CN116693715B - High-temperature-resistant modified guar gum and synthetic method thereof - Google Patents
High-temperature-resistant modified guar gum and synthetic method thereof Download PDFInfo
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- 229920002907 Guar gum Polymers 0.000 title claims abstract description 102
- 239000000665 guar gum Substances 0.000 title claims abstract description 102
- 229960002154 guar gum Drugs 0.000 title claims abstract description 102
- 235000010417 guar gum Nutrition 0.000 title claims abstract description 101
- 238000010189 synthetic method Methods 0.000 title description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 54
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 44
- GJFNRSDCSTVPCJ-UHFFFAOYSA-N 1,8-bis(dimethylamino)naphthalene Chemical compound C1=CC(N(C)C)=C2C(N(C)C)=CC=CC2=C1 GJFNRSDCSTVPCJ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 15
- 238000005956 quaternization reaction Methods 0.000 claims abstract description 10
- 238000006011 modification reaction Methods 0.000 claims abstract description 9
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 5
- 230000009471 action Effects 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 15
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 13
- 230000002194 synthesizing effect Effects 0.000 claims description 12
- 230000035484 reaction time Effects 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 24
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 11
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000001308 synthesis method Methods 0.000 abstract description 4
- 239000003208 petroleum Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000007787 solid Substances 0.000 description 36
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 27
- 229910052757 nitrogen Inorganic materials 0.000 description 23
- 238000006243 chemical reaction Methods 0.000 description 20
- 238000010438 heat treatment Methods 0.000 description 18
- 238000012360 testing method Methods 0.000 description 15
- 238000003756 stirring Methods 0.000 description 12
- 239000012153 distilled water Substances 0.000 description 10
- 238000001914 filtration Methods 0.000 description 10
- 230000001105 regulatory effect Effects 0.000 description 10
- 238000001816 cooling Methods 0.000 description 9
- 239000011259 mixed solution Substances 0.000 description 9
- 230000004048 modification Effects 0.000 description 9
- 238000012986 modification Methods 0.000 description 9
- 238000010992 reflux Methods 0.000 description 9
- 239000012530 fluid Substances 0.000 description 8
- 238000000643 oven drying Methods 0.000 description 8
- 238000004321 preservation Methods 0.000 description 8
- 230000002209 hydrophobic effect Effects 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 230000001965 increasing effect Effects 0.000 description 4
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 4
- 238000010008 shearing Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- 229920001938 Vegetable gum Polymers 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 2
- 229940106681 chloroacetic acid Drugs 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- OMDQUFIYNPYJFM-XKDAHURESA-N (2r,3r,4s,5r,6s)-2-(hydroxymethyl)-6-[[(2r,3s,4r,5s,6r)-4,5,6-trihydroxy-3-[(2s,3s,4s,5s,6r)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl]oxyoxan-2-yl]methoxy]oxane-3,4,5-triol Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@@H]1OC[C@@H]1[C@@H](O[C@H]2[C@H]([C@@H](O)[C@H](O)[C@@H](CO)O2)O)[C@H](O)[C@H](O)[C@H](O)O1 OMDQUFIYNPYJFM-XKDAHURESA-N 0.000 description 1
- 244000007835 Cyamopsis tetragonoloba Species 0.000 description 1
- 229920000926 Galactomannan Polymers 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003113 alkalizing effect Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- -1 carboxymethyl hydroxypropyl Chemical group 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229920013818 hydroxypropyl guar gum Polymers 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 230000009149 molecular binding Effects 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- 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
Abstract
The invention belongs to the technical field of petroleum exploitation, and particularly relates to high-temperature-resistant modified guar gum and a synthesis method thereof. The synthesis method comprises the following steps: under the action of catalyst hydrochloric acid, under the existence of solvent ethanol, N, N, N ', N' -tetramethyl-1, 8-naphthalene diamine and epoxy chloropropane undergo quaternization reaction; secondly, the quaternization reaction product and guar gum are subjected to modification reaction under alkaline conditions. The mol ratio of the epoxy chloropropane to the N, N, N ', N' -tetramethyl-1, 8-naphthalene diamine is 1.8-2.5: the mass ratio of the guar gum to the N, N, N ', N' -tetramethyl-1, 8-naphthalene diamine is 3-5:1. the guar gum has the advantages of wide raw material sources, simple synthesis, high apparent viscosity, less water insoluble matters, strong temperature resistance, strong antibacterial capability and the like, the apparent viscosity is more than 420mPa.s, the temperature resistance is more than 80 ℃, and the water insoluble matter content is less than 2.8%.
Description
Technical Field
The invention belongs to the technical field of petroleum exploitation, and particularly relates to high-temperature-resistant modified guar gum and a synthesis method thereof.
Background
Guar gum is a natural polymer water-soluble colloid separated from guar seeds, the chemical composition of the guar gum is mainly galactomannan, and the guar gum has the characteristics of good water solubility, viscosity, stability, heat resistance, large chemical modification potential and the like, and is applied to industries of petroleum drilling, building coating, textile printing and dyeing, food medicine, weapon and explosive and the like.
Although guar gum has good water solubility and thickening properties, raw guar gum tends to have the following disadvantages: the water-soluble polymer cannot be quickly swelled and hydrated, and the dissolution speed is low; high water insoluble content; the viscosity is not easy to control; is easily decomposed by microorganisms and cannot be stored for a long time. These drawbacks have limited the application of guar gum to a great extent, and therefore require a modification of its physicochemical properties, making it widely applicable.
In the exploitation process of an oil-gas field, the fracturing fluid used for achieving the purpose of increasing the yield and efficiency of a hypotonic reservoir through a hydraulic fracturing mode is prepared by taking modified guar gum as a thickening agent. The performance of the fracturing fluid has decisive influence on success and failure of fracturing construction, and the yield increasing effect is directly related. In recent years, a great deal of researches are carried out on the aspects of modifying guar gum molecules from the aspect of mechanism analysis of guar gum molecular structures, and the apparent viscosity, temperature resistance, antibacterial property and other performances of the obtained modified guar gum are further improved.
"study of carboxymethyl hydroxypropyl guar gum synthesis Process" published in volume 21 and phase 2 of the chemical journal of the time of chemical industry, the reported method adopts chloroacetic acid as a carboxymethylation etherifying agent, and the chloroacetic acid has high toxicity and causes great harm to the body by contacting or inhaling high-concentration steam; in addition, the acid is strong, and the corrosion to equipment is high.
CN102827300a discloses a preparation method and application of 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 up under the protection of nitrogen, slowly dripping a modifier, and heating up to 30-80 ℃ for modification reaction; and after the reaction is finished, adding organic acid to adjust the pH to 5-7, soaking and washing with ethanol, filtering, and vacuum drying a filter cake to obtain the hydrophobic modified guar gum. According to the invention, a hydrophobic alkyl long chain is introduced to the hydroxyl of guar gum, and the end group is a carboxylic acid group, so that the water-soluble speed of the guar gum is improved, the macromolecular quality characteristic of the guar gum is protected to the maximum extent, and the hydrophobic property of the guar gum is endowed. Compared with other modified guar gum, the hydrophobic guar gum has high molecular weight and good compatibility with cellulose, and increases the molecular binding force of cellulose-guar gum, thereby improving the paper strength, and can be used as a reinforcing agent and a surface sizing agent for the wet-end chemical process of papermaking. However, the modified guar gum provided by the invention has the advantages that only a single hydrophobic long chain is added, so that the solubility of the modified guar gum is greatly reduced, and the modified guar gum is unfavorable for quick liquid preparation on site.
Disclosure of Invention
The invention provides high-temperature-resistant modified guar gum and a synthesis method thereof, aiming at the defects of the prior art. The guar gum has the advantages of wide raw material sources, simple synthesis, high apparent viscosity, less water insoluble substances, strong temperature resistance, strong antibacterial capability and the like.
Therefore, in order to achieve the above purpose, in one aspect, the invention discloses a high temperature resistant modified guar gum, wherein the molecular structural formula of the high temperature resistant modified guar gum is as follows:。
in another aspect, the invention discloses a method for synthesizing high temperature resistant modified guar gum, which comprises the following steps: under the action of catalyst hydrochloric acid, under the existence of solvent ethanol, N, N, N ', N' -tetramethyl-1, 8-naphthalene diamine and epoxy chloropropane undergo quaternization reaction; secondly, the quaternization reaction product and guar gum are subjected to modification reaction under alkaline conditions.
The high-temperature resistant modified guar gum molecule is obtained by modifying common guar gum. Guar gum molecules are connected together through quaternized N, N, N ', N' -tetramethyl-1, 8-naphthalene diamine, so that the molecular weight is greatly increased, and the apparent viscosity is increased; two quaternary ammonium salts are introduced into the molecule, so that guar gum is converted from nonionic to ionic and is more soluble in water; the quaternary ammonium salt is introduced into the molecule, so that the guar gum has sterilization function, and the guar gum can be prepared in advance without being denatured by bacterial attack; the naphthalene ring structure is introduced into the molecule, so that the stability of the molecule can be improved, and the temperature resistance of the molecule can be improved; the quaternary ammonium salt in the molecule neutralizes the negative charge on the surface of the clay, so that the repulsive force between the clay is reduced, and the swelling prevention effect is achieved.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) The high-temperature resistant modified guar gum has wide sources of raw materials and simple synthesis and preparation processes;
(2) The high-temperature resistant modified guar gum has the characteristic of high apparent viscosity, and the apparent viscosity is more than 420mPa.s;
(3) The high-temperature-resistant modified guar gum has higher temperature resistance, and the temperature resistance is higher than 80 ℃;
(4) The high-temperature resistant modified guar gum has low water insoluble content which is less than 2.8 percent;
(5) The high-temperature resistant modified guar gum has strong antibacterial performance, and the viscosity retention rate is more than 92%.
Drawings
Fig. 1 is a viscosity temperature curve of the high temperature resistant modified guar gum of the present invention.
FIG. 2 is a high temperature resistant modified guar gum G of the invention 7 Is a spectrum of infrared light of (a) is obtained.
Description of the embodiments
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
According to a first aspect of the invention, the invention discloses a high temperature resistant modified guar gum, which has the following molecular structural formula:。
in a second aspect, the invention discloses a method for synthesizing high temperature resistant modified guar gum, which comprises the following steps: under the action of catalyst hydrochloric acid, under the existence of solvent ethanol, N, N, N ', N' -tetramethyl-1, 8-naphthalene diamine and epoxy chloropropane undergo quaternization reaction; secondly, the quaternization reaction product and guar gum are subjected to modification reaction under alkaline conditions.
In the present invention, preferably, the molar ratio of epichlorohydrin to N, N' -tetramethyl-1, 8-naphthalene diamine is 1.8 to 2.5:1, more preferably 2.2-2.5:1.
in the present invention, the catalyst hydrochloric acid is preferably used in an amount required to adjust the pH of an ethanol solution of N, N, N ', N' -tetramethyl-1, 8-naphthalene diamine and epichlorohydrin to 2-2.5.
In the present invention, preferably, the weight ratio of the solvent ethanol to the N, N' -tetramethyl-1, 8-naphthalene diamine is 15-20:1.
in the present invention, the quaternization reaction is preferably carried out for 24 to 48 hours, more preferably 32 to 40 hours.
In the present invention, preferably, the mass ratio of guar gum to N, N' -tetramethyl-1, 8-naphthalene diamine is 3-5:1, more preferably 3-4:1.
in the present invention, preferably, the alkaline condition is pH 12-13.
In the invention, preferably, the modification reaction time is 30-60min, and the temperature is 60-65 ℃; more preferably, the modification reaction time is 40-50min and the temperature is 60-62 ℃.
According to a more specific preferred embodiment, the method for synthesizing the high temperature resistant modified guar gum specifically comprises the following steps:
(1) Adding N, N, N ', N' -tetramethyl-1, 8-naphthalene diamine and solvent ethanol into a four-neck flask, starting stirring, adding epichlorohydrin dropwise by using a dropping funnel, adjusting the pH to 2-2.5 by using a catalyst hydrochloric acid after the dropwise addition is finished, and heating and refluxing for reaction for 24-48 hours; after the reaction is finished, the mixed solution is distilled under reduced pressure to obtain light yellow sticky solid; recrystallizing with ethyl acetate to obtain white solid;
(2) Adding guar gum and distilled water into a beaker, regulating the pH to 12-13, adding the white solid in the step (1), heating to 60-65 ℃, and carrying out heat preservation reaction;
(3) Adjusting pH to 7-7.5, adding ethanol, cooling to below 10deg.C, precipitating solid, filtering, and oven drying to obtain the final product.
Preferably, the weight ratio of distilled water to guar gum in step (2) is 5-6:1.
preferably, the weight ratio of ethanol to N, N, N ', N' -tetramethyl-1, 8-naphthalene diamine in step (3) is 4-6:1.
the synthesis reaction equation of the high temperature resistant modified guar gum is as follows:
。
in addition, the specific features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various possible combinations are not described further.
Moreover, any combination of the various embodiments of the invention can be made without departing from the spirit of the invention, which should also be considered as disclosed herein.
The invention will be further illustrated with reference to specific examples.
Examples
(1) Adding 0.1mol of N, N' -tetramethyl-1, 8-naphthalene diamine and 321g of solvent ethanol into a four-neck flask, starting stirring, dropwise adding 0.18mol of epichlorohydrin by using a dropping funnel, adjusting the pH value to 2 by using 2mol/L of catalyst hydrochloric acid after the dropwise adding is finished, and heating and refluxing for 24 hours; after the reaction is finished, the mixed solution is distilled under reduced pressure to obtain light yellow sticky solid; recrystallizing with ethyl acetate to obtain white solid;
(2) Adding 64.2g of guar gum and 385g of distilled water into a beaker, adjusting the pH to 12 by using 1mol/L sodium hydroxide, adding the white solid in the step (1), heating to 63 ℃, and carrying out heat preservation reaction for 30min;
(3) Regulating pH to 7 with 2mol/L hydrochloric acid, adding 100G ethanol, cooling to below 10deg.C, separating out solid, filtering, and oven drying to obtain high temperature resistant modified guar gum G 1 。
Examples
(1) Adding 0.1mol of N, N' -tetramethyl-1, 8-naphthalene diamine and 368g of solvent ethanol into a four-neck flask, starting stirring, dropwise adding 0.19mol of epichlorohydrin by using a dropping funnel, adjusting the pH to 2 by using 2mol/L of catalyst hydrochloric acid after the dropwise adding is finished, and heating and refluxing for 28h; after the reaction is finished, the mixed solution is distilled under reduced pressure to obtain light yellow sticky solid; recrystallizing with ethyl acetate to obtain white solid;
(2) Adding 77.8g guar gum and 428g distilled water into a beaker, adjusting the pH to 13 by using 1mol/L sodium hydroxide, adding the white solid in the step (1), heating to 62 ℃, and carrying out heat preservation reaction for 40min;
(3) Regulating pH to 7 with 2mol/L hydrochloric acid, adding 88G ethanol, cooling to below 10deg.C, separating out solid, filtering, and oven drying to obtain high temperature resistant modified guar gum G 2 。
Examples
(1) Adding 0.1mol of N, N' -tetramethyl-1, 8-naphthalene diamine and 354g of solvent ethanol into a four-neck flask, starting stirring, dropwise adding 0.2mol of epichlorohydrin by using a dropping funnel, adjusting the pH to 2.5 by using 2mol/L of catalyst hydrochloric acid after the dropwise adding is finished, and heating and refluxing for 30 hours; after the reaction is finished, the mixed solution is distilled under reduced pressure to obtain light yellow sticky solid; recrystallizing with ethyl acetate to obtain white solid;
(2) Adding 107g of guar gum and 585g of distilled water into a beaker, adjusting the pH to 12 by using 1mol/L sodium hydroxide, adding the white solid in the step (1), heating to 64 ℃, and carrying out heat preservation reaction for 50min;
(3) Regulating pH to 7 with 2mol/L hydrochloric acid, adding 88G ethanol, cooling to below 10deg.C, separating out solid, filtering, and oven drying to obtain high temperature resistant modified guar gum G 3 。
Examples
(1) Adding 0.1mol of N, N' -tetramethyl-1, 8-naphthalene diamine and 392g of solvent ethanol into a four-neck flask, starting stirring, dropwise adding 0.21mol of epichlorohydrin by using a dropping funnel, adjusting the pH to 2.1 by using 2mol/L of catalyst hydrochloric acid after the dropwise adding is finished, and heating and refluxing for 36h; after the reaction is finished, the mixed solution is distilled under reduced pressure to obtain light yellow sticky solid; recrystallizing with ethyl acetate to obtain white solid;
(2) 102g of guar gum and 510g of distilled water are added into a beaker, the pH is regulated to 12.5 by 1mol/L sodium hydroxide, the white solid in the step (1) is added, the temperature is raised to 63 ℃, and the reaction is carried out for 35min;
(3) Regulating pH to 7.5 with 2mol/L hydrochloric acid, adding 86G ethanol, cooling to below 10deg.C, separating out solid, filtering, and oven drying to obtain high temperature resistant modified guar gum G 4 。
Examples
(1) Adding 0.1mol of N, N' -tetramethyl-1, 8-naphthalene diamine and 400g of solvent ethanol into a four-neck flask, starting stirring, dropwise adding 0.22mol of epichlorohydrin by using a dropping funnel, adjusting the pH to 2.2 by using 2mol/L of catalyst hydrochloric acid after the dropwise adding is finished, and heating and refluxing for 40 hours; after the reaction is finished, the mixed solution is distilled under reduced pressure to obtain light yellow sticky solid; recrystallizing with ethyl acetate to obtain white solid;
(2) Adding 86.3g guar gum and 518g distilled water into a beaker, adjusting the pH to 13 by using 1mol/L sodium hydroxide, adding the white solid in the step (1), heating to 61 ℃, and carrying out heat preservation reaction for 45min;
(3) Adjusting pH to 7.5 with 2mol/L hydrochloric acid, adding 104G ethanol, cooling to below 10deg.C, separating out solid, filtering, and oven drying to obtain high temperature resistant modified guar gum G 5 。
Examples
(1) Adding 0.1mol of N, N' -tetramethyl-1, 8-naphthalene diamine and 388g of solvent ethanol into a four-neck flask, starting stirring, dropwise adding 0.23mol of epichlorohydrin by using a dropping funnel, adjusting the pH to 2.3 by using 2mol/L of catalyst hydrochloric acid after the dropwise adding is finished, and heating and refluxing for 42h; after the reaction is finished, the mixed solution is distilled under reduced pressure to obtain light yellow sticky solid; recrystallizing with ethyl acetate to obtain white solid;
(2) Adding 98.8g guar gum and 500g distilled water into a beaker, adjusting the pH to 12.5 by using 1mol/L sodium hydroxide, adding the white solid in the step (1), heating to 62 ℃, and carrying out heat preservation reaction for 50min;
(3) Adjusting pH to 7 with 2mol/L hydrochloric acid, adding 95g ethanol, and cooling to below 10deg.CSeparating out solid, filtering, drying to obtain the product, namely the high-temperature-resistant modified guar gum G 6 。
Examples
(1) Adding 0.1mol of N, N' -tetramethyl-1, 8-naphthalene diamine and 428g of solvent ethanol into a four-neck flask, starting stirring, dropwise adding 0.24mol of epichlorohydrin by using a dropping funnel, adjusting the pH to 2.4 by using 2mol/L of catalyst hydrochloric acid after the dropwise adding is finished, and heating and refluxing for 44h; after the reaction is finished, the mixed solution is distilled under reduced pressure to obtain light yellow sticky solid; recrystallizing with ethyl acetate to obtain white solid;
(2) Adding 81.2g guar gum and 444g distilled water into a beaker, adjusting the pH to 13 by using 1mol/L sodium hydroxide, adding the white solid in the step (1), heating to 65 ℃, and carrying out heat preservation reaction for 60min;
(3) Regulating pH to 7.2 with 2mol/L hydrochloric acid, adding 128G ethanol, cooling to below 10deg.C, separating out solid, filtering, and oven drying to obtain high temperature resistant modified guar gum G 7 。
Examples
(1) Adding 0.1mol of N, N' -tetramethyl-1, 8-naphthalene diamine and 412g of solvent ethanol into a four-neck flask, starting stirring, dropwise adding 0.25mol of epichlorohydrin by using a dropping funnel, adjusting the pH to 2.5 by using 2mol/L of catalyst hydrochloric acid after the dropwise adding is finished, and heating and refluxing for 48 hours; after the reaction is finished, the mixed solution is distilled under reduced pressure to obtain light yellow sticky solid; recrystallizing with ethyl acetate to obtain white solid;
(2) 88.4g guar gum and 468g distilled water are added into a beaker, the pH is regulated to 12.5 by 1mol/L sodium hydroxide, the white solid in the step (1) is added, the temperature is raised to 60 ℃, and the reaction is carried out for 55min under the heat preservation;
(3) Regulating pH to 7.3 with 2mol/L hydrochloric acid, adding 116G ethanol, cooling to below 10deg.C, separating out solid, filtering, and oven drying to obtain high temperature resistant modified guar gum G 8 。
Test example 1 apparent viscosity test
The evaluation method is carried out according to the requirements of 4.6 by referring to SY/T5764-2007 general technical requirement for vegetable gums for fracturing.
Apparent viscosity test results are shown in Table 1.
As can be seen from table 1: the high-temperature resistant modified guar gum G of the invention 1 、G 2 、G 3 、G 4 、G 5 、G 6 、G 7 、G 8 Apparent viscosity of greater than 420mPa.s, wherein G 7 Up to 5297 mpa.s; the apparent viscosity of guar gum before modification is 205mPa.s, which is obviously lower than that of guar gum after modification.
Test example 2 measurement of temperature resistance
The samples of test example 1 were tested for temperature resistance, the viscosity at different temperatures was tested with a haak rheometer, the apparent viscosity was recorded every 5 ℃ increase starting from 30 ℃, and when the viscosity was less than 50mpa.s, the test was stopped, the corresponding temperature being the temperature resistance temperature of the modified guar gum.
The viscosity-temperature curve test results are shown in FIG. 1, and the temperature-resistant test results are shown in Table 1.
As can be seen from table 1: the high-temperature resistant modified guar gum G of the invention 1 、G 2 、G 3 、G 4 、G 5 、G 6 、G 7 、G 8 The temperature resistance of (C) is higher than 80 ℃, wherein G 7 Up to 87 ℃; the temperature resistance of the guar gum before modification is 65 ℃ which is obviously lower than that of the guar gum after modification.
Test example 3 determination of Water insoluble substances
The evaluation method is carried out according to the requirements of 4.8 by referring to SY/T5764-2007 general technical requirement for vegetable gums for fracturing.
The results of the water insoluble content test are shown in Table 1.
As can be seen from table 1: the high-temperature resistant modified guar gum G of the invention 1 、G 2 、G 3 、G 4 、G 5 、G 6 、G 7 、G 8 The water-insoluble content of (2) is less than 2.8%, wherein G 7 Minimum 2.04%; the water insoluble content of the guar gum before modification is 5.68 percent, which is obviously higher than that of the guar gum after modification.
Test example 4 test of antibacterial ability
The evaluation method is carried out according to the requirement of 5.3 by referring to Q/SH1025 0784-2011 technical condition of bactericide for fracturing.
And (3) preparing a base solution: 1000 ml tap water is measured and poured into the sterile mixer, and the rotation speed of the sterile mixer is regulated until the vortex formed by the liquid can be seen from the top end of the central shaft of the blade of the mixer. Then, 5g (accurate to 0.001 g) guar gum was slowly added to form a uniform solution, stirring was stopped, and the mixture was allowed to stand in an electrothermal incubator at 30 ℃.
Preparing gel: the base solution 70 ml is measured and poured into a 100 ml beaker, a high-temperature stabilizer for fracturing 0.35 ml and liquid sodium hydroxide 0.30 ml are sequentially added under the stirring of a glass rod, the mixture is stirred uniformly, and then a cross-linking agent 0.35 ml is added under the stirring until uniform gel capable of being picked and hung is formed.
Viscosity measurement: the base fluids with constant temperature of 4h and 120 h are respectively prepared into gel, and then are put into an RT20 rheometer, and the temperature and shearing resistance of the fracturing fluid is measured according to 6.6 in SY/T5107-2005 water-based fracturing fluid performance evaluation method. Setting the temperature to 120 ℃ and setting the shearing rate of the rotor to 170s -1 Shearing for 90 min, and taking the average value of apparent viscosity corresponding to the last 10 min of shearing as the apparent viscosity of the gel.
Wherein:
r-maintenance rate of fracturing fluid viscosity,%;
h1-apparent gel viscosity in millipascal seconds (mpa.s) at constant temperature of 4h for the base fluid;
h2-apparent gel viscosity in millipascal seconds (mPas) at constant temperature 120 h of the base fluid.
The antibacterial ability test results are shown in Table 1.
TABLE 1 apparent viscosity, temperature resistance, water insolubles, antibacterial Capacity test results of modified guar gum
| Guar gum | Apparent viscosity, mPas | Temperature resistance, DEG C | Water insoluble, percent | Antibacterial ability, percent |
| G 1 | 455 | 83 | 2.48 | 93.0 |
| G 2 | 487 | 85 | 2.3 | 93.4 |
| G 3 | 429 | 82 | 2.74 | 93.9 |
| G 4 | 454 | 81 | 2.63 | 93.7 |
| G 5 | 498 | 85 | 2.26 | 94.1 |
| G 6 | 466 | 84 | 2.35 | 94 |
| G 7 | 527 | 87 | 2.04 | 94.3 |
| G 8 | 509 | 86 | 2.08 | 94.8 |
| Before transformation | 205 | 65 | 5.68 | 31.2 |
As can be seen from table 1: the high-temperature resistant modified guar gum G of the invention 1 、G 2 、G 3 、G 4 、G 5 、G 6 、G 7 、G 8 The antibacterial capacity of (2) is greater than 92%, wherein G 8 Up to 94.8%; the antibacterial capacity of the guar gum before modification is 31.2 percent, which is obviously lower than that of the guar gum after modification.
Test example 5 characterization of IR spectrum
High-temperature resistant modified guar gum G for products of the invention by adopting infrared spectrum 7 Characterization was performed and the results are shown in fig. 2.
In FIG. 2, 3447cm -1 Is the stretching vibration absorption peak of O-H in the molecule; 2922cm -1 Is the C-H bond stretching vibration absorption peak in the molecule; 1111cm -1 Is the flexible vibration absorption peak of guanidine gum ether C-O-C bond in the molecule; 949cm -1 Is the C-N bond expansion vibration absorption peak of quaternary ammonium salt in the molecule.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (9)
1. A method for synthesizing high temperature resistant modified guar gum, which is characterized by comprising the following steps: under the action of catalyst hydrochloric acid, under the existence of solvent ethanol, N, N, N ', N' -tetramethyl-1, 8-naphthalene diamine and epoxy chloropropane undergo quaternization reaction; secondly, the quaternization reaction product and guar gum are subjected to modification reaction under alkaline conditions;
the molecular structural formula of the reaction product is as follows:
2. the method for synthesizing the high-temperature-resistant modified guar gum according to claim 1, wherein the molar ratio of the epichlorohydrin to the N, N, N ', N' -tetramethyl-1, 8-naphthalene diamine is 1.8-2.5:1.
3. the method for synthesizing the high-temperature-resistant modified guar gum according to claim 2, wherein the molar ratio of the epichlorohydrin to the N, N, N ', N' -tetramethyl-1, 8-naphthalene diamine is 2.2-2.5:1.
4. the method for synthesizing the high-temperature-resistant modified guar gum according to claim 1, wherein the weight ratio of the solvent ethanol to the N, N, N ', N' -tetramethyl-1, 8-naphthalene diamine is 15-20:1.
5. the method for synthesizing the modified guar gum with high temperature resistance according to claim 1, wherein the quaternization reaction time is 24-48h.
6. The method for synthesizing the high-temperature-resistant modified guar gum according to claim 1, wherein the mass ratio of the guar gum to the N, N, N ', N' -tetramethyl-1, 8-naphthalene diamine is 3-5:1.
7. the method for synthesizing the high-temperature-resistant modified guar gum according to claim 6, wherein the mass ratio of the guar gum to the N, N, N ', N' -tetramethyl-1, 8-naphthalene diamine is 3-4:1.
8. the method for synthesizing the high-temperature-resistant modified guar gum according to claim 1, wherein the modification reaction time is 30-60min and the temperature is 60-65 ℃.
9. The method for synthesizing the high-temperature-resistant modified guar gum according to claim 8, wherein the modification reaction time is 40-50min and the temperature is 60-62 ℃.
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