CN109517179A - A kind of chain alkyl polyoxyethylene groups hydrophobically modified guar gum thickener and preparation method thereof - Google Patents
A kind of chain alkyl polyoxyethylene groups hydrophobically modified guar gum thickener and preparation method thereof Download PDFInfo
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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 present invention relates to a kind of chain alkyl polyoxyethylene groups hydrophobically modified guar gums of guar derivative technical field used in oil field fracturing and preparation method thereof.The chain alkyl polyoxyethylene groups hydrophobically modified guar gum, is prepared: a) guar gum by the raw material comprising following components；B) chain alkyl polyoxyethylene groups glycidol ether；Wherein, the molar ratio of the chain alkyl polyoxyethylene groups glycidol ether and guar gum is (0.01~0.5): 1, preferably (0.05~0.2): 1；The chain alkyl polyoxyethylene groups glycidol ether is the brejs glycidol ether independently synthesized.In addition, the present invention also uses dimethyl sulfoxide as solvent, quaternary ammonium base is catalyst, homogeneous reaction is carried out at room temperature, and reaction condition is mild, and reaction efficiency is high, gained chain alkyl polyoxyethylene groups hydrophobically modified guar products thickening properties significantly improve, and have a good application prospect.
Description
Technical field
The present invention relates to guar derivative technical fields used in oil field fracturing, furtherly, are related to a kind of length
Alkyl group polyoxyethylene groups hydrophobically modified guar gum thickener and preparation method thereof.
Background technique
Guar gum is widely used in the industries such as oil field, printing and dyeing, food, daily use chemicals, but the presence of guar gum original powder cannot be fast instant
Swollen and hydration, the disadvantages of solution rate is slow, water insoluble matter content is high, viscosity is not easy to control, endurance of cutting is poor, perishable, therefore
It generally requires to obtain the guar derivative of improved properties, such as hydroxypropyl melon by chemical modifications such as etherificate, oxidation and esterifications
Your glue, guar gum, carboxymethyl hydroxypropyl guar gum etc..
The hydrophobically modified of guar gum mainly passes through three classes reagent: the long alkane of bromo, long chain alkenyl succinic anhydride or long-chain
Alkyl/eneamide, long linear alkyl glycidyl ether are reacted with guar gum or hydroxypropyl guar gum, and long linear alkyl is grafted
On the hydroxyl of guar gum.It is domestic at present that brominated alkanes is mostly used to carry out hydrophobically modified greatly, such as Li Xueping (Li Xueping, Fang Cui,
Niu Chunmei waits the hydrophobic modification of guar gum to study [J] coal and chemical industry, 2008 (10): 24-26.) it reported with bromo 16
Alkane carries out hydrophobic modification to natural guar gum as hydrophobically modified monomer, and hydrophobic guar gum comprehensive performance obtained is preferable, with guar gum
Aqueous solution is greatly improved compared to the stability of modifyed guar gum solution, but brominated alkanes reaction efficiency is low, be corrosive and price is high
Expensive, long chain alkenyl succinic anhydride or chain alkyl/eneamide introduce group complexity, and alkyl glycidyl ether product is easily located
It manages and can prevent further to react.Foreign countries mostly use alkyl glycidyl ether, as R Lapasin et al. (Lapasin R,
LdeL,PriclS,etal.Flow properties of hydroxypropyl guar gum and its long-chain
Hydrophobic derivatives. [J] .Carbohydrate Polymers, 1995,28 (3): 195-202.) it has studied
It is grafted the rheological behavior of the hydroxypropyl guar gum derivative of glycidyl docosyl ether, wherein the glycidyl used
Docosane position linear paraffin, it is stronger that there are hydrophobicitys, and grafting rate is difficult to control, and easily leads to precipitating.Also, currently available technology
The hydrophobically modified of middle guar gum is usually all to carry out suspension reaction in the in the mixed solvent of a kind of low-molecular-weight alcohol and water, such as: different
The mixture of propyl alcohol, methanol, ethyl alcohol, ethylene glycol etc. and water, since reactant can only react in two-phase interface, reaction
Low efficiency；In addition, being reacted in the prior art mostly using strong inorganic base as catalyst, reaction temperature, can not generally at 50~80 DEG C
Cause guar gum macromolecular chain segment to be broken with avoiding, the viscosity of modified guar gum is greatly reduced, to weaken its application
Energy.
Summary of the invention
In order to solve the above-mentioned problems in the prior art, the present invention proposes that a kind of chain alkyl polyoxyethylene groups are hydrophobic
Modified guar thickener.Relate in particular to a kind of chain alkyl polyoxyethylene groups hydrophobically modified guar gum thickener and its system
Preparation Method.The present invention uses the chain alkyl glycidol ether with hydrophilic segment as hydrophobically modified group, using can be by Guar
The reaction medium that glue and hydrophobic agents all dissolve carries out homogeneous reaction at room temperature and carrys out modified guar.
One of the object of the invention is to provide a kind of chain alkyl polyoxyethylene groups hydrophobically modified guar gum thickener, by comprising
The raw material of following components is prepared:
A) guar gum；
B) chain alkyl polyoxyethylene groups glycidol ether；
Wherein, the molar ratio of the chain alkyl polyoxyethylene groups glycidol ether and guar gum is (0.01~0.5): 1,
It is preferred that (0.05~0.2): 1；
The chain alkyl polyoxyethylene groups glycidol ether can be selected from brejs glycidol ether.Specifically, the benzyl
Damp class glycidol ether can be selected from four polyethyleneglycol lauryl glycidol ethers, polyoxyethylene (10) cetyl glycidol
Ether, polyoxyethylene (20) cetyl glycidyl ether, polyoxyethylene (20) hexadecane ether glycidol ether, polyoxyethylene (2)
Octadecyl glycidol ether, polyoxyethylene (2) cetyl glycidyl ether, in polyoxyethylene (2) oil base glycidol ether
At least one；The preferred polyoxyethylene of brejs glycidol ether (10) cetyl glycidyl ether, polyoxyethylene
(20) cetyl glycidyl ether or polyoxyethylene (20) hexadecane ether glycidol ether.
The brejs glycidol ether is autonomous synthesis, and hydrophilic segment (polyoxyethylene) can increase the dissolution of product
Degree, the problem that grafting caused by avoiding long chain alkane hydrophobic grouping hydrophobicity too strong excessively causes product insoluble, glycidol
Ether is as reactive group, compared with bromo, improves reaction efficiency and prevents further reaction.The brejs glycidol
The preparation method of ether can as described in the patent application No. is 201610815855.9, herein full text introduce application No. is
201610815855.9 the preparation method in patent.
The preparation method is specific as follows:
The brejs glycidol ether can be prepared by the preparation method included the following steps:
1) Brij is dissolved in dry toluene, azeotropic water removing；The usage ratio of the Brij and dry toluene can be 1g
Brij is dissolved in 5~20mL dry toluene；
2) sodium hydride under nitrogen protection, is added into flask, sodium hydride and Brij molar ratio are 1:1~5:1, are added
Dry toluene；Then the Brij after water removal is re-dissolved in dry toluene, flask is added, stir 1~3h；In step 2),
The usage ratio of dry toluene can correspond to 3~10mL dry toluene for the Brij that 1g is not removed water；
3) propylene oxide being added in reactant again, propylene oxide and Brij molar ratio are 2:1~7:1,30 DEG C~60
5~8h is reacted at DEG C；
4) reactant is stood, solid-liquid is layered, and solvent is distilled off in liquid pressure-reducing and obtains brejs glycidol ether.
The second object of the present invention is to providing a kind of preparation of chain alkyl polyoxyethylene groups hydrophobically modified guar gum thickener
Method is prepared by method comprising the following steps:
The method includes alkalizing, react in advance, purify three steps:
1) pre- alkalization: the guar gum is soluble in water, stirring；Quaternary ammonium base is added, stirs at room temperature, solution is freezed dry
It is dry；Wherein, the quaternary ammonium base is selected from tetrabutylammonium hydroxide (TBAOH), tetraethyl ammonium hydroxide (TEAOH), tetramethyl hydrogen-oxygen
Change at least one of ammonium (TMAOH)；It is preferred that tetrabutylammonium hydroxide (TBAOH)；
2) solid that freeze-drying obtains is put into dimethyl sulfoxide, is stirred at room temperature 1~8 hour, is then added
Chain alkyl polyoxyethylene groups glycidol ether stirs 1~8 day at room temperature；
3) reactant is diluted with water, is then charged into bag filter, bag filter is put into water/alcohol mixture and is stirred thoroughly
Analysis, to remove unreacted brejs glycidol ether, quaternary ammonium base and dimethyl sulfoxide；Then it dialyses in water, to remove second
Alcohol.The solution dialysed is freeze-dried, obtains white fluffy solid to get the chain alkyl polyoxyethylene groups hydrophobically modified
Guar gum thickener.
In the step 1), the dosage of the water is 10~100 times of guar gum weight；
In the step 1), the molar ratio of the quaternary ammonium base and guar gum saccharide unit is (1~5): 1.
In the step 2), the dosage of the dimethyl sulfoxide is 10~100 times of guar gum weight.
In the step 3),
When reactant is diluted with water, the dosage of the water is 10~100 times of guar gum weight；
When bag filter is put into stirring dialysis in water/alcohol mixture, the dosage of the water/alcohol mixture is guar gum
100~10000 times of weight.
When bag filter to be stirred to dialysis into the water, the dosage of the water is 100~10000 times of guar gum weight.
In the step 3), in the water/alcohol mixture, water and ethyl alcohol volume ratio are (0.5~2): 1；Every 2~6 is small
When change a water/alcohol mixture, change altogether 2~6 times；
In the step 3), when dialysing in water, the dosage of the water is 100~10000 times of guar gum weight；Every 2
A water is changed within~6 hours, is changed altogether 2~4 times.
Effect of the invention
Firstly, the present invention is using the chain alkyl polyoxyethylene groups glycidol ether independently synthesized as modified monomer, packet
Polyoxyethylene (10) cetyl glycidyl ether, polyoxyethylene (20) cetyl glycidyl ether are included, preparation method exists
Application No. is mention in 201610815855.9 patent.The monomer contains hydrophilic segment and hydrophobic segment its hydrophilic segment simultaneously
(polyoxyethylene) can increase the solubility of product, avoid using long chain alkane lacking as hydrophobic grouping in previous invention merely
Point: being used only long chain alkane as hydrophobic grouping in previous invention, and the hydrophobicity of long chain alkane hydrophobic grouping is too strong, appropriate to be grafted
Rate range is relatively narrow, if grafting rate is too low, hydrophobic grouping can not form tridimensional network, does not have heat resistance and salt tolerance, nothing
Method realizes the thickening effect that hydrophobic association reaches, and causes product insoluble if grafting rate is excessively high, away from hydrophobically modified thickening
Original intention, therefore there is no the matured product of long chain alkane hydrophobically modified guar gum so far.
Secondly, the present invention takes glycidol ether as reactive group, glycidol ether is connect by terminal epoxy ring open loop
Branch is on the hydroxyl of guar gum saccharide unit, and compared with the halogenated hydrocarbons that domestic existing patent generallys use, reactivity is higher, favorably
In raising reaction efficiency and can prevent further to react.
Third, the present invention using can using organic reaction medium dimethyl sulfoxide that guar gum and hydrophobic agents all dissolve as
Solvent, quaternary ammonium base are catalyst, carry out homogeneous reaction at room temperature, and reaction condition is mild, are used in the prior art with the country
Compared in the method that water/alcohol mixed solvent carries out heterogeneous suspension reaction, reactant contact probability increase, reaction efficiency it is higher and
The distribution of product grafted moiety is relatively uniform, and product characteristics are uniform, avoids reaction temperature in most reactions at present higher by (50~80
DEG C) be used as guar gum caused by when catalyst to degrade using strong inorganic base (usually NaOH) again, and then reduce its thickening properties.
4th, after tested, significantly improved using hydrophobically modified guar products thickening properties obtained by the method for the present invention.
Detailed description of the invention
Fig. 1 is the hydrogen nuclear magnetic resonance spectrogram of synthesized polyoxyethylene (20) hexadecane ether glycidol ether of embodiment 1；
Fig. 2 is the nuclear-magnetism hydrogen of the chain alkyl polyoxyethylene groups hydrophobically modified guar gum thickener sample 2 of embodiment 1
Spectrogram；
Fig. 3 be embodiment 3 the chain alkyl polyoxyethylene groups hydrophobically modified guar gum thickener sample 4 with it is unmodified
Guar gum solution shear viscosity comparison diagram.
Specific embodiment
Below with reference to embodiment, the present invention is further illustrated.But the present invention is not restricted by the embodiments.
Embodiment 1
0.0089mol (5.89g) polyoxyethylene (10) cetyl ether is dissolved in dry toluene, azeotropic water removing.?
Under nitrogen protection, 0.044mol (1.05g) sodium hydride is added into flask, adds 58mL dry toluene, after then removing water
Brij be re-dissolved in 30mL dry toluene, be added flask, stir 1h.0.0623mol (3.60g) propylene oxide is added again
Enter into reactant, reacts 5h at 30 DEG C.It answers object to be put into 4 DEG C of refrigerators to stand overnight, is layered solid-liquid.Carefully liquid is isolated
Carry out and be evaporated under reduced pressure removing toluene, obtains product polyoxyethylene (20) hexadecane ether glycidol ether (code name Brij56-
Epoxide xm09-214), it is sample 1.Product is without being further purified, yield 95%.By product Brij56-epoxide
Xm09-214 is dissolved in deuterated chloroform (CDCl3), then hydrogen nuclear magnetic resonance spectrum analysis is carried out, hydrogen nuclear magnetic resonance spectrogram is shown in Fig. 1, according to peak
Reactivity 100% is calculated in area integral.
0.1g guar gum is dissolved in 4g water, is stirred 16 hours.It is added tetrabutylammonium hydroxide (TBAOH), TBAOH and melon
The molar ratio of your glycocoll unit is 3, is stirred 1 hour at room temperature.Solution is freeze-dried, white fluffy solid 0.47g is obtained.
White fluffy solid is put into the dimethyl sulfoxide (DMSO) of 4g, is stirred at room temperature 4 hours, it is poly- that chain alkyl is then added
Oxyethylene group glycidol ether sample 1, i.e. polyoxyethylene (20) hexadecane ether glycidol ether (code name Brij56-epoxide
Xm09-214), the molar ratio of chain alkyl polyoxyethylene groups glycidol ether and guar gum is 0.15.It stirs 4 days at room temperature.
Above-mentioned reactant is added in 10g water and is diluted, bag filter is then charged into, bag filter is put into water/ethyl alcohol of 1000g
Dialysis is stirred in (50:50v/v) mixture, is changed within every 2 hours water/ethyl alcohol (50:50v/v) mixture, is changed altogether 6 times, to go
Except unreacted brejs glycidol ether, quaternary ammonium base and dimethyl sulfoxide；Then it dialyses, changes in the water of 1000g within every 2 hours
Water changes 4 times, altogether to remove ethyl alcohol.The solution dialysed is transferred in round-bottomed flask from bag filter, is freeze-dried,
White fluffy solid is obtained, the chain alkyl polyoxyethylene groups hydrophobically modified guar gum thickener, referred to as sample 2 is made.?
Before carrying out nuclear magnetic spectrogram test, sample 2 is dissolved in heavy water, concentration 6mg/mL uses German Brooker DRX400 nuclear magnetic resonance
Instrument carries out hydrogen nuclear magnetic resonance spectrum analysis and carries out nuclear magnetic resonance spectroscopy, and gained nucleus magnetic hydrogen spectrum figure is shown in Fig. 2, is calculated by integrating peak areas
Obtain degree of substitution DS=0.02.
Embodiment 2
1g guar gum is dissolved in 100g water, is stirred 8 hours.It is added tetrabutylammonium hydroxide (TBAOH), TBAOH and melon
The molar ratio of your glycocoll unit is 5, stirs 1 hour at room temperature, solution is freeze-dried.The solid that freeze-drying obtains is put into
The dimethyl sulfoxide (DMSO) of 100g is stirred at room temperature 1 hour, chain alkyl polyoxyethylene groups glycidol ether is then added
The molar ratio of sample 1, chain alkyl polyoxyethylene groups glycidol ether and guar gum is 0.2.It stirs 1 day at room temperature.It will be above-mentioned
Reactant is diluted with 10g water, is then charged into bag filter, bag filter is put into water/ethyl alcohol (50:50v/v) mixture of 1000g
Stirring dialysis, changes water/ethyl alcohol (50:50v/v) mixture for every 6 hours, changes 2 times, then dialyse in the water of 1000g altogether,
It changes a water within every 6 hours, changes altogether 2 times.The solution dialysed is transferred in round-bottomed flask from bag filter, is freeze-dried, obtains
To white fluffy solid, the chain alkyl polyoxyethylene groups hydrophobically modified guar gum thickener, referred to as sample 3 is made.
Embodiment 3
1g guar gum is dissolved in the water of 20g, is stirred 24 hours.Be added tetrabutylammonium hydroxide (TBAOH), TBAOH with
The molar ratio of guar gum saccharide unit is 1, stirs 1 hour at room temperature, solution is freeze-dried.The solid that freeze-drying obtains is put
Enter in the dimethyl sulfoxide (DMSO) of 20g, is stirred at room temperature 8 hours, it is sweet that the shrink of chain alkyl polyoxyethylene groups is then added
The molar ratio of oily ether sample 1, chain alkyl polyoxyethylene groups glycidol ether and guar gum is 0.01, is stirred 8 days at room temperature.It will
Above-mentioned reactant is diluted with 100g water, is then charged into bag filter, and water/ethyl alcohol (50:50v/v) that bag filter is put into 1000g is mixed
It closes and stirs dialysis in object, change within every 3 hours water/ethyl alcohol (50:50v/v) mixture, change altogether 3 times, it is then saturating in 1000g water
Analysis, changes a water in every 3 hours, changes altogether 3 times.The solution dialysed is transferred in round-bottomed flask from bag filter, is freeze-dried,
White fluffy solid is obtained, the chain alkyl polyoxyethylene groups hydrophobically modified guar gum thickener, referred to as sample 4 is made.It will
Sample 4 is dissolved in the solution that water is configured to 4.8g/L, and same using 2000 rheometer test its rheological property of TA company, U.S. AR
Unmodified guar gum solution is compared under concentration, and modified product solution viscosity is substantially improved, and sees Fig. 3.
Claims (10)
1. a kind of chain alkyl polyoxyethylene groups hydrophobically modified guar gum thickener, by the raw material preparation comprising following components
At:
A) guar gum；
B) chain alkyl polyoxyethylene groups glycidol ether；
Wherein, the molar ratio of the chain alkyl polyoxyethylene groups glycidol ether and guar gum is (0.01~0.5): 1, preferably
(0.05~0.2): 1；
The chain alkyl polyoxyethylene groups glycidol ether is selected from brejs glycidol ether.
2. a kind of chain alkyl polyoxyethylene groups hydrophobically modified guar gum thickener according to claim 1, feature exist
In:
The brejs glycidol ether is selected from four polyethyleneglycol lauryl glycidol ethers, polyoxyethylene (10) cetyl
Glycidol ether, polyoxyethylene (20) cetyl glycidyl ether, polyoxyethylene (20) hexadecane ether glycidol ether, polyoxy
Ethylene (2) octadecyl glycidol ether, polyoxyethylene (2) cetyl glycidyl ether, polyoxyethylene (2) oil base shrink sweet
At least one of oily ether.
3. a kind of chain alkyl polyoxyethylene groups hydrophobically modified guar gum thickener according to claim 1, feature exist
In:
The brejs glycidol ether is prepared by the preparation method included the following steps:
1) Brij is dissolved in dry toluene, azeotropic water removing；
2) sodium hydride under nitrogen protection, is added into flask, sodium hydride and Brij molar ratio are 1:1~5:1, are added anhydrous
Toluene；Then the Brij after water removal is re-dissolved in dry toluene, flask is added, stir 1~3h；
3) propylene oxide is added in reactant again, propylene oxide and Brij molar ratio are 2:1~7:1, at 30 DEG C~60 DEG C
React 5~8h；
4) reactant is stood, solid-liquid is layered, and solvent is distilled off in liquid pressure-reducing and obtains brejs glycidol ether.
4. a kind of chain alkyl polyoxyethylene groups hydrophobically modified guar gum thickener according to claim 1, feature exist
It is prepared in by method comprising the following steps:
The method includes alkalizing, react in advance, purify three steps:
1) pre- alkalization: the guar gum is soluble in water, stirring；Quaternary ammonium base is added, stirs at room temperature, solution is freeze-dried；
2) solid that freeze-drying obtains is put into dimethyl sulfoxide, be stirred at room temperature, it is poly- that the chain alkyl is then added
Oxyethylene group glycidol ether stirs 1~8 day at room temperature；
3) reactant is diluted with water, is then charged into bag filter, bag filter is put into stir in water/alcohol mixture and is dialysed；So
It dialyses in water afterwards；The solution dialysed is freeze-dried, obtains white fluffy solid to get the chain alkyl polyoxyethylene
Base hydrophobically modified guar gum thickener.
5. described in any item a kind of chain alkyl polyoxyethylene groups hydrophobically modified guar gum thickenings according to claim 1~4
The preparation method of agent, it is characterised in that the following steps are included:
The method includes alkalizing, react in advance, purify three steps:
1) pre- alkalization: the guar gum is soluble in water, stirring；Quaternary ammonium base is added, stirs at room temperature, solution is freeze-dried；
2) solid that freeze-drying obtains is put into dimethyl sulfoxide, be stirred at room temperature, it is poly- that the chain alkyl is then added
Oxyethylene group glycidol ether stirs 1~8 day at room temperature；
3) reactant is diluted with water, is then charged into bag filter, bag filter is put into stir in water/alcohol mixture and is dialysed；So
It dialyses in water afterwards；The solution dialysed is freeze-dried, obtains white fluffy solid to get the chain alkyl polyoxyethylene
Base hydrophobically modified guar gum thickener.
6. a kind of preparation side of chain alkyl polyoxyethylene groups hydrophobically modified guar gum thickener according to claim 5
Method, it is characterised in that:
In the step 1), the molar ratio of the quaternary ammonium base and guar gum saccharide unit is (1~5): 1；
In the step 1), the dosage of the water is 10~100 times of guar gum weight；
In the step 2), the dosage of the dimethyl sulfoxide is 10~100 times of guar gum weight.
7. a kind of preparation side of chain alkyl polyoxyethylene groups hydrophobically modified guar gum thickener according to claim 5
Method, it is characterised in that:
The molar ratio of the chain alkyl polyoxyethylene groups glycidol ether and guar gum is (0.01~0.5): 1, preferably (0.05
~0.2): 1；
The chain alkyl polyoxyethylene groups glycidol ether is selected from brejs glycidol ether.
8. a kind of preparation side of chain alkyl polyoxyethylene groups hydrophobically modified guar gum thickener according to claim 5
Method, it is characterised in that:
The quaternary ammonium base is selected from least one of tetrabutylammonium hydroxide, tetraethyl ammonium hydroxide, tetramethylammonium hydroxide.
9. a kind of preparation side of chain alkyl polyoxyethylene groups hydrophobically modified guar gum thickener according to claim 5
Method, it is characterised in that:
In the step 3), the dosage of the water/alcohol mixture is 100~10000 times of guar gum weight；Water/the second
In alcohol mixture, water and ethyl alcohol volume ratio are (0.5~2): 1；It changes a water/alcohol mixture within every 2~6 hours, changes 2~6 altogether
It is secondary；
In the step 3), when dialysing in water, the dosage of the water is 100~10000 times of guar gum weight；Every 2~6 hours
A water is changed, is changed altogether 2~4 times.
10. a kind of preparation side of chain alkyl polyoxyethylene groups hydrophobically modified guar gum thickener according to claim 5
Method, it is characterised in that:
In the step 3), when reactant is diluted with water, the dosage of the water is 10~100 times of guar gum weight.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112500583A (en) * | 2020-11-23 | 2021-03-16 | 江南大学 | Hydrophobically modified xanthan gum solution and preparation method and application thereof |
| CN112646048A (en) * | 2019-10-12 | 2021-04-13 | 中国石油化工股份有限公司 | Hydrophobic benzyl modified guar gum thickener and preparation method and application thereof |
| CN115819635A (en) * | 2022-12-15 | 2023-03-21 | 沧州中润化学助剂有限公司 | Multifunctional alkali-free viscoelastic thickener for improving recovery ratio and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0055433A1 (en) * | 1980-12-30 | 1982-07-07 | Hoechst Aktiengesellschaft | Oxalkylated addition products from ethylene oxide-propylene oxide block polymers and bisglycidyl ethers, and their use |
| CN102827300A (en) * | 2012-08-30 | 2012-12-19 | 华南理工大学 | Preparation method and application of hydrophobic modified guar gum |
| WO2014139037A1 (en) * | 2013-03-15 | 2014-09-18 | University Of New Brunswick | Self-assembling polymer compositions for use in subterranean oil recovery |
-
2017
- 2017-09-18 CN CN201710839079.0A patent/CN109517179A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0055433A1 (en) * | 1980-12-30 | 1982-07-07 | Hoechst Aktiengesellschaft | Oxalkylated addition products from ethylene oxide-propylene oxide block polymers and bisglycidyl ethers, and their use |
| CN102827300A (en) * | 2012-08-30 | 2012-12-19 | 华南理工大学 | Preparation method and application of hydrophobic modified guar gum |
| WO2014139037A1 (en) * | 2013-03-15 | 2014-09-18 | University Of New Brunswick | Self-assembling polymer compositions for use in subterranean oil recovery |
Non-Patent Citations (3)
| Title |
|---|
| AHMAD BAHAMDAN等: "Hydrophobic guar gum derivatives prepared by controlled grafting processes", 《POLYMERS FOR ADVANCED TECHNOLOGIES》 * |
| FENGSAN ZHANG等: "Synthesis of 2-alkenyl-3-butoxypropyl guar gum with enhancedrheological properties", 《INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES》 * |
| 苗霞等: "缩水甘油基聚氧乙烯十六烷基醚疏水改性瓜尔胶", 《2014年博士后学术论坛——油气成藏理论与勘探开发技术论文集》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112646048A (en) * | 2019-10-12 | 2021-04-13 | 中国石油化工股份有限公司 | Hydrophobic benzyl modified guar gum thickener and preparation method and application thereof |
| CN112500583A (en) * | 2020-11-23 | 2021-03-16 | 江南大学 | Hydrophobically modified xanthan gum solution and preparation method and application thereof |
| CN112500583B (en) * | 2020-11-23 | 2022-06-24 | 无锡市德宁节能科技有限公司 | Hydrophobically modified xanthan gum solution and preparation method and application thereof |
| CN115819635A (en) * | 2022-12-15 | 2023-03-21 | 沧州中润化学助剂有限公司 | Multifunctional alkali-free viscoelastic thickener for improving recovery ratio and preparation method thereof |
| CN115819635B (en) * | 2022-12-15 | 2023-06-02 | 沧州中润化学助剂有限公司 | Multifunctional alkali-free viscoelastic thickener for improving recovery ratio and preparation method thereof |
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