CN111393538B - Zwitterionic hydrophobic modified guar gum and preparation method thereof - Google Patents
Zwitterionic hydrophobic modified guar gum and preparation method thereof Download PDFInfo
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- 229920002907 Guar gum Polymers 0.000 title claims abstract description 67
- 239000000665 guar gum Substances 0.000 title claims abstract description 67
- 229960002154 guar gum Drugs 0.000 title claims abstract description 67
- 235000010417 guar gum Nutrition 0.000 title claims abstract description 67
- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 125000000129 anionic group Chemical group 0.000 claims abstract description 23
- 244000007835 Cyamopsis tetragonoloba Species 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229940105325 3-dimethylaminopropylamine Drugs 0.000 claims abstract description 8
- IUNMPGNGSSIWFP-UHFFFAOYSA-N dimethylaminopropylamine Chemical compound CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000178 monomer Substances 0.000 claims abstract description 8
- 125000002091 cationic group Chemical group 0.000 claims abstract description 7
- 150000007524 organic acids Chemical class 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- 239000000243 solution Substances 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 12
- 239000012670 alkaline solution Substances 0.000 claims description 10
- 235000019441 ethanol Nutrition 0.000 claims description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 238000010992 reflux Methods 0.000 claims description 9
- 238000004821 distillation Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 150000003512 tertiary amines Chemical class 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 230000003113 alkalizing effect Effects 0.000 claims description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 3
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 claims description 2
- 239000002253 acid Substances 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 6
- 230000009881 electrostatic interaction Effects 0.000 abstract description 5
- 230000015784 hyperosmotic salinity response Effects 0.000 abstract description 5
- 230000001965 increasing effect Effects 0.000 abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 4
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 abstract description 2
- 229920006395 saturated elastomer Polymers 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 24
- 229920000642 polymer Polymers 0.000 description 9
- 239000000543 intermediate Substances 0.000 description 8
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 6
- 239000012530 fluid Substances 0.000 description 6
- 229920013818 hydroxypropyl guar gum Polymers 0.000 description 6
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 6
- 239000011976 maleic acid Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 5
- 230000008961 swelling Effects 0.000 description 5
- 230000008719 thickening Effects 0.000 description 5
- 239000002562 thickening agent Substances 0.000 description 5
- 150000001450 anions Chemical class 0.000 description 4
- 239000007806 chemical reaction intermediate Substances 0.000 description 4
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 4
- TUNFSRHWOTWDNC-UHFFFAOYSA-N Myristic acid Natural products CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- -1 hydroxypropyl Chemical group 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229920003169 water-soluble polymer Polymers 0.000 description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 125000003010 ionic group Chemical group 0.000 description 2
- 229920000831 ionic polymer Polymers 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000035772 mutation Effects 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/006—Heteroglycans, i.e. polysaccharides having more than one sugar residue in the main chain in either alternating or less regular sequence; Gellans; Succinoglycans; Arabinogalactans; Tragacanth or gum tragacanth or traganth from Astragalus; Gum Karaya from Sterculia urens; Gum Ghatti from Anogeissus latifolia; Derivatives thereof
- C08B37/0087—Glucomannans or galactomannans; Tara or tara gum, i.e. D-mannose and D-galactose units, e.g. from Cesalpinia spinosa; Tamarind gum, i.e. D-galactose, D-glucose and D-xylose units, e.g. from Tamarindus indica; Gum Arabic, i.e. L-arabinose, L-rhamnose, D-galactose and D-glucuronic acid units, e.g. from Acacia Senegal or Acacia Seyal; Derivatives thereof
- C08B37/0096—Guar, guar gum, guar flour, guaran, i.e. (beta-1,4) linked D-mannose units in the main chain branched with D-galactose units in (alpha-1,6), e.g. from Cyamopsis Tetragonolobus; Derivatives thereof
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- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/62—Compositions for forming crevices or fractures
- C09K8/66—Compositions based on water or polar solvents
- C09K8/68—Compositions based on water or polar solvents containing organic compounds
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/84—Compositions based on water or polar solvents
- C09K8/86—Compositions based on water or polar solvents containing organic compounds
- C09K8/88—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
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Abstract
The invention discloses a zwitter-ion hydrophobic modified guar gum which is characterized by comprising the following components in parts by weight: the structural formula is as follows:
R1is long chain organic acid, specifically long chain saturated acid with carbon chain of 6-14, or long chain unsaturated acid with carbon chain of 18-22; meanwhile, the invention also discloses a preparation method of the guar gum, which comprises the following steps: introducing an anionic monomer to the guar to form an anionic guar modified product; preparing a water-soluble amphiphilic cationic hydrophobic monomer from a hydrophobic long-chain, 3-dimethylamino propylamine and epichlorohydrin; water soluble amphiphilic cationic hydrophobic monomers are introduced into the anionic guar modified product to form an amphoteric hydrophobic modified product. According to the invention, the special electrostatic interaction of zwitterions and the hydrophobic association effect are fully utilized to endow the guar gum molecular chain with special dispersibility and rheological property, so that the guar gum has excellent solubility, viscosity increasing property, temperature resistance and salt tolerance.
Description
Technical Field
The invention relates to the technical field of oil and gas field development, in particular to zwitterionic hydrophobically modified guar gum and a preparation method thereof.
Background
At present, most oil fields enter the middle and later stages of development, most newly discovered reservoirs are low in permeability and poor in physical property, and the value of industrial development can be achieved only after the reservoirs are modified through fracturing and acidizing. And the effectiveness of fracturing depends largely on the properties of the fracturing fluid. The fracturing fluid must have sufficient viscosity to ensure that the proppant can smoothly reach the preset position of the fracture, and finally, a good reservoir transformation effect is achieved. In addition, changes in the mineralization of the formation, temperature, present significant challenges to the performance of the fracturing fluid.
The viscosity of the currently commonly used guar fracturing fluid is greatly reduced under the conditions of high temperature and high salt, the conventional method is to increase the dosage of guar, but the method not only increases the construction cost, but also increases the damage to a reservoir stratum.
Chinese patent publication No. CN102827300A, published as 2012, 12, and 19, discloses a preparation method and application of a hydrophobically modified guar gum, comprising the following steps: suspending guar gum in ionic liquid, adding an alkaline catalyst, and alkalizing at 10-40 ℃; gradually heating under the protection of nitrogen, slowly dropping a modifier, and heating to 30-80 ℃ for modification reaction; and after the reaction is finished, adding organic acid to adjust the pH value to 5-7, soaking and washing the mixture by using ethanol, filtering the mixture, and drying a filter cake in vacuum to obtain the hydrophobic modified guar gum. According to the scheme, the hydrophobic alkyl long chain is introduced to the hydroxyl group of the guar gum, the terminal group is a carboxylic acid group, the water-soluble speed of the guar gum is improved, the macromolecular mass characteristic of the guar gum is protected to the maximum extent, and the hydrophobic performance is endowed to the guar gum. However, the conventional hydrophobically modified guar gum represented by the above patent documents has a greatly reduced solubility due to the addition of only a single long hydrophobic chain, and is not favorable for rapid liquid preparation on site. Therefore, under the condition of not increasing the concentration of the thickening agent, the viscosity of the thickening agent is improved, and the salt and temperature resistance and the shearing resistance of the thickening agent are enhanced, so that the technical problem to be solved urgently is provided, and the technical problem has great production significance for yield increase modification of oil fields.
Disclosure of Invention
Aiming at the defects and shortcomings of the prior art, the invention provides the zwitter-ion hydrophobic modified guar gum, and the special electrostatic interaction and the hydrophobic association effect of the zwitter-ion are fully utilized to endow the guar gum molecular chain with special dispersibility and rheological property, so that the guar gum has excellent solubility, viscosity increasing property, temperature resistance and salt tolerance.
Meanwhile, the invention provides a preparation method of the zwitter-ion hydrophobic modified guar gum.
The invention is realized by adopting the following technical scheme:
a zwitterionic hydrophobically modified guar gum is characterized in that: the structural formula is as follows:
R1is long-chain organic acid, specifically long-chain saturated acid with carbon chain of 6-14, or long-chain unsaturated acid with carbon chain of 18-22.
The long-chain organic acid is n-hexanoic acid, n-octanoic acid, n-decanoic acid, n-dodecanoic acid, tetradecanoic acid, oleic acid or mesonic acid.
A preparation method of zwitterionic hydrophobically modified guar gum is characterized by comprising the following steps:
(1) introducing an anionic monomer into guar gum to form an anionic guar gum modified product for further use;
(2) preparing a water-soluble amphiphilic cationic hydrophobic monomer from a hydrophobic long-chain, 3-dimethylamino propylamine and epichlorohydrin;
(3) and introducing the prepared water-soluble amphiphilic cationic hydrophobic monomer into the anionic guar gum modified product to form an amphoteric hydrophobic modified product.
A preparation method of zwitterionic hydrophobically modified guar gum is characterized by comprising the following steps:
A. preparation of anionic guar gum: (1) putting a proper amount of alcohol-water solution into a flask; (2) adding 40-60 parts by weight of guar gum into a flask, setting the temperature to be 60 ℃, and stirring; (3) adding 2-4 parts by weight of alkaline catalyst, and stirring for 20-30 min; (4) adding 10-15 parts by weight of maleic anhydride into a flask, stirring, and reacting for 3-5h to obtain the anionic guar gum shown as formula 1:
B. preparation of water-soluble amphiphilic cationic hydrophobic monomer: (1) introducing nitrogen into the three-neck flask for 5-15min, and replacing the air in the flask; (2) adding long-chain organic acid and 3-dimethylaminopropylamine according to a molar ratio of 1: 1.1-1: 1.2; (3) dropwise adding 0.3-0.7 wt% of alkaline solution into the flask, raising the temperature to 120-170 ℃, reacting for 6-8 h, and then carrying out reduced pressure distillation to remove unreacted amine and generated water to obtain a tertiary amine product; (4) adding absolute ethyl alcohol serving as a solvent into a single-neck flask, heating to 70 ℃, adding a tertiary amine product and epoxy chloropropane into the flask according to the molar ratio of 1:1.1, adding a reflux pipe, reacting for 10 hours, and then performing rotary distillation to remove the solvent to finally obtain a paste intermediate, wherein the formula is as follows, and the formula is as follows 2:
C. preparation of zwitterionic hydrophobically modified guar gum
(1) Putting a proper amount of alcohol water solution into a flask, weighing a certain amount of anionic guar gum, adding the anionic guar gum into the flask, and stirring for dissolving; (2) dropwise adding a certain amount of alkaline solution, and alkalizing for 20 minutes; (3) weighing a certain amount of the paste intermediate, adding the paste intermediate into a reaction kettle, putting the flask into an oil bath pot, heating, adding a reflux pipe, stirring, and obtaining a product after 4-5 hours, wherein the product is represented by formula 3:
the weight ratio of the anionic guar gum to the alkaline solution to the paste intermediate is as follows: 100:4-5:0.25-0.5.
The anionic guar may also be carboxymethyl guar or sulfonated guar.
The alcohol aqueous solution in the step A or C is methanol, ethanol or isopropanol with the concentration of 80-95%.
The basic catalyst in step A is triethylamine.
The alkaline solution in step B is KOH solution.
The alkaline solution in step C is NaOH solution.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the invention, from the molecular structure, anions, cations and hydrophobic long chains are introduced into a guar gum main chain, the characteristics of a zwitterionic polymer and a hydrophobic association polymer are combined, electrostatic interaction and hydrophobic association are endowed to the guar gum main chain, a reversible space network structure is built among guar gum aqueous solutions, the space network structure of the guar gum aqueous solutions is denser, good dispersibility of guar gum derivatives is ensured, and meanwhile, the tackifying property and the temperature resistance and salt tolerance of the guar gum derivatives are improved.
2. By adopting the specific A, B, C three process steps and obtaining specific process parameters in the three steps through a plurality of tests, the better technical effect is obtained, and through the verification of the embodiments 1-4, the following results can be obtained: through detection, the viscosity swelling rate of the final product within 3min is 88-92%, and the water insoluble substance is 4.59-5.45%.
3. The preparation method is simple, and compared with the commonly used hydroxypropyl guar gum, referring to example 5, the product prepared by the preparation method is obvious in viscosity mutation phenomenon due to the mutual association of the hydrophobic long chains when the concentration is higher, and the thickening type of the product is higher than that of the commonly used guar gum modified product hydroxypropyl guar gum (HPG), so that the product is a fracturing fluid thickening agent with excellent thickening effect. In comparison with conventional hydroxypropyl guar (HPG), referring to example 6, it can be seen from the test results that the salt tolerance of the aqueous solution of the present invention is superior to that of conventional hydroxypropyl guar.
Drawings
The invention will be described in further detail with reference to the following description taken in conjunction with the accompanying drawings and detailed description, in which:
FIG. 1 is a graph showing comparative results of example 5;
FIG. 2 is a graph showing comparative results of example 6.
Detailed Description
The ionic macromolecular polymer endows a molecular chain with a large amount of charged ionic groups, the electrostatic repulsion of the ionic groups can enable the molecular chain to be easier to expand, the hydrodynamic volume of the molecular chain is increased, and the ionic macromolecular polymer is not only beneficial to quick dissolution of guar gum derivatives, but also beneficial to improvement of the viscosity of aqueous solutions of the guar gum derivatives. The amphoteric ionic polymer has both anionic and cationic charges in the molecular chain, and the electrostatic interaction between the charges of the amphoteric ionic polymer can be classified into repulsive force or attractive force depending on the relative number and pH value of two ions in the molecular chain. In recent years, the special properties of zwitterionic polymers have also become more and more appreciated by researchers in the world.
Hydrophobic modification is also a very important direction for current water-soluble polymers. The hydrophobic chains are gathered into clusters, so that the molecular chains are mutually wound and associated, a reversible spatial network structure is endowed to the polymer, the unique rheological property of the water-soluble polymer can be realized, and the thickening property of the polymer and the salt resistance, temperature resistance and shear resistance of the aqueous solution of the water-soluble polymer can be greatly improved.
According to the invention, from the molecular structure, anions, cations and hydrophobic long chains are introduced into a guar gum main chain, the characteristics of a zwitterionic polymer and a hydrophobic association polymer are combined, the electrostatic interaction and the hydrophobic association are endowed to the guar gum, the good dispersibility of the guar gum derivative is ensured, and the tackifying property, the temperature resistance and the salt tolerance of the guar gum derivative are increased.
Example 1
(1) Charging 85% ethanol water solution into a flask; adding 20g of guar gum into a flask under the stirring state, setting the temperature at 60 ℃, adding 1.2g of triethylamine, and uniformly stirring for 20-30 min; slowly adding 4.8g of maleic anhydride into the flask, uniformly stirring, and reacting for 3-5h to obtain the anionic guar gum.
(2) Introducing nitrogen into the three-neck flask for 10 min; adding n-dodecanoic acid and 3-dimethylaminopropylamine into a flask according to a molar ratio of 1: 1.1; dropwise adding 0.5 wt% KOH solution into the flask, raising the temperature to 120 ℃, reacting for 6h, and then distilling under reduced pressure to remove unreacted amine and generated water to obtain the tertiary amine product. Adding absolute ethyl alcohol serving as a solvent into a single-neck flask, heating to 70 ℃, adding a hydrophobic chain and epoxy chloropropane into the flask according to the molar ratio of 1:1.1, adding a reflux pipe, reacting for 10 hours, and then performing rotary distillation to remove the solvent to finally obtain a paste intermediate N-12.
(3) A proper amount of 85% ethanol aqueous solution is measured and filled into a flask, 40g of maleic acid guar gum is weighed and added into the flask, and the mixture is stirred uniformly until the maleic acid guar gum is fully dissolved. 2g of 20% NaOH solution is added dropwise and basified for 20 min. 0.2g of reaction intermediate N-12 was taken and added to the reaction vessel. And (3) putting the flask into an oil bath kettle, heating, adding a return pipe, stirring, and obtaining the product NGG-12 after 4 hours. The product was found to have a viscosity swelling ratio of 91.5% within 3min and a water-insoluble content of 4.59%.
Example 2
(1) Anionic guar was prepared as in example 1.
(2) Introducing nitrogen into a three-neck flask for 5min, and adding n-tetradecanoic acid and 3-dimethylaminopropylamine into the flask according to the molar ratio of 1: 1.1; dropwise adding 0.5 wt% KOH solution into the flask, raising the temperature to 170 ℃, reacting for 6h, and then distilling under reduced pressure to remove unreacted amine and generated water to obtain the tertiary amine product. Adding absolute ethyl alcohol serving as a solvent into a single-neck flask, heating to 70 ℃, adding a hydrophobic chain and epoxy chloropropane into the flask according to the molar ratio of 1:1.1, adding a reflux pipe, reacting for 10 hours, and then performing rotary distillation to remove the solvent to finally obtain a brown paste intermediate N-14.
(3) A proper amount of 85% ethanol water 4 solution is measured and put into a flask, 40g of maleic acid guar gum derivative is weighed and added into the flask, and the mixture is stirred uniformly until the maleic acid guar gum derivative is fully dissolved. 2g of 20% NaOH solution is added dropwise and basified for 20 min. 0.15g of reaction intermediate N-14 was taken and added to the reaction vessel. And (3) putting the flask into an oil bath kettle, heating, adding a return pipe, stirring, and obtaining the product NGG-14 after 4 hours. The product was found to have a viscosity swelling ratio of 88% within 3min and a water-insoluble content of 5.45%.
Example 3
(1) Anionic guar was prepared as in example 1.
(2) Introducing nitrogen into the three-neck flask for 10 min; adding oleic acid and 3-dimethylaminopropylamine into a flask according to a molar ratio of 1: 1.1; dropwise adding 0.5 wt% KOH solution into the flask, raising the temperature to 160 ℃, reacting for 6h, and then distilling under reduced pressure to remove unreacted amine and generated water to obtain the tertiary amine product. Adding absolute ethyl alcohol serving as a solvent into a single-neck flask, heating to 70 ℃, adding a hydrophobic chain and epoxy chloropropane into the flask according to the molar ratio of 1:1.1, adding a reflux pipe, reacting for 10 hours, and then performing rotary distillation to remove the solvent to finally obtain a brown paste intermediate N-18.
(3) A proper amount of 85% ethanol aqueous solution is measured and filled into a flask, 40 parts of maleic acid guar gum by weight is weighed and added into the flask, and the mixture is stirred uniformly until the maleic acid guar gum is fully dissolved. 2g of 20% NaOH solution is added dropwise and basified for 20 min. 0.1g of reaction intermediate N-18 was taken and added to the reaction vessel. And (3) putting the flask into an oil bath kettle, heating, adding a reflux pipe, stirring, and obtaining the product NGG-18 after 4 hours. The viscosity swelling rate of the product within 3min is 92% and the water insoluble matter is 5.02% through detection.
Example 4
(1) Anionic guar was prepared as in example 1.
(2) Introducing nitrogen into the three-neck flask for 10 min; adding the mole ratio of the mesonic acid to the 3-dimethylaminopropylamine into a flask; dropwise adding 0.5 wt% KOH solution into the flask, raising the temperature to 160 ℃, reacting for 6h, and then distilling under reduced pressure to remove unreacted amine and generated water to obtain the tertiary amine product. Adding absolute ethyl alcohol serving as a solvent into a single-neck flask, heating to 70 ℃, adding a hydrophobic chain and epoxy chloropropane into the flask according to the molar ratio of 1:1.1, adding a reflux pipe, reacting for 10 hours, and then performing rotary distillation to remove the solvent to finally obtain a brown paste intermediate N-22.
(3) A proper amount of 85% ethanol aqueous solution is measured and put into a flask, 40g of anion guar gum is weighed and added into the flask, and the mixture is stirred uniformly until the anion guar gum is fully dissolved. 2g of 20% NaOH solution is added dropwise and basified for 20 min. 0.15g of reaction intermediate N-22 was taken and added to the reaction vessel. And (3) putting the flask into an oil bath kettle, heating, adding a return pipe, stirring, and obtaining the product NGG-22 after 4 hours. The product was found to have a viscosity swelling ratio of 91% within 3min and a water-insoluble content of 5.1%.
Example 5
The four zwitterionic hydrophobically modified guar gums are prepared into aqueous solutions with the concentrations of 0.1%, 0.2%, 0.3%, 0.4%, 0.5% and 0.6%, and the solutions are tested at 170s-1The apparent viscosity is compared with that of the conventional hydroxypropyl guar gum, and as shown in the attached figure 1, when the concentration is higher, the phenomenon of viscosity mutation is obvious due to the mutual association of hydrophobic long chains, and the thickening type of the modified hydroxypropyl guar gum is higher than that of the conventional guar gum modified product hydroxypropyl guar gum (HPG). The present invention is a fracturing fluid thickener having an excellent thickening effect.
Example 6
The 4 zwitterionic hydrophobically modified guars described above were formulated as 0.5% aqueous solutions and tested for viscosity at different salt loadings and compared to conventional hydroxypropyl guar (HPG). Referring to the attached figure 2, the test results show that the salt resistance of the aqueous solution of the invention is superior to that of the conventional hydroxypropyl guar gum.
Claims (6)
1. A preparation method of zwitterionic hydrophobically modified guar gum is characterized by comprising the following steps:
A. preparation of anionic guar gum: (1) putting a proper amount of alcohol-water solution into a flask; (2) adding 40-60 parts by weight of guar gum into a flask, setting the temperature to be 60 ℃, and stirring; (3) adding 2-4 parts by weight of alkaline catalyst, and stirring for 20-30 min; (4) adding 10-15 parts by weight of maleic anhydride into a flask, stirring, and reacting for 3-5h to obtain the anionic guar gum shown as formula 1:
B. preparation of water-soluble amphiphilic cationic hydrophobic monomer: (1) introducing nitrogen into the three-neck flask for 5-15min, and replacing the air in the flask; (2) adding long-chain organic acid and 3-dimethylaminopropylamine according to a molar ratio of 1: 1.1-1: 1.2; (3) dropwise adding 0.3-0.7 wt% of alkaline solution into the flask, raising the temperature to 120-170 ℃, reacting for 6-8 h, and then carrying out reduced pressure distillation to remove unreacted amine and generated water to obtain a tertiary amine product; (4) adding absolute ethyl alcohol serving as a solvent into a single-neck flask, heating to 70 ℃, adding a tertiary amine product and epoxy chloropropane into the flask according to the molar ratio of 1:1.1, adding a reflux pipe, reacting for 10 hours, and then performing rotary distillation to remove the solvent to finally obtain a paste intermediate, wherein the formula is as follows, and the formula is as follows 2:
C. preparation of zwitterionic hydrophobically modified guar gum
(1) Putting a proper amount of alcohol water solution into a flask, weighing a certain amount of anionic guar gum, adding the anionic guar gum into the flask, and stirring for dissolving; (2) dropwise adding a certain amount of alkaline solution, and alkalizing for 20 minutes; (3) weighing a certain amount of the paste intermediate, adding the paste intermediate into a reaction kettle, putting the flask into an oil bath pot, heating, adding a reflux pipe, stirring, and obtaining a product after 4-5 hours, wherein the product is represented by formula 3:
the weight ratio of the anionic guar gum to the alkaline solution to the paste intermediate is as follows: 100:4-5:0.25-0.5.
2. The method for preparing the zwitterionic hydrophobically modified guar according to claim 1, which is characterized in that: the anionic guar gum is carboxymethyl guar gum or sulfonic guar gum.
3. The method for preparing the zwitterionic hydrophobically modified guar according to claim 1, which is characterized in that: the alcohol aqueous solution in the step A or C is methanol, ethanol or isopropanol with the concentration of 80-95%.
4. The method for preparing the zwitterionic hydrophobically modified guar according to claim 1, which is characterized in that: the basic catalyst in step A is triethylamine.
5. The method for preparing the zwitterionic hydrophobically modified guar according to claim 1, which is characterized in that: the alkaline solution in step B is KOH solution.
6. The method for preparing the zwitterionic hydrophobically modified guar according to claim 1, which is characterized in that: the alkaline solution in step C is NaOH solution.
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| CN102827300A (en) * | 2012-08-30 | 2012-12-19 | 华南理工大学 | Preparation method and application of hydrophobic modified guar gum |
| CN109517082A (en) * | 2017-09-18 | 2019-03-26 | 中国石油化工股份有限公司 | A kind of non-long linear alkyl hydrophobically modified hydroxyethyl guar gum thickener and preparation method thereof |
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| CN102827300A (en) * | 2012-08-30 | 2012-12-19 | 华南理工大学 | Preparation method and application of hydrophobic modified guar gum |
| CN109517082A (en) * | 2017-09-18 | 2019-03-26 | 中国石油化工股份有限公司 | A kind of non-long linear alkyl hydrophobically modified hydroxyethyl guar gum thickener and preparation method thereof |
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