribution of the Hydrophobic Cationic Monomer-Dimethyldodecyl (2-Acrylamidoethyl) Ammonium Bromide on the Solution Behavior Of Associating Acrylamide Copolymers, Macromolecules, 1993, 26 (22): 6121-6126), Volpert E etc. thinks effectively can destroy heat resistance and salt tolerance at methane amide as solvent, therefore static light scattering method can be adopted to measure absolute molecular weight (the Biggs S of HAWSP, Hill A, Selb J, Candau F, Copolymerization of Acrylamide and a Hdydrophobic Monomer in an Aqueous Micellar Medium:Effect of the Surfactant on the Copolymer Microstructure, J.Phys.Chem, 1992,96 (3), 1505-1511), except employing organic solvent, tensio-active agent (Branham K D, Davis D L, Middleton J C, et al, Water-Soluble Polymers.59.Investigation of the Effects of Polymer Microstructure on the Associative Behaviour of Amphiphilic Terpolymers of Acrylamide, Acrylic Acid and N-(4-decyl) phenyl Acryl-amide, Polymer, 1994, 35 (20): 4429-4436) and cyclodextrin (Islam M F, Jenkins R D, Bassett D R, et al, Single Chain Characterization of Hydrophobically Modified Polyelectrolytes Using Cyclodextrin/Hydrophobe Complexes, Macromolecules, 2000, 33 (7): 2480-2485) be also used to shield heat resistance and salt tolerance.Relative to abroad, the domestic research to heat resistance and salt tolerance is started late, and research work mainly concentrates on the sign of HAWSP solution supramolecular structure under heat resistance and salt tolerance existence condition.Fluorescent method, ultraviolet method and freeze-etching transmission electron microscope method is such as adopted to study the process (Han Lijuan forming network structure in HAWSP solution, the research of oil-gas mining hydrophobic associated polymer, Southwest Petroleum Institute Ph.D. Dissertation, Chengdu, Sichuan, in May, 2004); Adopt Multi-functional scanning probe microscope, observe structure and morphology (Wang Yubo, the Ye Zhongbin of association polymer AP-P4, Shi Xuezhi, hydrophobic associated polymer mass concentration on the impact of its structure and morphology, Xinjiang petroleum geology, 2008,29 (5): 638-640).
In a word, how the majority of the domestic and international correlative study work for heat resistance and salt tolerance in HAWSP solution at present eliminates the impact for solution pattern of heat resistance and salt tolerance or heat resistance and salt tolerance if concentrating on, the affecting laws of change for heat resistance and salt tolerance of solvent property is not all systematically studied in these work, does not especially provide by the realization of adjustment solvent composition the feasible method of heat resistance and salt tolerance regulation and control.The method of this regulation and control heat resistance and salt tolerance to the relation studying heat resistance and salt tolerance and HAWSP solution structure and rheological, and then verifies and develops hydrophobic associated polymer structural fluid theory to have important value.
Summary of the invention
The object of this invention is to provide a kind of association type polyacrylamide solution and preparation method thereof and application.
Association type polyacrylamide solution provided by the invention, is made up of the association type polyacrylamide as solute and the mixed solution be made up of methane amide and water as solvent;
Or, by the association type polyacrylamide as solute with form as the methane amide of solvent;
Or, by the association type polyacrylamide as solute with form as the water of solvent.
The product of above-mentioned association type polyacrylamide all for being obtained 40 ~ 60 DEG C of reactions 6 ~ 10 hours by 0.7 ~ 1.0mol acrylamide, 0.15 ~ 0.3mol sodium acrylate and 0.001 ~ 0.01mol hexadecyldimethyl benzyl ammonium allylic bromination ammonium, is preferably the product obtained 50 DEG C of reactions 8 hours by 0.8mol acrylamide, 0.2mol sodium acrylate and 0.005mol hexadecyldimethyl benzyl ammonium allylic bromination ammonium; The molecular weight of described association type polyacrylamide is 0.50 × 10
6~ 8.0 × 10
6g/mol, preferably 4.2 × 10
6g/mol;
Described by the association type polyacrylamide as solute and the mixed solution be made up of methane amide and water as solvent, the volume percent of described methane amide and water is 0 ~ 100%, the volume percent of preferred methane amide is 70%, and the volume percent of described methane amide and water is not all 0;
Described association type concentration of polyacrylamide solution is 500 ~ 5000mg/L, preferred 2000mg/L.
The method of the above-mentioned solution of preparation provided by the invention, comprises the steps:
1) be dissolved in methane amide by described association type polyacrylamide, mixing obtains described association type polyacrylamide mother liquor;
2) by described step 1) methane amide of gained volume to be the association type polyacrylamide mother liquor of x mL and volume be d mL and volume be that the water of w mL mixes, and obtains described association type polyacrylamide solution;
Wherein, the concentration expressed in percentage by volume of known described methane amide is y, the concentration of described association type polyacrylamide is cmg/L, the volume of described solution system is v mL, according to formula I, formula II and formula III, x, w and d and described relational expression between y, c and v, can obtain the concrete numerical value of described x, w and d;
W=v (1-y) (formula II)
The method step 1) in, described association type polyacrylamide is react at 40 ~ 60 DEG C the product obtained for 6 ~ 10 hours by 0.7 ~ 1.0mol acrylamide, 0.15 ~ 0.3mol sodium acrylate and 0.001 ~ 0.01mol hexadecyldimethyl benzyl ammonium allylic bromination ammonium, is preferably the product obtained 50 DEG C of reactions 8 hours by 0.8mol acrylamide, 0.2mol sodium acrylate and 0.005mol hexadecyldimethyl benzyl ammonium allylic bromination ammonium; The molecular weight of described association type polyacrylamide is 0.50 × 10
6~ 8.0 × 10
6g/mol, preferably 4.2 × 10
6g/mol; The volume percent of described methane amide and water is 0 ~ 100%, preferably 70%; Described association type polyacrylamide is dissolved in carboxamide Step, and temperature is 35-55 DEG C, preferably 45 DEG C, and the time is 2-8 hour, preferably 6 hours.The concentration of described association type polyacrylamide mother liquor is 10000mg/L.
Described step 2) mix in step, temperature is 25-45 DEG C, preferably 30 DEG C, and the time is 1-4 hour, preferably 2 hours.In described solution system, association type concentration of polyacrylamide solution c is 500 ~ 5000mg/L, and the concentration expressed in percentage by volume y of methane amide is 0 ~ 100%, and preferred association type concentration of polyacrylamide solution is 2000mg/L, methane amide concentration expressed in percentage by volume 70%.
The invention provides a kind of can the method for heat resistance and salt tolerance power in Effective Regulation association type polyacrylamide solution, its core content is the regulation and control that the proportionlity by changing each component of solvent compositions realizes to heat resistance and salt tolerance, thus obtain the serial HAWSP solution with different heat resistance and salt tolerance, its ultimate principle is: by the polarity regulating the proportionlity of methane amide and water effectively can change solvent system, thus realize the regulation and control to heat resistance and salt tolerance.In solvent composition, the ratio of water is higher, then the polarity of solvent is stronger, and the heat resistance and salt tolerance in HAWSP solution is stronger; Otherwise, increase methane amide ratio then heat resistance and salt tolerance weaken.
Under solvent combination condition provided by the invention, the HAWSP solution with different heat resistance and salt tolerance can be prepared easily, thus provide basic experimental conditions for the mutual relationship systematically studying heat resistance and salt tolerance and HAWSP solution structure and rheological characteristics, such as adopt the characterization methods such as scanning electron microscope, atomic force microscope, dynamic light scattering to study the impact of heat resistance and salt tolerance for multimolecules reaction model and solution pattern; Adopt steady state rheology and dynamic rheology technique study heat resistance and salt tolerance to the affecting laws of solution Macro-Rheological Characterization;
Adopt method preparing association type polyacrylamide solution provided by the present invention, effectively can eliminate heat resistance and salt tolerance, polymer molecule is made to be in monomolecular dispersion state in the solution, for the unit molecule form and feature thereof studying HAWSP provides experiment condition;
A certain proportion of pure water is comprised in solvent combination provided by the present invention, be convenient to preparation containing the electrolytical target liquid of dissimilar small molecules, thus the character of Study Polymer Melts solution under being readily embodied in the condition eliminating polyelectrolyte effect, therefore the present invention is also applicable to the research work of various polyelectrolyte type hydrophobic association polymer solution;
Method provided by the present invention can study HAWSP from a monomolecular dispersion ball of string → small scale multimolecules reaction model → big scale multimolecules reaction model → building process of overall supramolecular network structure and the relation of heat resistance and salt tolerance, thus for checking with development HAWSP solution supramolecule is theoretical and structural fluid is theoretical provides feasible experimental technique scheme;
Solvent composition of the present invention is the mixed solvent system of methane amide and water, has the simple advantage of preparation, and does not have detrimentally affect to the health of operator and environment.
The present invention adopts the multiple characterizing methods such as rheology, UV spectrum, scanning electronic microscope systematically to have studied the relation of solvent composition and heat resistance and salt tolerance, finally obtain a kind of range of solvents composition that can regulate and control heat resistance and salt tolerance in association type polyacrylamide solution, the strong and weak different serial HAWSP solution of heat resistance and salt tolerance can be obtained by the proportionlity changing each component in solvent compositions.
Accompanying drawing explanation
Fig. 1 be in the present invention methane amide volumetric concentration on the impact of association type polyacrylamide solution steady state shearing viscosity;
Fig. 2 be in the present invention methane amide volumetric concentration on the impact of association type polyacrylamide solution storage modulus;
Fig. 3 be in the present invention methane amide volumetric concentration on the impact of association type polyacrylamide solution turbidity;
Fig. 4 be in the present invention methane amide volumetric concentration on the impact of association type polyacrylamide solution UV spectrum;
Fig. 5 ~ 7 be in the present invention methane amide volumetric concentration on the impact of association type polyacrylamide solution structure and morphology;
Fig. 8 be in the present invention methane amide volumetric concentration on the impact of the size distribution intermediate value of polymer molecule in association type polyacrylamide solution;
Fig. 9 be in the present invention methane amide volumetric concentration on the impact of association type polyacrylamide solution intrinsic viscosity;
Figure 10 be in the present invention sodium chloride concentration on the impact of association type polyacrylamide solution intrinsic viscosity.
Embodiment
Embodiment 1,
1) within 8 hours, be dissolved in methane amide by association type polyacrylamide in 35 DEG C of stirrings, mixing obtains association type polyacrylamide mother liquor; The concentration of this association type polyacrylamide mother liquor is 10000mg/L;
This association type polyacrylamide is formed by 0.8mol acrylamide, 0.2mol sodium acrylate and the copolymerization of 0.005mol hexadecyldimethyl benzyl ammonium allylic bromination ammonium, and molecular weight is 4.2 × 10
6g/mol.In this polymerization procedure, temperature is 50 DEG C, and the time is 8 hours;
2) by step 1) methane amide of gained volume to be the association type polyacrylamide mother liquor of x mL and volume be d mL and volume be that the water of w mL mixes, and obtains the solution system of different methane amide concentration expressed in percentage by volume y (being respectively 10%, 20%, 30%, 40%, 50%, 70%, 90%, 100%);
Wherein, set the concentration c of association type polyacrylamide used in this solution system and be 2000mg/L, the cumulative volume v of each solution system is 100mL; According to following x, w and the relation between d and y, c and v such as formula shown in I-formula III, described step 1 used can be obtained) in the volume x mL of association type polyacrylamide mother liquor x concrete numerical value and learn the concrete numerical value that the concrete numerical value of d in the volume d mL of methane amide and required volume of water are w in w mL:
W=v (1-y) (formula II)
In this mixing step, temperature is 25 DEG C, and the time is 4 hours.
In addition, the blank that methane amide concentration expressed in percentage by volume is 0 is set.
The relation of methane amide volumetric concentration and heat resistance and salt tolerance in solution system:
In the solution system of a, different methane amide volumetric concentration (being respectively 0,10%, 30%, 50%, 70%, 100%), the experimental result of HAWSP steady state shearing viscosity is shown in Fig. 1.
As can see from Figure 1, as methane amide volumetric concentration > 30%, the steady state shearing viscosity of solution tends towards stability, illustrate that in solution, overall associative structure is broken, HAWSP molecule is dispersed in formamide/water mixed solvent with the form of monomolecular dispersion state or molecular clustering.Therefore, by adjusting the volumetric concentration of methane amide, the power of HAWSP solution heat resistance and salt tolerance can be regulated and controled.
B, methane amide volumetric concentration are on the impact of storage modulus
(Storage modulus, G ') are used for characterizing the elasticity of fluid storage modulus, have reacted the intensity of the network structure formed by hydrophobic grouping Interpolymer Association in the intensity of network structure in HAWSP solution, particularly solution.Test the variation tendency of HAWSP storage modulus in the mixed solvent of different methane amide volumetric concentration (being respectively 0,10%, 30%, 50%, 70%, 100%), can react the Changing Pattern of heat resistance and salt tolerance in the change solution with solvent polarity, experimental result is shown in Fig. 2.
The experimental result of Fig. 2 shows: along with the increase of methane amide volumetric concentration, storage modulus reduces rapidly, as methane amide volumetric concentration > 30%, storage modulus kept stable, illustrates that now overall associative structure is broken in solution.
C, methane amide volumetric concentration are on the impact of turbidity
When containing the particulate of suspension and colloidal state in water, the aqueous solution will produce turbid phenomenon by water, and the degree of its muddiness is called turbidity, and unit is NTU.HAWSP solution also shows certain turbidity, and the size of its turbidity value is directly related with the power of hydrophobic association microcell in solution and quantity.Along with the increase of methane amide volumetric concentration, the polarity of solvent dies down gradually, and heat resistance and salt tolerance weakens gradually, and hydrophobic association microcell also can change thereupon, can react this change procedure by the turbidity or transmittance measuring solution.
The experimental result of Fig. 3 shows, when methane amide volumetric concentration is increased to 50% from 10%, the turbidity of HAWSP solution declines fast, as methane amide volumetric concentration > 50%, the turbidity of HAWSP solution significantly reduces, and illustrates that the hydrophobic association microcell in HAWSP solution significantly reduces.
D, methane amide volumetric concentration are on the impact of UV spectrum
Interval at 320 ~ 330nm, the HAWSP solution uv-absorbing intensity of different methane amide volumetric concentration (being respectively 0,10%, 20%, 30%, 40%, 70%, 90%) and the relation curve of methane amide volumetric concentration are as shown in Figure 4.
Shown by the test result of Fig. 4, when methane amide volumetric concentration is greater than 40%, the hydrophobic microcell in HAWSP solution is broken, and its overall associative structure is broken.
The experimental result of the characterization methods such as comprehensive shear viscosity, storage modulus, turbidity and UV spectrum is analyzed, can find, along with the increase of methane amide volumetric concentration, the heat resistance and salt tolerance of HAWSP solution constantly weakens, the overall network structure spreading all over whole solution system changes multimolecules reaction model into rapidly, and along with the further increase of methane amide volumetric concentration, the yardstick of multimolecules reaction model reduces gradually and disappears.Therefore, solvent provided by the invention can regulate and control the power of HAWSP solution heat resistance and salt tolerance.
Embodiment 2,
1) within 4 hours, be dissolved in methane amide by association type polyacrylamide in 70 DEG C of stirrings, mixing obtains association type polyacrylamide mother liquor; The concentration of this association type polyacrylamide mother liquor is 10000mg/L;
This association type polyacrylamide is formed by 0.8mol acrylamide, 0.2mol sodium acrylate and the copolymerization of 0.005mol hexadecyldimethyl benzyl ammonium allylic bromination ammonium, and molecular weight is 4.2 × 10
6g/mol.In this polymerization procedure, temperature is 50 DEG C, and the time is 8 hours;
2) by step 1) methane amide of gained volume to be the association type polyacrylamide mother liquor of x mL and volume be d mL and volume be that the water of w mL mixes, and obtains the solution system of different methane amide concentration expressed in percentage by volume y (being respectively 0%, 20%, 70%); Solution system;
Wherein, set the concentration c of association type polyacrylamide used in this solution system and be 500mg/L, the cumulative volume v of each solution system is 150mL; According to following x, w and the relation between d and y, c and v such as formula shown in I-formula III, described step 1 used can be obtained) in the volume x mL of association type polyacrylamide mother liquor x concrete numerical value and learn the concrete numerical value that the concrete numerical value of d in the volume d mL of methane amide and required volume of water are w in w mL:
W=v (1-y) (formula II)
In this mixing step, temperature is 30 DEG C, and the time is 3 hours.
Adopt XL30 scanning electronic microscope (SEM) to observe the quick freezing of the 500mg/LHAWSP solution of different methane amide volumetric concentration (being respectively 0,20%, 70%), vacuum-drying, ion sputtering film coating sample, experimental result is as Fig. 5 ~ 7.
As can be seen from Figure 5, the HAWSP distilled water solution of 500mg/L is multi-layer Network Framework, is connect form by the molecule chain bundle of different scale; As can be seen from Figure 6, methane amide volumetric concentration be 20%, HAWSP strength of solution is in the solution of 500mg/L, overall network structure has not existed, and HAWSP molecule mainly exists with the form of multimolecules reaction model, and its diameter is generally 2 ~ 5 μm; As can be seen from Figure 7, methane amide volumetric concentration be 70%, HAWSP strength of solution is in the solution of 500mg/L, cannot find the structure with multimolecules reaction model feature, in solution, associative structure is broken.The structure and morphology observed result of association type polyacrylamide solution illustrates the increase along with methane amide volumetric concentration, heat resistance and salt tolerance in HAWSP solution weakens gradually, and solution structure there occurs the change procedure of overall supramolecular network structure → multimolecules reaction model → monomolecular dispersion ball of string.
Embodiment 3,
1) within 6 hours, be dissolved in methane amide by association type polyacrylamide in 45 DEG C of stirrings, mixing obtains association type polyacrylamide mother liquor; The concentration of this association type polyacrylamide mother liquor is 10000mg/L;
This association type polyacrylamide is formed by 0.8mol acrylamide, 0.2mol sodium acrylate and the copolymerization of 0.005mol hexadecyldimethyl benzyl ammonium allylic bromination ammonium, and molecular weight is 4.2 × 10
6g/mol.In this polymerization procedure, temperature is 50 DEG C, and the time is 8 hours;
2) by step 1) methane amide of gained volume to be the association type polyacrylamide mother liquor of x mL and volume be d mL and volume be that the water of w mL mixes, and obtains the solution system of different methane amide concentration expressed in percentage by volume y (being respectively 10%, 30%, 50%, 70%, 85% and 100%); Solution system;
Wherein, set the concentration c of association type polyacrylamide used in this solution system and be 500mg/L, the cumulative volume v of each solution system is 300mL; According to following x, w and the relation between d and y, c and v such as formula shown in I-formula III, described step 1 used can be obtained) in the volume x mL of association type polyacrylamide mother liquor x concrete numerical value and learn the concrete numerical value that the concrete numerical value of d in the volume d mL of methane amide and required volume of water are w in w mL:
W=v (1-y) (formula II)
In this mixing step, temperature is 35 DEG C, and the time is 2 hours.
In addition, the blank that methane amide concentration expressed in percentage by volume is 0 is set.
Adopt the hydrodynamic radius being measured the polymkeric substance in the 500mg/L HAWSP solution of different methane amide volumetric concentration by correlator BI-9000AT type photon correlation spectrometer (Brookhaven Co.USA).Optical maser wavelength 532.0nm, scattering angle 90 °, probe temperature is 30 ± 0.1 DEG C; Distilled water and the formamide solvent of preparation sample adopt 0.2 μm of membrane filtration, and polymers soln adopts 2.0 μm of membrane filtration dedustings.The relation of the volumetric concentration (being set to 0,10%, 30%, 50%, 70%, 85% and 100% respectively) of association type polyacrylamide molecular particle size distributed median and methane amide is shown in Fig. 8.
As can be seen from Figure 8, when methane amide volumetric concentration is for increase to 10% from 0%, be in the solution of 500mg/L at association type concentration of polyacrylamide, size distribution intermediate value have dropped an order of magnitude, drops to 544.8nm from 5621nm; When methane amide volumetric concentration is greater than after 30%, size distribution intermediate value fluctuates between 170nm to 230nm.Experimental result shows, along with weakening of heat resistance and salt tolerance in solution, the hydrodynamic size of association type polyacrylamide amine molecule reduces gradually and tends towards stability, and describe in strong heat resistance and salt tolerance solution, association polymer exists with molecule aggregates form; And in weak heat resistance and salt tolerance solution, association polymer exists with monomolecular dispersion state.
Embodiment 4,
1) within 4 hours, be dissolved in methane amide by association type polyacrylamide in 50 DEG C of stirrings, mixing obtains association type polyacrylamide mother liquor; The concentration of this association type polyacrylamide mother liquor is 10000mg/L;
This association type polyacrylamide is formed by 0.8mol acrylamide, 0.2mol sodium acrylate and the copolymerization of 0.005mol hexadecyldimethyl benzyl ammonium allylic bromination ammonium, and molecular weight is 4.2 × 10
6g/mol.In this polymerization procedure, temperature is 50 DEG C, and the time is 8 hours;
2) by step 1) methane amide of gained volume to be the association type polyacrylamide mother liquor of x mL and volume be d mL and volume be that the water of w mL mixes, and obtains the solution system of different concentration of forma;
Wherein, the concentration expressed in percentage by volume y of methane amide is respectively the solution system of 30%, 50%, 60%, 70% and 80%, and the concentration c of association type polyacrylamide used in this solution system is 1000mg/L, and the cumulative volume v of solution system is 100mL; X, w and the relation between d and y, c and v are such as formula shown in I-formula III.
In this mixing step, temperature is 45 DEG C, and the time is 1 hour.
The subject matter that the test of HAWSP intrinsic viscosity exists shows two aspects: one is the ball of string structure that Intramolecular association effect makes polymkeric substance present more to tighten, and shows as less intrinsic viscosity; Two is multimolecules reaction model that Interpolymer Association is formed, and the intrinsic viscosity of polymkeric substance is increased greatly, and both of these case all can cause comparatively big error.Therefore, HAWSP intrinsic viscosity test problem be solved, must heat resistance and salt tolerance be eliminated, make the polymer molecule in solution be in monomolecular dispersion state.
Adopt the solvent composition of regulation and control HAWSP solution heat resistance and salt tolerance provided by the invention, when methane amide volumetric concentration is enough large, heat resistance and salt tolerance can be eliminated completely.
At employing solvent compositions provided by the invention simultaneously, in association type polyacrylamide solution system, add small molecules electrolyte sodium chloride, with the polyelectrolyte effect between shielded polymer molecular chain, get final product the intrinsic viscosity of Accurate Determining HAWSP.
Methane amide volumetric concentration is on the impact of intrinsic viscosity
The degree that the intrinsic viscosity of polymkeric substance in different solvents can reflect the convergence of a macromole ball of string, curl./ the Changing Pattern of Interpolymer Association behavior and heat resistance and salt tolerance can be reflected in HAWSP molecular chain molecule by comparing the intrinsic viscosity Changing Pattern of HAWSP in different solvents environment.
Test the intrinsic viscosity of association type polyacrylamide in different volumes concentration (being set to 30%, 50%, 60%, 70% and 80% respectively) formamide soln, intrinsic viscosity calculation formula is Fedors equation, and experimental result is shown in Fig. 9.(intrinsic viscosity test condition: polymkeric substance starting point concentration is 1000mg/L, sodium chloride concentration is 0.5M, dilution type Ubbelohde viscometer internal diameter 0.66mm, probe temperature 30 DEG C, and experiment concrete steps are with reference to GB 12005.1-89).
Experimental result shows, when methane amide volumetric concentration is 30 ~ 70%, For Intrinsic Viscosity Measurements results change is larger, illustrate within the scope of this, methane amide volumetric concentration is comparatively large on the impact of HAWSP molecular conformation, and its hydrodynamic volume constantly changes, when methane amide volumetric concentration >=70%, intrinsic viscosity test result keeps stable, illustrates that now associative structure is broken completely in solution, the molecular conformation kept stable of HAWSP.
Sodium chloride concentration is on the impact of intrinsic viscosity
Sodium-chlor belongs to small molecules ionogen, has considerable influence to the interaction between the serial polyelectrolyte type HAWSP molecular chain that the present invention relates to.Sodium chloride concentration (be respectively 0,0.1mol/L, 0.25mol/L, 0.5mol/L, 1.0mol/L) is shown in Figure 10 to the impact of HAWSP intrinsic viscosity test value.(intrinsic viscosity test condition: polymkeric substance starting point concentration is 1000mg/L, methane amide volumetric concentration is 70%, dilution type Ubbelohde viscometer internal diameter 0.66mm, probe temperature 30 DEG C, and experiment concrete steps are with reference to GB12005.1-89).
As can be seen from the experimental result of Figure 10, after NaCl concentration is greater than 0.25M, can play the effect of shielding polyelectrolyte effect, the impact of concentration on intrinsic viscosity continuing to increase sodium-chlor is less, and intrinsic viscosity value tends towards stability.
As from the foregoing, by adjusting the volumetric concentration of methane amide, when the volumetric concentration of methane amide reaches 70%, the association between hydrophobic grouping can be eliminated, making polymers soln be in monomolecular dispersion state; And the concentration adding small molecules electrolyte sodium chloride is after being greater than 0.25M, shield the polyelectrolyte effect of association type polyacrylamide solution, the characteristic 0 viscosity number value of therefore testing with this understanding is actual value, and this molecular weight for viscosimetry test HAWSP provides condition.
Claims (3)
1. one kind can the method for heat resistance and salt tolerance power in Effective Regulation association type polyacrylamide solution, it is characterized in that: described association type polyacrylamide solution, be made up of the association type polyacrylamide as solute and the mixed solution be made up of methane amide and water as solvent;
Or, by the association type polyacrylamide as solute with form as the methane amide of solvent;
Or, by the association type polyacrylamide as solute with form as the water of solvent;
Described solution prepares according to the method comprised the steps:
1) be dissolved in methane amide by described association type polyacrylamide, mixing obtains described association type polyacrylamide mother liquor; The concentration of described association type polyacrylamide mother liquor is 10000mg/L;
2) by described step 1) methane amide of gained volume to be the association type polyacrylamide mother liquor of x mL and volume be d mL and volume be that the water of w mL mixes, and obtains described association type polyacrylamide solution;
Wherein, the concentration expressed in percentage by volume of known described methane amide is y, the concentration of described association type polyacrylamide is cmg/L, the volume of described solution system is v mL, according to formula I, formula II and formula III, x, w and d and described relational expression between y, c and v, can obtain the concrete numerical value of described x, w and d;
W=v (1-y) (formula II)
The product of described association type polyacrylamide all for being obtained 40 ~ 60 DEG C of reactions 6 ~ 10 hours by 0.7 ~ 1.0mol acrylamide, 0.15 ~ 0.3mol sodium acrylate and 0.001 ~ 0.01mol hexadecyldimethyl benzyl ammonium allylic bromination ammonium; The molecular weight of described association type polyacrylamide is 0.50 × 10
6~ 8.0 × 10
6g/mol;
Described by the association type polyacrylamide as solute and the mixed solution be made up of methane amide and water as solvent, the volume percent of described methane amide and water is 0 ~ 100%, and the volume percent of described methane amide and water is not all 0;
Described association type concentration of polyacrylamide solution is 500 ~ 5000mg/L;
Described step 1) described association type polyacrylamide is dissolved in carboxamide Step, and temperature is 35-55 DEG C, and the time is 2-8 hour;
Described step 2) mix in step, temperature is 25-45 DEG C, and the time is 1-4 hour;
Described step 2) in, association type concentration of polyacrylamide solution c is 500 ~ 5000mg/L, and the concentration expressed in percentage by volume y of methane amide is 0 ~ 100%.
2. method according to claim 1, is characterized in that: the product of described association type polyacrylamide all for being obtained 50 DEG C of reactions 8 hours by 0.8mol acrylamide, 0.2mol sodium acrylate and 0.005mol hexadecyldimethyl benzyl ammonium allylic bromination ammonium; The molecular weight of described association type polyacrylamide is 4.2 × 10
6g/mol;
Described by the association type polyacrylamide as solute and the mixed solution be made up of methane amide and water as solvent, the volume percent of described methane amide is 70%;
Described association type concentration of polyacrylamide solution is 2000mg/L.
3. method according to claim 1, is characterized in that: described step 2) in, association type concentration of polyacrylamide solution c is 2000mg/L, and the concentration expressed in percentage by volume y of methane amide is 70%.
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| "Influence of the Hydrophobe Structure on Composition,Microstructure, and Rheology in Associating Polyacrylamides Prepared by Micellar Copolymerization";Edgar Volpert et al.;《Macromolecules》;19960226;第39卷(第5期);第1452-1463页 * |
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