CN111875737B - Phenylboronic acid polymer, preparation method thereof and application thereof in modified xanthan gum - Google Patents
Phenylboronic acid polymer, preparation method thereof and application thereof in modified xanthan gum Download PDFInfo
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Abstract
The invention discloses a phenylboronic acid polymer, a preparation method thereof and application of the phenylboronic acid polymer in modified xanthan gum. The structural formula of the phenylboronic acid polymer is shown as a formula I. After the phenylboronic acid polymer and the xanthan gum are compounded, the viscosity of a xanthan gum solution is obviously increased, wherein the viscosity increasing range of a polymer P-1.0% with the molar ratio of the phenylboronic acid monomer being 1.0 mol% in pure water to the xanthan gum solution is 43.8%, the viscosity increasing range of the polymer P-1.0% in 8074mg/L mineralized water is 56.4%, and the existence of a micro-crosslinking structure in a compounding system is proved through a rheological curve. The xanthan gum modified by the phenylboronic acid polymer has good ageing resistance and degradability in pure water and mineralized water, and meanwhile, a compound system has strong anti-interference performance on ethylene glycol and 1, 3-propylene glycol. The compound system of the phenylboronic acid polymer and the xanthan gum can be used as a polymer oil displacement agent, and can improve the viscosity of a displacement fluid, enlarge swept volume and improve the recovery ratio.
Description
Technical Field
The invention relates to a phenylboronic acid polymer, a preparation method thereof and application of the phenylboronic acid polymer in modified xanthan gum, and belongs to the technical field of polymer flooding.
Background
At present, the polymer oil displacement agent commonly used in oil fields comprises two main types of artificial synthetic polymers and natural polymers, wherein the two main types of artificial synthetic polymers and natural polymers are represented by partially Hydrolyzed Polyacrylamide (HPAM) and derivatives thereof and xanthan gum (XC). Xanthan gum is an extracellular polysaccharide produced by fermentation of xanthomonas sp,d-glucose, D-mannose and D-glucitol are mixed according to a molar ratio of 2.8: 2.0: 2.0, the molecular weight of which can reach 2 x 106～5×107g/mol. Compared with partially Hydrolyzed Polyacrylamide (HPAM), the xanthan gum still has higher viscosity under the conditions of high temperature and high mineralization degree, has stronger shear resistance, is not easy to be absorbed by reservoir rock, and can successfully adjust the oil wettability in an oil layer so as to improve the recovery ratio. However, xanthan gum has high production cost, large consumption, limited temperature resistance and is easy to be thermally degraded in a high-temperature oil layer. Therefore, modification of xanthan gum by means of nano composite hybridization, hydrophobic modification, branched modification, supermolecule self-assembly and the like is expected to improve the temperature resistance, reduce the consumption and improve the oil displacement effect.
Disclosure of Invention
The invention aims to provide a phenylboronic acid polymer, a preparation method thereof and application of the phenylboronic acid polymer in modified xanthan gum, wherein Acrylamide (AM), N- (3-dimethylaminopropyl) acrylamide (DMAPAM) and 3-acrylamidophenylboronic Acid (AMBB) are copolymerized to obtain a copolymer of three monomers, namely the phenylboronic acid polymer; the phenylboronic acid polymer has a remarkable tackifying effect on xanthan gum, and can improve the ageing degradation resistance of the xanthan gum and the anti-interference performance of the xanthan gum on ethylene glycol and 1, 3-propylene glycol.
The structural formula of the phenylboronic acid polymer provided by the invention is shown as a formula I:
in formula I, x, y and z represent the molar content of the corresponding structural unit in the polymer, respectively, x: y: z is 85-89.9: 10: 0.1 to 5, preferably 89 to 89.9: 10: 0.1-1, 89: 10: 1 or 89.9: 10: 0.1 to 0.1;
the polymer of phenylboronic acid has a weight average molecular weight of no greater than 105g/mol。
The phenylboronic acid polymer may be prepared as follows:
under the condition of inert atmosphere and initiator, the acrylamide, N- (3-dimethylaminopropyl) acrylamide and 3-acrylamide phenylboronic acid are subjected to free radical polymerization reaction to obtain the product.
In the above preparation method, the initiator may be a water-soluble initiator, such as azobisisobutylamidine dihydrochloride (AIBA), potassium persulfate, or ammonium persulfate, etc., preferably AIBA.
In the preparation method, the temperature of the free radical polymerization reaction is 55-80 ℃, the time is 3-15 h, for example, the reaction is carried out for 10h at 70 ℃.
In the above preparation method, the molar ratio of the acrylamide, the N- (3-dimethylaminopropyl) acrylamide and the 3-acrylamidophenylboronic acid may be 85 to 89.9: 10: 0.1 to 5, preferably 89 to 89.9: 10: 0.1-1, 89: 10: 1 or 89.9: 10: 0.1.
the phenylboronic acid polymer can be used for modifying xanthan gum and is compounded with a xanthan gum aqueous solution, the addition amount of the phenylboronic acid polymer can be 0-600 mg/L, and the mass-volume concentration of the xanthan gum can be 1-5 g/L, preferably 2 g/L.
According to the system formed by compounding the phenylboronic acid polymer and the xanthan gum, a dynamic borate bond is formed by the phenylboronic acid polymer and the xanthan gum (which has a repeated structure of various sugar ring units and contains a large amount of primary and secondary alcohol hydroxyl structures), so that the micro-crosslinking tackifying effect is achieved, compared with the xanthan gum, the viscosity of the compounding system is remarkably enhanced, for example, when the molar content of the phenylboronic acid monomer in the phenylboronic acid polymer is 1.0%, the tackifying amplitude of the phenylboronic acid polymer to a xanthan gum solution is 43.8%, and the tackifying amplitude in 8074mg/L mineralized water is up to 56.4%.
Compared with the viscosity of a xanthan gum solution and the viscosity of a compound system of the phenylboronic acid polymer and the xanthan gum, which are disclosed by the invention, in the aging process, the viscosity of all the solutions is gradually reduced along with the increase of time, but compared with a simple xanthan gum solution, the viscosity of the compound system is slowly reduced, because dynamic boric acid ester bonds are formed between boric acid groups and structural units of the xanthan gum, under the condition that the main structure of the xanthan gum is damaged, the viscosity losing speed of the compound system is effectively delayed due to the connection effect of the phenylboronic acid polymer, and the viscosity property of the phenylboronic acid polymer is improved while the anti-aging degradation capability of the xanthan gum is obviously improved.
The invention also considers the viscosity change of the complex system in the aging process of the mineralized water, the viscosity of all the solutions is gradually reduced along with the increase of time as the aging process of the complex system in the mineralized water is the same as that in the pure water, but the tackifying effect of the complex system in the mineralized water is stronger than that in the pure water due to the existence of CO in the mineralized water2 3-And HCO3 -The solution is weakly alkaline, borate is better activated, the binding capacity between the borate and the structural unit of xanthan gum is stronger, and stronger thickening property is shown.
The binding capacity of the boric acid polymer and hydroxyl in the xanthan gum structural unit is higher than that of the boric acid polymer and hydroxyl in the xanthan gum structural unit, and the binding capacity of the boric acid polymer and the hydroxyl in the xanthan gum structural unit is higher than that of the boric acid polymer and the ethylene glycol and 1, 3-propylene glycol, so that the compound system has stronger anti-interference performance on the ethylene glycol and the 1, 3-propylene glycol.
According to the invention, functional monomers of 3-acrylamidophenylboronic acid, Acrylamide (AM) and N- (3-dimethylaminopropyl) acrylamide (DMAPAM) are subjected to free radical copolymerization initiated by azobisisobutylamidine dihydrochloride (AIBA) in an aqueous solution to synthesize three phenylboronic acid polymers P (AM-co-DMAPAM-co-AMBB) with different copolymerization ratios, and the weight average molecular weights of the polymers are 10 measured by light scattering5Has better solubility under g/mol.
After the phenylboronic acid polymer and the xanthan gum are compounded, the viscosity of a xanthan gum solution is obviously increased, wherein the viscosity increasing range of a polymer P-1.0% with the molar ratio of the phenylboronic acid monomer being 1.0 mol% in pure water to the xanthan gum solution is 43.8%, the viscosity increasing range of the polymer P-1.0% in 8074mg/L mineralized water is 56.4%, and the existence of a micro-crosslinking structure in a compounding system is proved through a rheological curve. The xanthan gum modified by the phenylboronic acid polymer has good ageing resistance and degradability in pure water and mineralized water, and meanwhile, a compound system has strong anti-interference performance on ethylene glycol and 1, 3-propylene glycol. The compound system of the phenylboronic acid polymer and the xanthan gum can be used as a polymer oil displacement agent, and the recovery ratio can be improved.
Drawings
FIG. 1 shows a nuclear magnetic hydrogen spectrum of polymer P (AM-co-DMAPAM-co-AMBB) (FIG. 1(a)) and a nuclear magnetic hydrogen spectrum of sample P-1.0% (FIG. 1 (b)).
FIG. 2 is an infrared spectrum of polymer P (AM-co-DMAPAM-co-AMBB).
FIG. 3 shows the viscosity of the formulated system as a function of the amount of phenylboronic acid polymer P (AM-co-DMAPAM-co-AMBB) (xanthan gum content 2.0 g/L).
FIG. 4 is a plot of viscosity as a function of shear rate for xanthan gum (2.0g/L) formulated with varying concentrations of polymer P-1.0%.
FIG. 5 is a plot of elastic (G ') and viscous (G') moduli as a function of frequency for xanthan gum (2.0G/L) formulated with varying concentrations of polymer P-1.0%.
FIG. 6 shows the aging resistance of xanthan gum (2.0g/L) in pure water with varying concentrations of the polymer P-1.0% complexing system at 65 ℃.
FIG. 7 shows the aging resistance of xanthan gum (2.0g/L) and different concentrations of polymer P-1.0% complexing system in mineralized water at 65 ℃.
FIG. 8 shows the effect of ethylene glycol (FIG. 8(a)) and 1, 3-propanediol (FIG. 8(b)) (10.0g/L) on the aging resistance of xanthan gum (2.0g/L) formulated with varying concentrations of polymer P-1.0%.
Detailed Description
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The materials, reagents and equipment used in the following examples are as follows:
3-aminobenzeneboronic acid, acryloyl chloride, N- (3-dimethylamino) propylacrylamide (DMAPAM), azodiisobutylaminum dihydrochloride (AIBA), acrylamide, deuterated dimethyl sulfoxide and deuterated water, and the analytically pure, Beijing Bailingwei science and technology Limited; sodium hydroxide, acrylamide, hydrochloric acid, alkaline alumina (100-200 meshes), sodium chloride, potassium chloride, calcium chloride, magnesium chloride, sodium sulfate, sodium carbonate, sodium bicarbonate, ethanol and diethyl ether, and the Chinese medicines are gathered into groupsChemical reagents, Inc. Deionized water was produced using a Milli-Q ultrapure water system and had a resistivity of 18.2M Ω. cm. The total mineralization of the mineralized water used in the experiment was 8074mg/L, with the main ion content (mg/L) as follows: na (Na)++K+2804、Ca2+222、Mg2+83、CO3 2-48、HCO3 -559、SO4 2-25、Cl-4332。
Bruker AVANCE 400MHz superconducting nuclear magnetic resonance spectrometer, Bruker, germany; agilent model 6520 quadrupole time-of-flight tandem mass spectrometer, Agilent corporation, usa; agilent Cary 630 fourier transform infrared spectrometer, Agilent corporation, usa; vario EL cube elemental analyzer, Elementer, Germany; brookfield DV3T viscometer, Brookfield corp; DAWN HELEOS model multi-angle laser light scattering apparatus, Wyatt USA; HAAKE MARS III Torque rheometer, Thermo Fisher Inc., USA.
The 3-acrylamidophenylboronic Acid (AMBB) used in the following examples was prepared as follows:
the synthetic route is as follows:
3-Aminophenylboronic acid (2.0782g,15.2mmol) was dissolved in 10% by weight aqueous NaOH (25mL) to turn tan, and the reaction flask was placed in an ice bath. Acryloyl chloride (2.5mL,30.8mmol) was slowly added to the reaction mixture, which was allowed to cool to room temperature, and stirred for 18 h. After the reaction, black solid lumps were formed in the solution, and the reaction solution was adjusted to pH 3 with HCl solution, resulting in gray powder. Filter and wash the solid with ice water. The crude product was dissolved by heating with 30% by volume aqueous ethanol (20mL), and after hot filtration, the solution was allowed to stand overnight at room temperature to precipitate brown crystals. Filtration and drying of the product in a vacuum oven to constant weight gave 903.1mg of 3-acrylamidophenylboronic acid as brown crystalline product in 31.2% yield.
1H NMR(DMSO-d6,400MHz),δ:10.08(s,1H,NH),8.04(s,2H,OH),7.88(s,1H,ArH),7.82(d,J＝9.1Hz,1H,ArH),7.50(d,J＝7.3Hz,1H,ArH),7.28(t,J＝7.7Hz,1H,ArH),6.45(dd,J＝17.0,10.1Hz,1H,CH2＝CH),6.24(dd,J＝17.0,2.1Hz,1H,CH2＝CH),5.74(dd,J＝10.1,2.1Hz,1H,CH2＝CH).13C NMR(DMSO-d6,101MHz),δ:163.50,138.64,132.47,129.75,128.22,127.09,125.82,121.77.HRMS(m/z):[M+H]+Calculated 191.0868,192.0832, test value 191.0839,192.0908.
Example 1 Synthesis of terpolymer P (AM-co-DMAPAM-co-AMBB)
The synthetic route is as follows:
the N- (3-dimethylaminopropyl) acrylamide contains p-Methoxyphenol (MEHQ) as a polymerization inhibitor, and a monomer is purified before polymerization, wherein the processing method comprises the following steps: and (3) separating and purifying the monomer N- (3-dimethylaminopropyl) acrylamide through an alkaline alumina (100-200 meshes) chromatographic column (the column height is 8cm), leaching with anhydrous ether, drying the eluent in a vacuum drying oven for 24 hours after rotary evaporation, and changing the monomer from yellow before removal of the polymerization inhibitor to colorless.
The polymerization steps are as follows: acrylamide (AM), N- (3-dimethylaminopropyl) acrylamide (DMAPAM) and 3-acrylamidophenylboronic Acid (AMBB) are weighed according to the proportion in table 1, dissolved in deionized water (the total mass fraction of the three monomers is 10 percent), and vacuumized and introduced with N2Removing oxygen for three times, injecting azodiisobutyl amidine dihydrochloride (AIBA) dissolved in water in advance into a reaction bottle by using a syringe, vacuumizing and introducing N2Three times, and the reaction is carried out for 10 hours at 70 ℃. After the reaction is finished, the viscosity of the solution is obviously increased, water is added into the reaction solution until the concentration is 20g/L, and the mixture is stirred until the homogeneous phase is used as a polymer mother solution for standby.
TABLE 1 copolymerization ratio of Polymer P (AM-co-DMAPAM-co-AMBB), amount of initiator
Structural characterization of P (AM-co-DMAPAM-co-AMBB):
1. nuclear magnetic resonance spectrum
Taking a small amount of polymer P (AM-co-DMAPAM-co-AMBB) mother liquor, dialyzing in pure water for three days at room temperature through an MWCO 1000 dialysis bag, and freeze-drying the dialyzate to obtain a final polymer sample. The test sample is dissolved by deuterium and prepared into a solution with the mass fraction of about 1 percent, the solution is loaded into a nuclear magnetic tube with the caliber of 5mm, and the nuclear magnetic resonance spectrogram is obtained by scanning 128 times at 298K, and is shown in figure 1.
Three polymer P (AM-co-DMAPAM-co-AMBB) samples of different monomer ratios: the nuclear magnetic hydrogen spectra of P-0.1%, P-1.0%, and P-5.0% are shown in FIG. 1 (a). As can be seen, the C-H signal of the benzene ring in the copolymer is around 7.4ppm (denoted by f in the figure), the methyl signal peak of the structural unit N- (3-dimethylaminopropyl) acrylamide is at 2.7ppm (denoted by e in the figure), the methylene signal peaks are at 3.1 and 1.8ppm (denoted by C and d in the figure), the methylene signal peak of the copolymer backbone is at 1.5ppm (denoted by a in the figure), and the methine signal peak is at 2.1ppm (denoted by b in the figure). Namely, proton signal peaks of acrylamide, N- (3-dimethylaminopropyl) acrylamide and 3-acrylamidophenylboronic acid which are three structural units in the polymer can be found in a nuclear magnetic hydrogen spectrum diagram, and the successful synthesis of the terpolymer P (AM-co-DMAPAM-co-AMBB) is proved.
The nuclear magnetic hydrogen spectrum and signal attribution of sample P-1.0% are shown in FIG. 1 b. Calculated from the integral (100-15.10/2-3.62/4): (15.10/2): (3.62/4) obtaining the molar ratio n (AM) of the three structural units in the sample P-1.0%: n (dmapam): n (AMBB) 91.54: 7.55: 0.91, and a monomer feed ratio of 89.0: 10.0: 1.0 is not very different. The molar ratio of the three structural units in sample P-5.0% was found to be 81.60 by the same integral calculation method: 12.13: 6.27, monomer feed ratio 85.0: 10.0: 5.0 approach. The three-monomer copolymerization process can be proved to be close to ideal copolymerization. The molar ratio of the structural units is not calculated because the C-H signal peak of the benzene ring in the P-0.1% sample is weak and the integral error is large.
2. Infrared spectroscopy
The lyophilized polymer sample was passed through an Agilent Cary 630ATR sampling accessoryTesting, wherein the scanning range is 4000-650 cm-1。
Three polymer P (AM-co-DMAPAM-co-AMBB) samples of different monomer ratios: the infrared spectra of P-0.1%, P-1.0%, and P-5.0% are shown in FIG. 2. It can be seen that 3336cm-1And 3192cm-1Is represented by-NH2And a stretching vibration absorption peak of phenylboronic acid group-OH, 1655cm-1At 1608cm, which is an amide group C ═ O stretching vibration absorption peak-1Is represented by-NH21560cm in bending vibration absorption peak-11446cm at the bending vibration absorption peak of-NHR-1The position is a vibration absorption peak of a benzene ring framework. That is, absorption peaks of acrylamide, N- (3-dimethylaminopropyl) acrylamide and 3-acrylamidophenylboronic acid which are three structural units in the polymer can be found in an infrared spectrogram, and the successful synthesis of the terpolymer P (AM-co-DMAPAM-co-AMBB) is proved.
3. Elemental analysis
About 5mg of the polymer sample obtained by lyophilization was precisely weighed, and the content of C, H, N elements in the polymer was measured by a Vario EL cube element analyzer, Elementer, Germany.
TABLE 2 analysis of elemental composition in Polymer P (AM-co-DMAPAM-co-AMBB) samples
Three polymer P (AM-co-DMAPAM-co-AMBB) samples of different monomer ratios: the results of the elemental analyses for P-0.1%, P-1.0%, and P-5.0% are shown in Table 2, and the actual molar ratio of each monomer in the polymer can be calculated from the C, H, N content in the polymer and monomer. Comparing the monomer feeding ratio with the actual molar ratio of the monomers in the polymer shows that: the actual molar ratio of each monomer in the three polymers was not much different from the polymerization batch ratio, as shown in table 2. The three comonomers are all acrylic monomers, the polymerization activities are similar and close to ideal copolymerization, and the mixture ratio of the copolymer composition and the monomers is not greatly different.
4. Absolute weight average molecular weight test of Polymer
The absolute weight average molecular weight measuring instrument for the polymer was a multi-angle laser light scattering instrument of the model DAWN HELEOS, Wyatt, USA. The light source is 50mW GaAs linear polarization laser with wavelength 658nm, and the fixed deca-octagon detector array is used for synchronously measuring and collecting light scattering signals at 22.5-147.0 deg., and the molecular mass measurement range is 103～109g/mol. The dn/dc is measured by an Optilab rEX extensional differential refractometer, and the light source and the laser wavelength are the same as those of a laser light scattering instrument.
Dissolving a polymer sample obtained by freeze-drying with 0.1mol/L NaCl solution to prepare 8 concentration gradient solutions (the concentration interval is 0.5-5 mg/mL), filtering by a 0.8 mu M cellulose ester material filter head (Millipore) to remove dust and particles, placing in a special light scattering bottle, carrying out sample injection measurement in sequence from thin to thick, and obtaining the weight average molecular weight M of the polymer through a Zimm chart of a test resultwAnd a second coefficient of virility A2。
TABLE 3 static light scattering data for Polymer P (AM-co-DMAPAM-co-AMBB)
Zimm graphs of the polymers P-0.1%, P-1.0% and P-5.0% plotted from data collected by static light scattering were calculated to obtain the weight average molecular weight and the second dimensional coefficient, respectively, and the results are shown in Table 3. The weight average molecular weights of the polymers are all 105The polymer with the lower molecular weight has shorter dissolution time and can better meet the polymer injection requirement of offshore oil fields.
The second coefficient of merit is a measure of the internal repulsion between the polymer chain segments and the energetic interaction between the polymer chain segments and the solvent molecules, which compete with each other. A. the2The polymer is a positive value, which represents that a polymer chain expands due to solvation and a polymer coil stretches, and the solvent at the moment is a good solvent of the polymer, so that the spontaneous tendency of the dissolving process is strong; a. the20, which represents that the solution meets the properties of an ideal solution, the solvent is called theta solvent, and the temperature is called theta temperature; a. the2Is negativeThe value represents the polymer chain contraction, and the solvent in this case is a poor solvent for the polymer. Second dimensional coefficient A of three polymers P (AM-co-DMAPAM-co-AMBB)2As a result of the measurement, it was found that the polymer was in a stretched state in a 0.1mol/L NaCl solution and had good stability and solubility.
Example 2 modification study of Polymer P (AM-co-DMAPAM-co-AMBB) on Xanthan Gum
The xanthan gum is stirred and dissolved by deionized water at room temperature to prepare xanthan gum mother liquor with the mass concentration of 2.5g/L, the xanthan gum mother liquor and 20g/L phenylboronic acid polymer mother liquor are mixed and diluted to the target compound concentration according to the proportion, and the mixture is stirred and mixed uniformly at room temperature. The concentration of the xanthan gum in the compound solution is 2.0g/L, and the concentrations of the phenylboronic acid polymer are 0, 20, 100, 200, 300, 400, 500 and 600mg/L respectively. According to standard Q/HS2032-[21]And measuring the viscosity of the compound solution to evaluate the tackifying performance of the compound system.
1. Tackifying of built systems
The xanthan gum concentration is 2.0g/L, and the viscosity of the compound system changes with the addition of the phenylboronic acid polymer P (AM-co-DMAPAM-co-AMBB) as shown in FIG. 3. It can be seen that when the molar ratio of the phenylboronic acid monomer in the polymer is 0.1 mol% and 1.0 mol%, the viscosity of the formulated system increases significantly with increasing polymer usage. For sample P-1.0%, namely the molar ratio of the phenylboronic acid monomer in the polymer is 1.0 mol%, when the dosage is 600mg/L, the viscosity of the compounded system is increased from 169.3mPa & s initially to 243.2mPa & s, the viscosity increase rate is as high as 43.8%, and the result proves that the phenylboronic acid polymer and the xanthan gum achieve the effect of micro-crosslinking and tackifying through forming dynamic borate bonds. When the molar ratio of the phenylboronic acid monomer in the polymer is 5.0 mol%, the viscosity of the compound system is reduced because the flocculation phenomenon easily occurs due to the excessively high crosslinking density between the polymer and the xanthan gum.
2. Rheology test
The rheological test instrument is an HAAKE MARS III rheometer, and a rotary shearing experiment and an oscillating shearing experiment are both tested at 25 ℃ by adopting a rotary drum and a CC24 rotor. Preparation method of xanthan gum and phenylboronic acid polymer compound solution and solution in thickening testThe preparation method is the same. In the rotary shearing experiment, the scanning range of the shearing rate is 0.02-10 s-1(ii) a In the oscillation shearing experiment, the stress is 0.1Pa, and the frequency scanning range is 0.01-1 Hz.
The change curve of the viscosity of the xanthan gum and polymer P-1.0% compound system along with the shear rate is shown in FIG. 4, the viscosity values of the compound system are all higher than that of a single xanthan gum solution in the tested shear rate range, and the viscosity increase amplitude of the compound system is larger along with the increase of the concentration of the polymer P-1.0%. All solutions exhibited the same property with increasing shear rate, i.e. the viscosity of the solution did not change before it decreased significantly. This is because the molecular conformation of xanthan gum in solution and xanthan gum forming micro-cross-linked structure with polymer P-1.0% is not changed along with the shearing force field basically under the low shearing rate, and the entanglement between high molecular chains and dynamic borate bond are not destroyed basically under the low shearing rate. Under the condition of high shear rate, when partial xanthan gum molecules in the solution are subjected to the action of a high shear force field, molecular chains are changed from an intertwined disordered structure into an orientation along the direction of the shear force field, the orderliness of the molecules in the system is increased, and the phenomenon of shear thinning is shown. In a compound system, due to the existence of a micro-crosslinking structure, the resistance of the compound system to a shearing force field is enhanced, and molecular chains are more difficult to convert from disordered distribution to ordered distribution, so that higher viscosity is expressed in the shearing force field.
Viscoelasticity testing of xanthan gum formulated with polymer P-1.0% as shown in fig. 5, the elastic (G') and viscous (G ") moduli of all solutions increase with increasing frequency over the frequency range tested. For xanthan solutions, in the low frequency range, G "> G', its properties are mainly viscosity; in the high frequency range, G '> G ", whose properties are dominated by elasticity, the intersection of G' with G" occurs at 0.07 Hz. Compared with a pure xanthan gum solution, the viscosity modulus and the elastic modulus of a xanthan gum and polymer P-1.0% compound system are both greatly increased, wherein the increase of G' is more obvious, and the xanthan gum and the phenylboronic acid polymer form a micro-crosslinking system through a dynamic borate bond, so that the xanthan gum and the phenylboronic acid polymer have partial gel property. In a compound system, when the dosage of the polymer P-1.0% is larger, G' is always larger than G ", and no intersection point exists in a tested frequency range, so that the system is proved to have a stronger space grid structure and more obvious gel property. However, the G' value of the compounded system was always low, indicating that all solutions were always in solution.
3. Anti-aging property of complex system in pure water
The xanthan gum is respectively stirred and dissolved by deionized water and mineralized water with the mineralization degree of 8074mg/L at room temperature to prepare xanthan gum mother liquor with the mass concentration of 2.5g/L, the xanthan gum mother liquor and 20g/L phenylboronic acid polymer mother liquor are mixed and diluted to the target compound concentration according to the proportion, and the mixture is stirred and mixed uniformly at room temperature. The concentration of the xanthan gum in the compound solution is 2.0g/L, and the concentrations of the phenylboronic acid polymer are 0, 20, 100, 200, 300, 400, 500 and 600mg/L respectively. And sealing the solution, placing the solution in a constant temperature incubator at 65 ℃, and measuring the viscosity of the compound solution under different aging times according to the standard Q/HS2032-2018 so as to evaluate the aging resistance of the compound system.
The viscosity of the xanthan gum and polymer P-1.0% in pure water during aging varied as shown in FIG. 6, and the viscosity of all solutions gradually decreased with time. In the aging degradation process, the reduction of the solution viscosity is caused by the breakage and damage of the molecular structure of the xanthan gum in the solution, but compared with a simple xanthan gum solution, the viscosity of the compound system is reduced slowly, because a dynamic boric acid ester bond is formed between a boric acid group and a structural unit of the xanthan gum, and under the condition that the main structure of the xanthan gum is damaged, the viscosity losing speed of the compound system is effectively delayed due to the connection effect of a phenylboronic acid polymer. The phenylboronic acid polymer obviously improves the anti-aging degradation capability of the xanthan gum while improving the viscosity property of the xanthan gum.
In order to investigate the influence of salt on the viscosity and the aging resistance of a compound system, i.e. the stability of the system under the condition of actually applied mineralization, the viscosity change of the compound system in the aging process of mineralized water with the mineralization of 8074mg/L was studied, as shown in FIG. 7. As with the aging process in pure water, the viscosity of all solutions gradually increased with timeAnd (4) descending. However, the viscosity increasing effect of the compound system in mineralized water is stronger than that of pure water, the viscosity of xanthan gum is increased from 165.2mPa & s to 258.3mPa & s (the addition amount of polymer P-1.0% is 600mg/L), the viscosity increasing rate is as high as 56.4%, and the viscosity increasing rate in pure water under the same conditions is 43.8%. This is due to the presence of CO in the mineralized water3-And HCO3 2-The solution is weakly alkaline, borate is better activated, the binding capacity between the borate and the structural unit of xanthan gum is stronger, and stronger thickening property is shown.
4. Interference immunity
The xanthan gum is stirred and dissolved by deionized water at room temperature to prepare xanthan gum mother liquor with the mass concentration of 2.5g/L, the xanthan gum mother liquor is mixed and diluted with ethylene glycol or 1, 3-propylene glycol and 20g/L phenylboronic acid polymer mother liquor according to a proportion to a target compound concentration, and the xanthan gum is stirred and mixed uniformly at room temperature. The concentration of the xanthan gum in the compound solution is 2.0g/L, the concentration of the ethylene glycol or the 1, 3-propylene glycol is five times of that of the xanthan gum, namely 10.0g/L, and the concentrations of the phenylboronic acid polymers are 0, 20, 100, 200, 300, 400, 500 and 600mg/L respectively. And sealing the solution, placing the solution in a constant temperature incubator at 65 ℃, and measuring the viscosity of the compound solution under different aging times according to the standard Q/HS2032-2018 so as to evaluate the anti-interference performance of the compound system.
The boric acid group and the hydroxyl in the structural unit of the xanthan gum realize micro-crosslinking tackifying through forming a dynamic boric acid ester bond, but in the practical application process, if the cis-1, 2-or 1, 3-diol structural polyalcohol and the derivative thereof exist in the environment, the polyalcohol may react with the boric acid to form a five-membered or six-membered ring structure, and the tackifying property of the boric acid polymer on the xanthan gum is further influenced. Based on this, ethylene glycol and 1, 3-propanediol (10.0g/L) in an amount 5 times that of xanthan gum were added to the complex system, respectively, and the thickening property and the aging resistance of the complex system in the presence of a large amount of polyol were investigated. As shown in FIG. 8, in the presence of ethylene glycol and 1, 3-propylene glycol, the initial viscosity of the compounded system was not greatly reduced, and the anti-aging degradation ability was not much different from that of the compounded system without the addition of polyol. The bonding capability of the boric acid polymer and hydroxyl in the xanthan gum structural unit is higher than that of the boric acid polymer and the hydroxyl in the xanthan gum structural unit, and the complex system is proved to have stronger anti-interference performance on ethylene glycol and 1, 3-propylene glycol.
Claims (2)
1. The application of the phenylboronic acid polymer shown as the formula I in modified xanthan gum;
in formula I, x, y and z represent the molar content of the corresponding structural unit in the polymer, respectively, x: y: z is 85-89.9: 10: 0.1 to 5;
the polymer of phenylboronic acid has a weight average molecular weight of no greater than 105g/mol。
2. Use according to claim 1, characterized in that: the application is represented by any one of the following 1) to 3):
1) increasing the viscosity of the xanthan gum;
2) improving the aging degradation resistance of the xanthan gum;
3) the anti-interference performance of the xanthan gum on ethylene glycol and 1, 3-propylene glycol is improved.
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| US20050203256A1 (en) * | 2002-05-14 | 2005-09-15 | Mathias Destarac | Poymer obtained by means of controlled radical polymerisation comprising at least one boronate function, association thereof with a ligand compound and uses of same |
| CN102353653A (en) * | 2011-06-29 | 2012-02-15 | 南开大学 | Rapid response hydrogel film glucose optical sensor |
| US20140110120A1 (en) * | 2012-10-24 | 2014-04-24 | Halliburton Energy Services, Inc. | Oligomeric and Polymeric Electronically-Modified Boronic Acids and Methods of Using the Same |
| CN104628940A (en) * | 2013-11-15 | 2015-05-20 | 中国石油化工股份有限公司 | Acrylamide copolymer, as well as preparation method and application thereof |
| CN105294931A (en) * | 2015-01-30 | 2016-02-03 | 江南大学 | High molecular coagulant, as well as preparation method and application thereof |
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| US20050203256A1 (en) * | 2002-05-14 | 2005-09-15 | Mathias Destarac | Poymer obtained by means of controlled radical polymerisation comprising at least one boronate function, association thereof with a ligand compound and uses of same |
| CN102353653A (en) * | 2011-06-29 | 2012-02-15 | 南开大学 | Rapid response hydrogel film glucose optical sensor |
| US20140110120A1 (en) * | 2012-10-24 | 2014-04-24 | Halliburton Energy Services, Inc. | Oligomeric and Polymeric Electronically-Modified Boronic Acids and Methods of Using the Same |
| CN104628940A (en) * | 2013-11-15 | 2015-05-20 | 中国石油化工股份有限公司 | Acrylamide copolymer, as well as preparation method and application thereof |
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