CN114149513B - Carboxymethyl dihydroxypropyl modified guar gum and preparation method and application thereof - Google Patents
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- 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 polysaccharide molecular chains of the solution is improved, the viscosity of the solution at the same concentration is increased, the guar gum fracturing fluid serving as a 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 a little, 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 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, -CH 2 COOM or
The carboxymethyl dihydroxypropyl modified guar gum simultaneously contains-CH 2 COOM and
m is H, na, K or NH 4 Wherein k is 1 to 3, and n and m are independently 10000 to 20000.
Preferably, the carboxymethyl dihydroxypropyl modified guar gum has a carboxymethyl degree of substitution of 0.01 to 2.
Preferably, the carboxymethyl dihydroxypropyl modified guar gum has a carboxymethyl degree of substitution of 0.02 to 1.
Preferably, the substitution degree of dihydroxypropyl in the carboxymethyl dihydroxypropyl modified guar gum is 0.05 to 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 is 100000-1500000 daltons.
Preferably, the ratio of the weight average molecular weight to the number average molecular weight is 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.
Preferably, the etherification reaction is followed by adjusting the pH value of the obtained etherification reaction product to 5 to 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 quantity of crosslinkable cis-dihydroxy sites, but also improves the extension degree of polysaccharide molecular chains of a solution, increases the viscosity of the solution at the same concentration, has excellent crosslinking performance and reduced use concentration when 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, -CH 2 COOM or
And the carboxymethyl dihydroxypropyl modified guar gum simultaneously contains-CH 2 COOM and
m is H, na, K or NH 4 Wherein k is 1 to 3, and n and m are independently 10000 to 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-CH 2 COOM, when R is a carboxymethyl substituent
When, a dihydroxypropyl substituent is represented.
In the present invention, the carboxymethyl substitution degree in the carboxymethyl dihydroxypropyl modified guar gum is preferably 0.01 to 2, and more preferably 0.02 to 1.
In the invention, the substitution degree of dihydroxypropyl in the carboxymethyl dihydroxypropyl modified guar gum is preferably 0.05 to 3, and more preferably 0.1 to 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 carboxymethyl dihydroxypropyl modified guar gum preferably has a weight average molecular weight of 200000 to 2500000 daltons and a number average molecular weight of 100000 to 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 alkalized product, an anionic etherifying agent solution and a nonionic 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 nonionic etherifying agent in the nonionic 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 present invention, the mass ratio of the alkaline solution to guar gum is preferably 0.05 to 5:1.
in the present invention, the dispersion solvent preferably includes one or more of water, ethanol, acetone, isopropanol, and dioxane.
In the present invention, the mass ratio of the dispersion solvent to the guar gum is preferably 0.2 to 15:1.
in the present invention, the time of the alkalization reaction is preferably 0.2 to 2 hours, and the temperature is preferably room temperature.
In the present invention, the alkalization reaction is preferably carried out in a reaction tank.
After obtaining the alkalized product, mixing the alkalized product, an anionic etherifying agent solution and a nonionic 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 nonionic etherifying agent in the nonionic etherifying agent solution comprises propylene oxide 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 present invention, the mass ratio of the anionic etherifying agent to the guar gum in the anionic etherifying agent solution is preferably 0.02 to 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 present invention, the mass ratio of the nonionic etherifying agent to the guar gum in the nonionic etherifying agent solution is preferably 0.05 to 4.0:1.
in the present invention, the temperature of the etherification reaction is preferably 5 to 100 ℃, more preferably 35 to 90 ℃, and the time is preferably 0.5 to 6.0 hours.
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 manner of adding in portions is preferably such that the anionic etherifying agent solution is added first and then the nonionic etherifying agent solution is added, or the nonionic etherifying agent solution is added first and then the anionic etherifying agent solution is added, or both of them are added intermittently and repeatedly.
In the present invention, it is preferable that the etherification reaction is followed by adjusting the pH of the resulting etherification reaction product to 5 to 8.5.
In the present invention, the neutralizing agent used for adjusting the pH to 5 to 8.5 preferably includes one or more of acetic acid, carbon dioxide, phosphoric acid, citric acid and polyphosphoric acid, and the amount of the neutralizing agent used in the present invention is not particularly limited, and it is sufficient to ensure that the pH is adjusted to 5 to 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 to 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, introducing nitrogen to remove oxygen, carrying out an alkalization reaction for 30 minutes, heating to raise the temperature of the materials to 80 ℃, adding 30 parts of a 30% sodium chloroacetate aqueous solution, reacting for 60 minutes, 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 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 desolvation, using 200 parts of ethanol each time, carrying out air flow drying and superfine grinding on the washing materials to obtain a finished product, and marking as a No. 1 sample.
FIG. 1 is a sample No. 1 obtained by hydrolysis with trifluoroacetic acid 1 H-NMR spectrum, wherein the chemical shift is between 4.59 and 5.52ppm and belongs to the peak signal of hydrogen anomer of galactose mannose after hydrolysis of guar gum, and the chemical shift is substituent carboxymethyl CH at 4.28 to 4.55ppm 2 The peak output signal of (1) 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 output signals of dihydroxypropyl group and sugar hydroxyl group are overlapped in a duck palm peak between 3.22 ppm and 4.28ppm, the substitution degree of dihydroxypropyl group 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, the peak area after substitution is 1.
Example 2
Adding 100 parts of guar gum powder, 350 parts of ethanol and 100 parts of 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 20% sodium chloroacetate aqueous solution by mass concentration, reacting for 60 minutes, adding 40 parts of 75% epoxypropanol, 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 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 obtaining a finished product, namely a sample No. 2, after carrying out airflow drying and superfine grinding on the washing materials. By using 1 The degree of substitution is determined by the extraction of the carboxymethyl group in the H-NMR spectrumThe substitution degree and the substitution degree of dihydroxypropyl group were 0.06 and 0.44, respectively.
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 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 using 1 The 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 a 30% sodium hydroxide aqueous solution, introducing nitrogen to remove oxygen, carrying out an alkalization reaction for 30 minutes, heating to raise the temperature of the material to 80 ℃, adding 60 parts of 3-chloropropanediol with the mass concentration of 75%, 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 a 10% phosphoric acid solution to adjust the pH value to between 6 and 8, washing the material twice by using 80% ethanol after centrifugal desolvation, wherein the dosage of 200 parts each time, and carrying out airflow drying and superfine grinding on the washed material to obtain a finished product, namely a sample No. 4. Sample No. 4 is dihydroxypropyl modified guar gum, does not contain carboxymethyl modification, and is used as a reference object for the performance of the carboxymethyl dihydroxypropyl modified guar gum. It is composed of 1 The H-NMR spectrum is shown in figure 2, and no obvious carboxymethyl CH exists between 4.28 and 4.55ppm 2 The 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 magnetism 1 H-NMR analysisCarboxymethyl degree of substitution (CM-DS) and dihydroxypropyl degree of substitution (DHP-DS).
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 instrument w And M n 。
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, centrifuging for 30 min at the rotating speed of 3000 r/min, pouring out supernatant, adding about 50g of ultrapure water into precipitate, uniformly stirring, putting the mixture into the centrifuge again, centrifuging for 20 min at 3000 r/min, pouring out the supernatant, and baking the precipitate in an oven at 105 ℃ for constant weight.
Method for calculating water-insoluble substance:
water insoluble content = precipitate mass × 8/sample mass × 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 measurement, 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:
3 min viscosity release = μ 1/μ 3 × 100%
5 min viscosity release = μ 2/μ 3 × 100%
Table 2 shows the measurement results of the water-insoluble substances, viscosities, and thickening tests of different samples, and it can be seen that the modified guar gums containing both carboxymethyl groups and dihydroxypropyl groups and having the substitution degrees of both carboxymethyl groups and dihydroxypropyl groups, samples nos. 1 to 3, have lower water-insoluble substances, higher viscosities, and similar thickening rates, as compared to the guar gum modified with sample No. 4 only dihydroxypropyl groups.
TABLE 2 measurement results of water-insoluble substances, viscosity and thickening tests of different samples
The temperature resistance rheological property test of the fracturing fluid formula comprises the following steps: respectively preparing 0.35wt% of sample No. 1, 0.35wt% of sample No. 4 and 0.4wt% of concentration base liquid, adjusting the pH value of the base liquid to 11.5, adding 0.5wt% of organic boron crosslinking agent OBC-2 (Kyokun oilfield chemical technology Co., ltd.) into the base liquid, stirring to a state capable of being hung, forming jelly glue, and adopting RS6000 rotational rheometer of Saimefeyer company to carry out jelly glue for 170s -1 The 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, sample No. 1, whose 0.35wt% concentration has better temperature resistance than 0.4wt%, 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 (8)
1. A carboxymethyl dihydroxypropyl modified guar gum has a structure shown in formula I:
in the formula I, R is independently-H, -CH 2 COOM or
And the carboxymethyl dihydroxypropyl modified guar gum simultaneously contains-CH 2 COOM and
wherein M is H, na, K or NH 4 K is 1 to 3, and n and m are 10000 to 20000 independently;
the carboxymethyl substitution degree in the carboxymethyl dihydroxypropyl modified guar gum is 0.01 to 2;
the substitution degree of dihydroxypropyl in the carboxymethyl dihydroxypropyl modified guar gum is 0.05 to 3.
2. The carboxymethyl dihydroxypropyl modified guar according to claim 1, characterized in that the carboxymethyl substitution degree in the carboxymethyl dihydroxypropyl modified guar is 0.02 to 1.
3. 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 0.1 to 1.8.
4. 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.
5. The carboxymethyl dihydroxypropyl modified guar according to claim 4, characterized in that the ratio of the weight average molecular weight to the number average molecular weight is 1.1 to 3.5:1.
6. the preparation method of the carboxymethyl dihydroxypropyl modified guar gum according to any one of claims 1 to 5, 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 alkalized product, an anionic etherifying agent solution and a nonionic 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 nonionic etherifying agent in the nonionic etherifying agent solution comprises propylene epoxide alcohol and/or 3-chloropropanediol.
7. The preparation method according to claim 6, characterized in that after the etherification reaction, the pH value of the obtained etherification reaction product is adjusted to 5 to 8.5.
8. The application of the carboxymethyl dihydroxypropyl modified guar gum as defined in any one of claims 1 to 5 as a fracturing thickening agent in the field of oil and gas fracturing.
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| CN202111613458.0A CN114149513B (en) | 2021-12-27 | 2021-12-27 | Carboxymethyl dihydroxypropyl modified guar gum and preparation method and application thereof |
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| CN114149513B true CN114149513B (en) | 2022-10-11 |
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Citations (7)
| 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 |
| 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 |
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| ITVA20060068A1 (en) * | 2006-11-17 | 2008-05-18 | Lamberti Spa | PROCEDURE FOR THE PREPARATION OF GULI CATIONICO GLIOSSALATO |
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Patent Citations (7)
| 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 |
| 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 |
|---|
| 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;刘传杰;《功能材料》;20190331;第03159-03164页 * |
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