CN114149513A - Carboxymethyl dihydroxypropyl modified guar gum and preparation method and application thereof - Google Patents
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- 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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Abstract
The invention provides carboxymethyl dihydroxypropyl modified guar gum and a preparation method and application thereof, belonging to the technical field of thickening agents. The structure is shown as formula I, so that the number of cross-linkable cis-dihydroxy sites is ensured, the stretching degree of a polysaccharide molecular chain of the solution is improved, the solution viscosity under the same concentration is increased, the guar gum fracturing fluid material has excellent cross-linking performance and reduced use concentration, and the cleaning performance of the guar gum fracturing fluid is improved; through the adjustment of the substitution degree of the carboxymethyl and dihydroxypropyl functional groups, the control of the content of the water-insoluble substances, the solution viscosity and the crosslinking performance can be realized, the performances of ultralow water-insoluble substances, quick tackifying and low use amount are achieved, the comprehensive performance of the guar gum as the fracturing fluid is greatly improved, and the use cost is reduced.
Description
Technical Field
The invention relates to the technical field of thickening agents, and particularly relates to carboxymethyl dihydroxypropyl modified guar gum and a preparation method and application thereof.
Background
The guar gum is mainly obtained from guar beans of leguminous plants in India, Pakistan and other countries, the solution of the guar gum can be crosslinked with borate, organic boron and an organic metal crosslinking agent to form jelly glue, and the jelly glue has good sand carrying capacity, so the guar gum is widely applied to the field of oil field fracturing. However, the common guar gum has the defects of low dissolution speed and high content of water-insoluble substances, the low dissolution speed cannot meet the requirement of on-site fracturing quick fluid preparation, the high content of residues after fracturing fluid gel breaking is easily caused by the high content of the water-insoluble substances, the oil gas extraction effect is influenced, the application of the guar gum in the fracturing field is limited by the defects, and the application range of the guar gum is generally required to be expanded by chemical modification.
The chemical modification of guar gum comprises nonionic modification, ionized modification and simultaneous modification of nonionic and ionized, wherein the nonionic modification mainly comprises hydroxypropyl modification and hydroxyethyl modification, the interaction of hydrogen bonds among galactomannan molecules in the guar gum can be reduced through the nonionic modification, the dissolution speed of the guar gum is improved, the content of water insoluble substances is reduced, and the main products comprise hydroxypropyl guar gum and hydroxyethyl guar gum; the method comprises the following steps of performing ionization modification, wherein the anion modification comprises carboxymethyl and sulfonic modification, the cation modification mainly comprises 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride modification, hydrophilic groups are introduced on guar gum galactomannan molecular chains through the ionization modification, so that the solubility of the guar gum galactomannan molecular chains can be greatly improved, the solution viscosity is improved, and main products comprise carboxymethyl guar gum, sulfonic guar gum and cation guar gum; the nonionic and ionized guar gum modified simultaneously combines the advantages of more than two modifications, so that the comprehensive performance of the product is improved, and the main products comprise carboxymethyl hydroxypropyl guar gum and hydroxypropyl cationic guar gum.
The chemical modification described above improves the overall performance of the guar, but at the same time brings about some negative effects. The existing chemical modification method generally replaces hydroxyl on guar gum galactomannan with etherifying agent functional group through etherification reaction, and the substitution reaction causes the cis-dihydroxy content of guar gum galactomannan to be reduced. According to the crosslinking mechanism, the reduction in cis-dihydroxy groups results in a reduction in the sites on the guar galactomannan that are crosslinkable with the crosslinking agent, and a reduction in crosslinking performance. On the other hand, if the substitution degree is lower, the crosslinking performance is reduced less, but the improvement effect of the water-insoluble substance is not obvious, so that the existing modified guar gum product has the condition that the water-insoluble substance and the crosslinking performance are mutually contradictory, and the result of controlling the water-insoluble substance and the crosslinking performance to be good cannot be achieved.
Disclosure of Invention
In view of the above, the invention aims to provide a carboxymethyl dihydroxypropyl modified guar gum, and a preparation method and application thereof. The carboxymethyl dihydroxypropyl modified guar gum provided by the invention simultaneously meets the requirements of low water insoluble substance, high crosslinking capacity and quick dissolution.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides carboxymethyl dihydroxypropyl modified guar gum, which has a structure shown in a formula I:
in the formula I, R is independently-H, -CH2COOM or
The carboxymethyl dihydroxypropyl modified guar gum simultaneously contains-CH2COOM and
m is H, Na, K or NH4K is 1-3, and n and m are independently 10000-20000.
Preferably, the carboxymethyl substitution degree in the carboxymethyl dihydroxypropyl modified guar gum is 0.01-2.
Preferably, the carboxymethyl substitution degree in the carboxymethyl dihydroxypropyl modified guar gum is 0.02-1.
Preferably, the substitution degree of dihydroxypropyl in the carboxymethyl dihydroxypropyl modified guar gum is 0.05-3.
Preferably, the substitution degree of dihydroxypropyl in the carboxymethyl dihydroxypropyl modified guar gum is 0.1-1.8.
Preferably, the weight-average molecular weight of the carboxymethyl dihydroxypropyl modified guar gum is 200000-2500000 daltons, and the number-average molecular weight of the carboxymethyl dihydroxypropyl modified guar gum is 100000-1500000 daltons.
Preferably, the ratio of the weight average molecular weight to the number average molecular weight is 1.1-3.5: 1.
the invention also provides a preparation method of the carboxymethyl dihydroxypropyl modified guar gum, which comprises the following steps:
mixing guar gum, an alkaline solution and a dispersing solvent under a protective atmosphere to carry out an alkalization reaction to obtain an alkalization product;
and mixing the alkalization product, an anionic etherifying agent solution and a non-ionic etherifying agent solution under a protective atmosphere to carry out etherification reaction to obtain the carboxymethyl dihydroxypropyl modified guar gum, wherein the anionic etherifying agent in the anionic etherifying agent solution comprises one or more of sodium chloroacetate, potassium chloroacetate and chloroacetic acid, and the non-ionic etherifying agent in the non-ionic etherifying agent solution comprises propylene epoxide alcohol and/or 3-chloropropanediol.
Preferably, the etherification reaction is followed by adjusting the pH value of the obtained etherification reaction product to 5-8.5.
The invention also provides application of the carboxymethyl dihydroxypropyl modified guar gum in the technical scheme as a fracturing thickening agent in the field of oil and gas fracturing.
The invention provides carboxymethyl dihydroxypropyl modified guar gum, which not only ensures the number of cross-linkable cis-dihydroxy sites, but also improves the stretching degree of polysaccharide molecular chains in a solution, increases the solution viscosity under the same concentration, has excellent cross-linking performance and reduced use concentration when being used as a fracturing fluid material, and improves the cleaning performance of guar gum fracturing fluid; through the adjustment of the substitution degree of the carboxymethyl and dihydroxypropyl functional groups, the control of the content of the water-insoluble substances, the solution viscosity and the crosslinking performance can be realized, the performances of ultralow water-insoluble substances, quick tackifying and low use amount are achieved, the comprehensive performance of the guar gum as the fracturing fluid is greatly improved, and the use cost is reduced. The carboxymethyl dihydroxypropyl modified guar gum provided by the invention has the performances of ultralow water-insoluble substance, quick tackifying, high viscosity, low usage amount and the like, and has the function of effectively promoting cost reduction and efficiency improvement when being used as a fracturing thickening agent.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of the carboxymethyl dihydroxypropyl modified guar obtained in example 1;
FIG. 2 is a nuclear magnetic hydrogen spectrum of a modified guar gum prepared by a comparative example;
FIG. 3 is the temperature resistant rheological curves of samples No. 1 and No. 4 of the present invention.
Detailed Description
The invention provides carboxymethyl dihydroxypropyl modified guar gum, which has a structure shown in a formula I:
in the formula I, R is independently-H, -CH2COOM or
The carboxymethyl dihydroxypropyl modified guar gum simultaneously contains-CH2COOM and
m is H, Na, K or NH4K is 1-3, and n and m are independently 10000-20000.
In the invention, n, m and k in the formula I are polymerization degrees, wherein n is the polymerization degree of a mannose unit without a galactose branch on guar gum, m is the polymerization degree of a galactose branch on guar gum, and k is the polymerization degree of dihydroxypropyl.
In the present invention, R is-CH2COOM, when R is carboxymethyl
When, dihydroxypropyl substituents are represented.
In the invention, the carboxymethyl substitution degree in the carboxymethyl dihydroxypropyl modified guar gum is preferably 0.01-2, and more preferably 0.02-1.
In the invention, the substitution degree of dihydroxypropyl in the carboxymethyl dihydroxypropyl modified guar gum is preferably 0.05-3, and more preferably 0.1-1.8.
In the present invention, the substitution degree is defined as the ratio of the number of moles of the substituent group to the number of moles of the saccharide unit in the guar gum.
In the invention, the weight average molecular weight of the carboxymethyl dihydroxypropyl modified guar gum is preferably 200000-2500000 daltons, and the number average molecular weight of the carboxymethyl dihydroxypropyl modified guar gum is preferably 100000-1500000 daltons.
In the present invention, the ratio of the weight average molecular weight to the number average molecular weight is preferably 1.1 to 3.5: 1.
the invention also provides a preparation method of the carboxymethyl dihydroxypropyl modified guar gum, which comprises the following steps:
mixing guar gum, an alkaline solution and a dispersing solvent under a protective atmosphere to carry out an alkalization reaction to obtain an alkalization product;
and mixing the alkalization product, an anionic etherifying agent solution and a non-ionic etherifying agent solution under a protective atmosphere to carry out etherification reaction to obtain the carboxymethyl dihydroxypropyl modified guar gum, wherein the anionic etherifying agent in the anionic etherifying agent solution comprises one or more of sodium chloroacetate, potassium chloroacetate and chloroacetic acid, and the non-ionic etherifying agent in the non-ionic etherifying agent solution comprises propylene epoxide alcohol and/or 3-chloropropanediol.
According to the invention, guar gum, an alkaline solution and a dispersing solvent are mixed for an alkalization reaction under a protective atmosphere to obtain an alkalization product.
In the present invention, the protective atmosphere is preferably nitrogen.
In the present invention, the guar gum is preferably guar gum pieces or guar gum powder.
In the present invention, the alkaline solution preferably includes one or more of an aqueous sodium hydroxide solution, an aqueous potassium hydroxide solution, and an aqueous tetramethylammonium hydroxide solution.
In the present invention, the mass concentration of the alkaline solution is preferably 2% to the normal temperature saturated solution concentration.
In the invention, the mass ratio of the alkaline solution to the guar gum is preferably 0.05-5: 1.
in the present invention, the dispersion solvent preferably includes one or more of water, ethanol, acetone, isopropanol, and dioxane.
In the invention, the mass ratio of the dispersing solvent to the guar gum is preferably 0.2-15: 1.
in the invention, the time of the alkalization reaction is preferably 0.2-2 h, and the temperature is preferably room temperature.
In the present invention, the alkalization reaction is preferably carried out in a reaction tank.
After the alkalization product is obtained, the alkalization product, an anionic etherifying agent solution and a nonionic etherifying agent solution are mixed for etherification reaction under the protective atmosphere to obtain the carboxymethyl dihydroxypropyl modified guar gum, wherein the anionic etherifying agent in the anionic etherifying agent solution comprises one or more of sodium chloroacetate, potassium chloroacetate and chloroacetic acid, and the nonionic etherifying agent in the nonionic etherifying agent solution comprises propylene epoxide alcohol and/or 3-chloropropanediol.
In the present invention, the protective atmosphere is preferably nitrogen.
In the present invention, the solvent of the anionic etherifying agent solution preferably includes one or more of water, ethanol, isopropanol and acetone.
In the present invention, the mass concentration of the anionic etherifying agent solution is preferably 5% to 100%.
In the invention, the mass ratio of the anionic etherifying agent to the guar gum in the anionic etherifying agent solution is preferably 0.02-2.0: 1.
in the present invention, the solvent of the nonionic etherifying agent solution preferably includes one or more of water, ethanol, isopropanol and acetone.
In the present invention, the mass concentration of the nonionic etherifying agent solution is preferably 5% to 100%.
In the invention, the mass ratio of the nonionic etherifying agent in the nonionic etherifying agent solution to the guar gum is preferably 0.05-4.0: 1.
in the invention, the temperature of the etherification reaction is preferably 5-100 ℃, more preferably 35-90 ℃, and the time is preferably 0.5-6.0 h.
In the present invention, the anionic etherifying agent solution and the nonionic etherifying agent solution are preferably added in a batch manner or in a combined manner.
In the present invention, the batch addition method is preferably to add the anionic etherifying agent solution first and then add the nonionic etherifying agent solution, or to add the nonionic etherifying agent solution first and then add the anionic etherifying agent solution, or to add both intermittently and repeatedly.
In the invention, after the etherification reaction, the pH value of the obtained etherification reaction product is preferably adjusted to 5-8.5.
In the invention, the neutralizing agent used for adjusting the pH value to 5-8.5 preferably comprises one or more of acetic acid, carbon dioxide, phosphoric acid, citric acid and polyphosphoric acid, and the dosage of the neutralizing agent is not particularly limited, so that the pH value can be adjusted to 5-8.5.
After the pH value is adjusted to 5-8.5, the method preferably further comprises the steps of washing, drying, crushing and screening in sequence to obtain the carboxymethyl dihydroxypropyl modified guar gum.
In the present invention, the solvent used for the washing preferably includes one or more of water, ethanol, acetone, isopropanol, and dioxane.
The present invention is not particularly limited in terms of the specific manner of drying, pulverizing and sieving, and may be implemented in a manner known to those skilled in the art.
The invention also provides application of the carboxymethyl dihydroxypropyl modified guar gum in the technical scheme as a fracturing thickening agent in the field of oil and gas fracturing.
To further illustrate the present invention, the following examples are provided to describe the carboxymethyl dihydroxypropyl modified guar of the present invention in detail, and the preparation method and application thereof, but they should not be construed as limiting the scope of the present invention.
Example 1
Adding 100 parts of guar gum powder, 300 parts of ethanol and 70 parts of a 30% sodium hydroxide aqueous solution by mass concentration into a reaction kettle, introducing nitrogen to remove oxygen, carrying out an alkalization reaction for 30 minutes, heating to raise the temperature of the material to 80 ℃, adding 30 parts of a 30% sodium chloroacetate aqueous solution by mass concentration, reacting for 60 minutes, adding 60 parts of 75% 3-chloropropanediol by mass concentration, continuing the reaction for 120 minutes at the temperature of 80 ℃, reducing the temperature to below 35 ℃ after the reaction is finished, carrying out a neutralization reaction by using 10 parts of 10% phosphoric acid solution to adjust the pH value to be between 6 and 8, washing the material twice by using 80% ethanol after carrying out centrifugal desolventization, using 200 parts of the material each time, and carrying out air flow drying and superfine grinding on the washing material to obtain a finished product which is marked as a No. 1 sample.
FIG. 1 is a sample No. 1 obtained by hydrolysis with trifluoroacetic acid1An H-NMR spectrum, wherein the chemical shift is between 4.59 and 5.52ppm and belongs to a peak signal of the galactose mannose anomer hydrogen after guar gum hydrolysis, and the chemical shift is a substituent carboxymethyl CH at 4.28 to 4.55ppm2The peak emergence signal indicates that a carboxymethyl group is successfully substituted on guar gum, the substitution degree is determined to be 0.09 through peak area calculation, the peak emergence signals of dihydroxypropyl and sugar hydroxyl are overlapped in a duck palm peak between 3.22 ppm and 4.28ppm, the substitution degree of dihydroxypropyl is determined through the increase of the peak area, the ratio of the original guar gum isocephalic hydrogen 4.24 ppm to 4.55ppm to the duck palm peak area is 1:6, the peak area after substitution is 1:8.3, and the substitution degree of dihydroxypropyl is 0.46 through calculation.
Example 2
Adding 100 parts of guar gum powder, 350 parts of ethanol and 100 parts of a 10% sodium hydroxide aqueous solution by mass concentration into a reaction kettle, introducing nitrogen to remove oxygen, carrying out an alkalization reaction for 30 minutes, heating to raise the temperature of the materials to 85 ℃, adding 30 parts of a 20% sodium chloroacetate aqueous solution by mass concentration, reacting for 60 minutes, adding 40 parts of 75% epoxypropanol by mass concentration, continuing to react for 120 minutes at the temperature of 85 ℃, reducing the temperature to be below 35 ℃ after the reaction is finished, carrying out a neutralization reaction by using 10 parts of a 10% phosphoric acid solution to adjust the pH value to be between 6 and 8, washing the materials twice by using 80% ethanol after centrifugal desolventization, wherein the dosage is 200 parts each time, and carrying out airflow drying and superfine grinding on the washing materials to obtain a finished product which is marked as a No. 2 sample. By using1The degree of substitution was found to be 0.06 and 0.44 for carboxymethyl and dihydroxypropyl, respectively, as measured by H-NMR spectroscopy.
Example 3
Adding 100 parts of guar gum powder, 300 parts of ethanol and 80 parts of sodium hydroxide aqueous solution with the mass concentration of 40% into a reaction kettle, introducing nitrogen to remove oxygen, carrying out an alkalization reaction for 30 minutes, heating to raise the temperature of the material to 80 ℃, adding 50 parts of sodium chloroacetate aqueous solution with the mass concentration of 30%, reacting for 60 minutes, adding 70 parts of 3-chloropropanediol with the mass concentration of 75%, continuing to react for 120 minutes at the temperature of 75 ℃, reducing the temperature to below 35 ℃ after the reaction is finished, carrying out a neutralization reaction by using 10 parts of 10% phosphoric acid solution to adjust the pH value to be between 6 and 8, washing the material twice by using 80% of ethanol after carrying out centrifugal desolventization, using 200 parts of the washing material each time, and carrying out air flow drying and superfine grinding on the washing material to obtain a finished product which is marked as a No. 3 sample. By using1The degree of substitution was found to be 0.15 and 0.58 for carboxymethyl and dihydroxypropyl, respectively, by H-NMR spectroscopy.
Comparative example
Adding 100 parts of guar gum powder, 300 parts of ethanol and 60 parts of 30% sodium hydroxide aqueous solution into a reaction kettle, introducing nitrogen to remove oxygen, carrying out alkalization reaction for 30 minutes, heating to raise the temperature of the material to 80 ℃, adding 60 parts of 75% 3-chloropropanediol, continuing to react for 120 minutes at the temperature of 80 ℃, reducing the temperature to below 35 ℃ after the reaction is finished, carrying out neutralization reaction by using 10 parts of 10% phosphoric acid solution to adjust the pH value6-8, after the materials are subjected to centrifugal desolventization, the materials are washed twice by using 80% ethanol, the dosage of each time is 200 parts, and the washing materials are subjected to airflow drying and superfine grinding to obtain a finished product, which is marked as a No. 4 sample. Sample No. 4 is dihydroxypropyl modified guar gum, does not contain carboxymethyl modification, and is used as a reference object of the performance of the carboxymethyl dihydroxypropyl modified guar gum. It is composed of1The H-NMR spectrum is shown in figure 2, and no obvious carboxymethyl CH exists at 4.28-4.55 ppm2The peak signal is shown, indicating that sample No. 4 has no carboxymethyl substitution, and the dihydroxypropyl degree of substitution is calculated to be 0.47.
Sample detection assay
The method for testing the substitution degree of the carboxymethyl dihydroxypropyl modified guar gum comprises the following steps: subjecting the test sample to hydrolysis with trifluoroacetic acid to form monosaccharides, using 600M nuclear magnetism1The degree of carboxymethyl substitution (CM-DS) and the degree of dihydroxypropyl substitution (DHP-DS) were analyzed by H-NMR.
The molecular weight determination method of the carboxymethyl dihydroxypropyl modified guar gum comprises the following steps: dissolving a sample into ultrapure water, preparing the mass concentration of the sample to be 0.03-0.1%, and testing the M by adopting a MALLS-GPC-VISC light scattering combined instrumentwAnd Mn。
TABLE 14 degree of substitution and molecular weight structural information for the samples
Determination of water-insoluble matter: adding 398.4mL of purified water into a stirring cup of a 1000mL Wuyi mixing and adjusting device, setting the stirring speed to 3000 r/min, accurately weighing 1.6 g of sample, quickly pouring the sample into the stirring cup, stirring for 5 min, pouring out, standing at 25 ℃ for 2h, putting 50g of slurry into a centrifugal tube, putting the centrifugal tube into a centrifuge tube at the rotating speed of 3000 r/min, centrifuging for 30 min, pouring out supernatant, adding about 50g of ultrapure water into precipitate, uniformly stirring, putting the precipitate into the centrifuge again, centrifuging for 20 min at 3000 r/min, pouring out supernatant, and baking the precipitate in an oven at 105 ℃ for constant weight.
Method for calculating water-insoluble substance:
the content of water-insoluble matter (sediment mass. times.8/sample mass. times.100%)
And (3) viscosity measurement: adding 400mL of purified water into a stirring cup of a 1000mL Wuyi mixing and blending device, setting the stirring speed to 3000 revolutions per minute, accurately weighing 2.4 g of sample, quickly pouring the sample into the stirring cup, stirring at a high speed for 2 minutes, pouring the sample out, standing at 25 ℃ for 2 hours, then pouring the slurry into a FANN35 viscometer measuring cup for measuring, and carrying out viscosity test, wherein the rotational speed of the viscometer is 300 revolutions per minute.
And (3) thickening speed measurement:
adding 400mL of purified water at 25 ℃ into a stirring cup of a 1000mL Wuyi mixing and blending device, setting the stirring speed to 1500 revolutions per minute, then adding 1.92 g of sample, stirring for 2.5 minutes, pouring the stirred slurry into a FANN35 viscometer measuring cup, starting the viscometer to test, wherein the rotational speed of the viscometer is 300 revolutions per minute, and the testing process ensures that the temperature of the slurry is 25 ℃, and recording the viscosities of mu 1, mu 2 and mu 3 for 3 minutes, 5 minutes and 60 minutes respectively.
Viscosity release rate calculation formula:
viscosity release rate at 3 min ═ μ 1/. mu.3X100%
Viscosity release rate at 5 min ═ μ 2/. mu.3X100%
Table 2 shows the measurement results of the water-insoluble substances, viscosity and viscosity increasing experiments of different samples, and it can be seen that compared with the guar gum modified by dihydroxypropyl group only in sample No. 4, the modified guar gums containing both carboxymethyl group and dihydroxypropyl group and having the substitution degree are lower in water-insoluble substances, higher in viscosity and similar in viscosity increasing speed in sample nos. 1 to 3.
TABLE 2 measurement results of water-insoluble substances, viscosity and thickening tests of different samples
The temperature-resistant rheological property experiment test of the fracturing fluid formula comprises the following steps: preparing base solutions with the concentrations of 0.35 wt% for sample No. 1, 0.35 wt% for sample No. 4 and 0.4 wt%, respectively, adjusting the pH value of the base solutions to 11.5, and adding 0.5 wt% of organic solvent into the base solutionsStirring boron crosslinking agent OBC-2 (Kunshan Jinguki oil field chemical technology Co., Ltd.) to suspension state to form jelly glue, wherein the jelly glue is prepared by using RS6000 rotational rheometer of Saimer Feishel company at 170s-1The rheological property of the material is tested by shearing frequency and 120 ℃. FIG. 3 shows the test results of the above three samples, and it can be seen from the figure that sample No. 4, in which the temperature resistance is better than 0.4 wt% at a concentration of 0.35 wt% of sample No. 1, can effectively reduce the use concentration by more than 10%.
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner. It should be noted that, for those skilled in the art, without departing from the principle of the present invention, several improvements and modifications can be made, and these improvements and modifications should also be construed as the protection scope of the present invention.
Claims (10)
1. The carboxymethyl dihydroxypropyl modified guar gum has the structure shown in the formula I:
in the formula I, R is independently-H, -CH2COOM or
The carboxymethyl dihydroxypropyl modified guar gum simultaneously contains-CH2COOM and
m is H, Na, K or NH4K is 1-3, and n and m are independently 10000-20000.
2. The carboxymethyl dihydroxypropyl modified guar according to claim 1, characterized in that the degree of substitution of carboxymethyl in the carboxymethyl dihydroxypropyl modified guar is 0.01 to 2.
3. The carboxymethyl dihydroxypropyl modified guar according to claim 1 or 2, characterized in that the degree of substitution of carboxymethyl in the carboxymethyl dihydroxypropyl modified guar is 0.02 to 1.
4. The carboxymethyl dihydroxypropyl modified guar according to claim 1, characterized in that the substitution degree of dihydroxypropyl groups in the carboxymethyl dihydroxypropyl modified guar is 0.05 to 3.
5. The carboxymethyl dihydroxypropyl modified guar according to claim 1 or 4, characterized in that the substitution degree of dihydroxypropyl groups in the carboxymethyl dihydroxypropyl modified guar is 0.1 to 1.8.
6. The carboxymethyl dihydroxypropyl modified guar according to claim 1, characterized in that the weight average molecular weight of the carboxymethyl dihydroxypropyl modified guar is 200000 to 2500000 daltons and the number average molecular weight is 100000 to 1500000 daltons.
7. The carboxymethyl dihydroxypropyl modified guar according to claim 1 or 6, characterized in that the ratio of the weight average molecular weight to the number average molecular weight is 1.1 to 3.5: 1.
8. the preparation method of the carboxymethyl dihydroxypropyl modified guar gum according to any one of claims 1 to 7, characterized by comprising the following steps:
mixing guar gum, an alkaline solution and a dispersing solvent under a protective atmosphere to carry out an alkalization reaction to obtain an alkalization product;
and mixing the alkalization product, an anionic etherifying agent solution and a non-ionic etherifying agent solution under a protective atmosphere to carry out etherification reaction to obtain the carboxymethyl dihydroxypropyl modified guar gum, wherein the anionic etherifying agent in the anionic etherifying agent solution comprises one or more of sodium chloroacetate, potassium chloroacetate and chloroacetic acid, and the non-ionic etherifying agent in the non-ionic etherifying agent solution comprises propylene epoxide alcohol and/or 3-chloropropanediol.
9. The preparation method according to claim 8, characterized by further comprising adjusting the pH value of the obtained etherification reaction product to 5-8.5 after the etherification reaction.
10. The application of the carboxymethyl dihydroxypropyl modified guar gum as claimed in any one of claims 1 to 7 in the field of oil and gas fracturing as a fracturing thickening agent.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115894733A (en) * | 2022-11-23 | 2023-04-04 | 昆山京昆油田化学科技有限公司 | Sulfur-containing modified guar gum and preparation method and application thereof |
| CN115894736A (en) * | 2022-12-30 | 2023-04-04 | 河南省化工研究所有限责任公司 | Modified guar gum and preparation method and application thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4096326A (en) * | 1976-10-13 | 1978-06-20 | Hercules Incorporated | Dihydroxypropyl cellulose |
| CN1123551A (en) * | 1993-04-15 | 1996-05-29 | 阿克佐诺贝尔公司 | Method of making amide modified carboxyl-containing polysaccharide and fatty amidemodified polysaccharide so obtainable |
| CN101420974A (en) * | 2006-02-15 | 2009-04-29 | 蒂卡莱克梅德尔公司 | Methods of manufacturing corticosteroid solutions |
| CN101563367A (en) * | 2006-11-17 | 2009-10-21 | 蓝宝迪有限公司 | Procedure for the preparation of purified cationic guar |
| US20100004197A1 (en) * | 2006-11-17 | 2010-01-07 | Lamberti Spa | Procedure for the preparation of glyoxalated cationic guar |
| CN101790541A (en) * | 2007-06-07 | 2010-07-28 | 蒙特利尔大学 | High-amylose sodium carboxymethyl starch sustained release excipient and preparation method thereof |
| CN104277138A (en) * | 2014-10-30 | 2015-01-14 | 山东广浦生物科技有限公司 | Method for preparing carboxymethyl hydroxyalkyl guar gum powder by virtue of one-step etherification |
| CN113087817A (en) * | 2021-05-24 | 2021-07-09 | 昆山京昆油田化学科技有限公司 | Guar gum derivative and preparation method and application thereof |
-
2021
- 2021-12-27 CN CN202111613458.0A patent/CN114149513B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4096326A (en) * | 1976-10-13 | 1978-06-20 | Hercules Incorporated | Dihydroxypropyl cellulose |
| CN1123551A (en) * | 1993-04-15 | 1996-05-29 | 阿克佐诺贝尔公司 | Method of making amide modified carboxyl-containing polysaccharide and fatty amidemodified polysaccharide so obtainable |
| CN101420974A (en) * | 2006-02-15 | 2009-04-29 | 蒂卡莱克梅德尔公司 | Methods of manufacturing corticosteroid solutions |
| CN101563367A (en) * | 2006-11-17 | 2009-10-21 | 蓝宝迪有限公司 | Procedure for the preparation of purified cationic guar |
| US20100004197A1 (en) * | 2006-11-17 | 2010-01-07 | Lamberti Spa | Procedure for the preparation of glyoxalated cationic guar |
| CN101790541A (en) * | 2007-06-07 | 2010-07-28 | 蒙特利尔大学 | High-amylose sodium carboxymethyl starch sustained release excipient and preparation method thereof |
| CN104277138A (en) * | 2014-10-30 | 2015-01-14 | 山东广浦生物科技有限公司 | Method for preparing carboxymethyl hydroxyalkyl guar gum powder by virtue of one-step etherification |
| CN113087817A (en) * | 2021-05-24 | 2021-07-09 | 昆山京昆油田化学科技有限公司 | Guar gum derivative and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 刘传杰: "阳离子羧甲基羟丙基瓜尔胶的制备及其助留助滤性能研究", 《功能材料》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115894733A (en) * | 2022-11-23 | 2023-04-04 | 昆山京昆油田化学科技有限公司 | Sulfur-containing modified guar gum and preparation method and application thereof |
| CN115894733B (en) * | 2022-11-23 | 2024-04-02 | 昆山京昆油田化学科技有限公司 | Sulfur-containing modified guar gum and preparation method and application thereof |
| CN115894736A (en) * | 2022-12-30 | 2023-04-04 | 河南省化工研究所有限责任公司 | Modified guar gum and preparation method and application thereof |
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