CN103896295A - Alkylphenol polyoxyethylene carboxylate (sulfonate) betaine modified organic soil and preparation method thereof - Google Patents
Alkylphenol polyoxyethylene carboxylate (sulfonate) betaine modified organic soil and preparation method thereof Download PDFInfo
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Abstract
The invention relates to an alkylphenol polyoxyethylene carboxylate (sulfonate) betaine modified organic soil and a preparation method thereof, and aims to solve the problem that the gel-forming rate of organic soil is low in white oil in the prior art. The modified organic soil comprises the following components: (1) sodium bentonite; and (2) alkylphenol polyoxyethylene carboxylate (sulfonate) betaine; wherein the formula of the component (2) is represented in the description, in the formula, the M represents an alkali metal or an alkali earth metal, the R represents a C1-C20 alkyl group, and n is an integer in a range of 1 to 30. The modified organic soil well solves the problem mentioned above, and is capable of being applied to an oil-based drilling fluid system taking white oil as the basic oil.
Description
Technical field
The present invention relates to organophilic clay of a kind of alkylphenol polyoxyethylene carboxylic acid (sulfonic acid) betaine salt modification and preparation method thereof.
Background technology
Organophilic clay normally the hydrophilic clay of high dispersing and cats product (quaternary ammonium salt) that ion-exchange absorption has occurred is prepared.Because the long hydrocarbon chain of tensio-active agent covers clay wafer surface, make it to form hydrophobic surface, simultaneously owing to entering the volume effect of chip layer surface active agent ion, increase chip layer distance.Just because of these constructional features, make organophilic clay there is good thixotropy, thickening property, suspension and collosol stability, thereby be widely used as anti-settling agent, rheological agent, oil drilling slurry thickening material, the stablizer of daily chemical product etc. of paint, ink/coating.
Typical organophilic clay reaction is as follows:
Na-soil+[(R
1r
2r
3r
4n)
+x
-] → soil-NR
1r
2r
3r
4+ Na
+x
-
The quality of organophilic clay depends primarily on the kind of clay, and type, carbochain length and the level of coverage on surface of clay and the preparation condition of cats product, as temperature, pH value etc.At present, generally use cats product for the modification of clay, as Trimethyllaurylammonium bromide, palmityl trimethyl ammonium chloride etc.Adopt other properties-correcting agent to prepare the report of organophilic clay less.CN1138593A adopts H
3pO
4react with hexanolactam, generate the organic agent of phosphoric acid hexanolactam, then this organic agent is joined and in clay water solution, carry out ion-exchange, make between hexanolactam positively charged ion interposed layer, form organophilic clay, but the organophilic clay that this method generates is the poor colloid of mobility, wetting ability is stronger, water a large amount of in system can only be removed by distillation, and therefore energy consumption is very high; CN101624515A has reported a kind of organophilic clay that can be used for white oil and preparation method thereof, adopt quaternary cationics and nonionogenic tenside jointly as properties-correcting agent, clay is carried out to modification, the organophilic clay obtaining plastic rate in white oil is high, but owing to using two kinds of tensio-active agents, experimental procedure is comparatively loaded down with trivial details.
Oil base drilling fluid is because the restriction that is subject to cost, environmental requirement develops slower always, the block of application is also less, along with existing oilfield reserve declines day by day, and the exploitation in new exploratory area can run into various bad grounds and environment, be badly in need of the organophilic clay that oil base drilling fluid is used of preparing of excellent property, to solve existing organophilic clay low problem of plastic rate in the oil base drilling fluid system taking white oil as base oil.In alkylphenol polyoxyethylene carboxylic acid (sulfonic acid) betaine salt surfactant structure, oleophylic carbochain is longer, the organic ion with certain three-dimensional arrangement enters inorganic mineral interlayer there is interlayer structure, after modification, interlamellar spacing obviously increases, insertion effect is remarkable, makes organophilic clay after the modification plastic rate in white oil higher.What invention was described carries out modification by alkylphenol polyoxyethylene carboxylic acid (sulfonic acid) betaine salt tensio-active agent to hydrophilic clay just, and the organophilic clay of preparation goes out the preparation method of the organophilic clay that plastic rate is high in white oil.
Summary of the invention
One of technical problem to be solved by this invention is organophilic clay lower problem of plastic rate in white oil in current production technology, and a kind of organophilic clay of new alkylphenol polyoxyethylene carboxylic acid (sulfonic acid) betaine salt modification is provided.This organophilic clay has advantages of that plastic rate is higher in white oil.Two of technical problem to be solved by this invention is to provide a kind of preparation method of organophilic clay of alkylphenol polyoxyethylene carboxylic acid (sulfonic acid) the betaine salt modification corresponding with one of technical solution problem.
In order one of to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: the organophilic clay of a kind of alkylphenol polyoxyethylene carboxylic acid (sulfonic acid) betaine salt modification, comprises following component in mass fraction:
(1) 0.5～30 part of sodium bentonite;
(2) 0.05～20 part of alkylphenol polyoxyethylene carboxylic acid (sulfonic acid) betaine salt;
Wherein, the general molecular formula of component (2) is:
Or
In formula, M be in basic metal any one, R is C
1～C
20alkyl, n is the arbitrary integer in 1～30.
In technique scheme, sodium bentonite preferred version is commercially available wilkinite; Basic metal preferred version is selected from sodium or potassium; R preferred version is C
4～C
16alkyl or alkenyl in one; The span preferred version of the polymerization degree n of Soxylat A 25-7 is 2～20.
For solve the problems of the technologies described above two, the technical solution used in the present invention is as follows: the preparation method of the organophilic clay of a kind of alkylphenol polyoxyethylene carboxylic acid (sulfonic acid) betaine salt modification, comprises the following steps:
1) sodium bentonite of aequum is distributed in water, after high-speed stirring, removes impurity by suspension method, make it to form stable suspension system a;
2) alkylphenol polyoxyethylene carboxylic acid (sulfonic acid) betaine salt of aequum is mixed with water, form homogeneous system b;
3) under high-speed stirring, system b being added drop-wise in system a, is 25～100 DEG C in temperature of reaction, reacts and within 0.5～24 hour, obtain product c under normal pressure; Wherein, the mass ratio of alkylphenol polyoxyethylene carboxylic acid (sulfonic acid) betaine salt and sodium bentonite is 1:1～20;
4) by step 3) the product c that obtains washing, then product c is dried at 80～120 DEG C of temperature, obtain the particulate below granularity 78 μ m, be the organophilic clay of alkylphenol polyoxyethylene carboxylic acid (sulfonic acid) betaine salt modification.
In technique scheme, alkylphenol polyoxyethylene carboxylic acid (sulfonic acid) betaine salt is 1:3～12 with the quality of sodium bentonite than preferable range; Temperature of reaction preferable range is 25～95 DEG C; Reaction times preferable range is 1～20 hour.
The organophilic clay of prepared alkylphenol polyoxyethylene carboxylic acid (sulfonic acid) the betaine salt modification of the present invention, compared with commercially available organophilic clay, the inventor is surprised to find it and in white oil, has advantages of that plastic rate is higher, its plastic rate in white oil can reach 80.2%, has obtained good technique effect.
Brief description of the drawings
In the present invention, all trimethyl-glycine modification organophilic clays all adopt following methods to characterize: X-ray diffraction (XRD), on Rigaku Rigaku D/Max-rB X-ray diffractometer, carry out, note spectrum scanning continuously, CuK α (λ=0.154) radiation, monochromatic tube, pipe is pressed 40kV, pipe stream 100mA, scanning speed 2
o/ min, sweep limit 2 θ=0～40
o; Thermogravimetic analysis (TGA) (TGA), adopts Perkin-Elmer 7 series of heat analytical systems, and temperature range is room temperature～1000 DEG C, and temperature rise rate is 10 DEG C/min, nitrogen atmosphere; Fourier infrared absorption spectrum (FTIR), adopt Nicolet USA 5DX FTIR spectrophotometer, sample KBr compressing tablet, gained spectrogram contrasts with standard infrared spectrum, determine the chemical structure of sample, to reach the Infrared Characterization to compound of the present invention.
Fig. 1 is that amyl group (R=5) phenol polyethenoxy ether (n=2) carboxylic acid sodium trimethyl-glycine modification organophilic clay contrasts figure with commercially available sodium bentonite infrared absorption spectrum;
Fig. 2 is amyl group (R=5) phenol polyethenoxy ether (n=2) hydroxyl sulfoacid potassium trimethyl-glycine modification organophilic clay and commercially available sodium bentonite infrared absorption spectrum;
Fig. 3 is that nonyl (R=9) phenol polyethenoxy ether (n=7) carboxylic acid sodium trimethyl-glycine modification organophilic clay contrasts collection of illustrative plates with commercially available sodium bentonite XRD;
Fig. 4 is that nonyl (R=9) phenol polyethenoxy ether (n=7) carboxylic acid sodium trimethyl-glycine modification organophilic clay contrasts collection of illustrative plates with commercially available sodium bentonite TGA;
Fig. 5 is that nonyl (R=9) phenol polyethenoxy ether (n=7) hydroxyl sulfoacid sodium trimethyl-glycine modification organophilic clay contrasts collection of illustrative plates with commercially available sodium bentonite XRD;
Fig. 6 is that nonyl (R=9) phenol polyethenoxy ether (n=7) hydroxyl sulfoacid sodium trimethyl-glycine modification organophilic clay contrasts collection of illustrative plates with commercially available sodium bentonite TGA;
Fig. 7 is that dodecyl phenol polyethenoxy ether (n=20) carboxylic acid sodium trimethyl-glycine modification organophilic clay contrasts collection of illustrative plates with commercially available sodium bentonite XRD;
Fig. 8 is that dodecyl phenol polyethenoxy ether (n=20) hydroxyl sulfoacid sodium trimethyl-glycine modification organophilic clay contrasts collection of illustrative plates with nonyl (R=9) phenol polyethenoxy ether (n=7) hydroxyl sulfoacid sodium trimethyl-glycine modification organophilic clay TGA.
Below by embodiment, the present invention is further elaborated.
Embodiment
[embodiment 1]
Synthesizing of amyl group (R=5) phenol polyethenoxy ether (n=2) carboxylic acid sodium trimethyl-glycine modification organophilic clay
1) commercially available 50g sodium bentonite is distributed in 600g water, after high-speed stirring, adopts suspension method to remove impurity, make it to form stable suspension system a;
2) 25g amyl group (R=5) phenol polyethenoxy ether (n=2) carboxylic acid sodium trimethyl-glycine (massfraction is 40%) is mixed with 150g water, form homogeneous system b;
3) under high-speed stirring, b is added drop-wise in a, under normal pressure, reacts 20 hours at 30 DEG C;
4) by the 3rd) the product washing that obtains of step 5 times, then product is dried at 80 DEG C of temperature, pulverize, obtain the particulate below granularity 78 μ m, i.e. amyl group (R=5) phenol polyethenoxy ether (n=2) carboxylic acid sodium trimethyl-glycine modification organophilic clay.
Fig. 1 is amyl group (R=5) phenol polyethenoxy ether (n=2) carboxylic acid sodium trimethyl-glycine modification organophilic clay and commercially available sodium bentonite infrared absorption spectrum, can find out, the infrared absorpting light spectra of amyl group (R=5) phenol polyethenoxy ether (n=2) carboxylic acid sodium type trimethyl-glycine modification organophilic clay is at 2942cm
-1and 2872cm
-1present obvious C-H stretching vibration peak, at 1466cm
-1there is the flexural vibration peak of C-H, at 1514cm
-1there is the stretching vibration peak of phenyl ring.As can be seen here, organically-modified soil and the original soil difference on infrared absorption spectrum, is mainly to make interlayer structure that variation occur because organic ion enters inorganic mineral interlayer.
[embodiment 2]
With [embodiment 1], difference substitutes the properties-correcting agent of amyl group (R=5) phenol polyethenoxy ether (n=2) carboxylic acid sodium trimethyl-glycine as organophilic clay using amyl group (R=5) phenol polyethenoxy ether (n=2) hydroxyl sulfoacid potassium trimethyl-glycine.
Fig. 2 is amyl group (R=5) phenol polyethenoxy ether (n=2) hydroxyl sulfoacid potassium trimethyl-glycine modification organophilic clay and commercially available sodium bentonite infrared absorption spectrum, can find out, the infrared absorpting light spectra of amyl group (R=5) phenol polyethenoxy ether (n=2) hydroxyl sulfoacid potassium trimethyl-glycine modification organophilic clay is at 2935cm
-1and 2856cm
-1present obvious C-H stretching vibration peak, at 1464cm
-1there is the flexural vibration peak of C-H, at 1510cm
-1there is the stretching vibration peak of phenyl ring.As can be seen here, organically-modified soil and the original soil difference on infrared absorption spectrum, is mainly to make interlayer structure that variation occur because organic ion enters inorganic mineral interlayer.
[embodiment 3]
Synthesizing of nonyl (R=9) phenol polyethenoxy ether (n=7) carboxylic acid sodium trimethyl-glycine modification organophilic clay
1) commercially available 45g sodium bentonite is distributed in 600g water, after high-speed stirring, adopts suspension method to remove impurity, make it to form stable suspension system a;
2) 9g nonyl (R=9) phenol polyethenoxy ether (n=7) carboxylic acid sodium trimethyl-glycine (massfraction is 50%) is mixed with 100g water, form homogeneous system b;
3) under high-speed stirring, b is added drop-wise in a, at 80 DEG C, under normal pressure, reacts 4 hours;
4) by the 3rd) the product washing that obtains of step 3 times, then product is dried at 120 DEG C, pulverize, obtain the particulate below granularity 78 μ m, i.e. nonyl (R=9) phenol polyethenoxy ether (n=7) carboxylic acid sodium type trimethyl-glycine modification organophilic clay.
Fig. 3 is that nonyl (R=9) phenol polyethenoxy ether (n=7) carboxylic acid sodium trimethyl-glycine modification organophilic clay contrasts collection of illustrative plates with commercially available wilkinite XRD.Wilkinite is moisture stratiform sial saline minerals, utilizes d (001) value that X-ray diffractometer records can reflect the interlamellar spacing situation after montmorillonite intercalation modifying.D (001) value of original soil is 1.23nm, and after modification, existing suitable organic cation enters into original soil interlayer.D (001) the face diffraction peak of organophilic clay moves to little angular direction, due to the long carbon chain lengths of nonyl (R=9) phenol polyethenoxy ether (n=7) carboxylic acid sodium trimethyl-glycine and with the steric effect of three-dimensional arrangement, after making its modification, interlamellar spacing obviously increases, and d (001) value reaches 2.01nm.As can be seen from the figure betaine type properties-correcting agent enters between bentonite bed, mainly interlamellar spacing is exerted an influence, and structure and the pattern of other parts of wilkinite do not change.
Fig. 4 is that nonyl (R=9) phenol polyethenoxy ether (n=7) carboxylic acid sodium trimethyl-glycine modification organophilic clay contrasts collection of illustrative plates with commercially available wilkinite TGA, enters the quantity of interlayer in order to analyze the thermostability of original soil and organic ion.As we know from the figure, there is adsorbing the weightlessness of free water in original soil near 56.8 DEG C, and weight loss is 10.01%, 677.7 DEG C of weight losses reach 14.38%, for losing interlayer in conjunction with due to water, after this to 1000 DEG C substantially without weightless, illustrates structure and the stable performance of original soil below 1000 DEG C.By contrast, nonyl (R=9) phenol polyethenoxy ether (n=7) carboxylic acid sodium type trimethyl-glycine modification organophilic clay only had 1.4% weight loss before 306.9 DEG C, 366.8 DEG C time because the most of organic cation combustion decomposition of interlayer weight loss reaches 23.8%, after this temperature, weightlessness slows down, be mainly decomposing again of the remaining organic cation of interlayer and resolvent thereof, 1000 DEG C time, weight loss reaches 37.5%, conforms with the industry standard of weight loss 33～41%.
[embodiment 4]
With [embodiment 3], difference substitutes the properties-correcting agent of nonyl (R=9) phenol polyethenoxy ether (n=7) carboxylic acid sodium trimethyl-glycine as organophilic clay using nonyl (R=9) phenol polyethenoxy ether (n=7) hydroxyl sulfoacid sodium trimethyl-glycine.
Fig. 5 is that nonyl (R=9) phenol polyethenoxy ether (n=7) hydroxyl sulfoacid sodium trimethyl-glycine modification organophilic clay contrasts collection of illustrative plates with commercially available wilkinite XRD.Wilkinite is moisture stratiform sial saline minerals, utilizes d (001) value that X-ray diffractometer records can reflect the interlamellar spacing situation after montmorillonite intercalation modifying.D (001) value of original soil is 1.23nm, and after modification, existing suitable organic cation enters into original soil interlayer.D (001) the face diffraction peak of organophilic clay moves to little angular direction, due to the long carbon chain lengths of nonyl (R=9) phenol polyethenoxy ether (n=7) hydroxyl sulfoacid sodium trimethyl-glycine and with the steric effect of three-dimensional arrangement, after making its modification, interlamellar spacing increases, and d (001) value reaches 1.60nm.As can be seen from the figure betaine type properties-correcting agent enters between bentonite bed, mainly interlamellar spacing is exerted an influence, and structure and the pattern of other parts of wilkinite do not change.
Fig. 6 is that nonyl (R=9) phenol polyethenoxy ether (n=7) hydroxyl sulfoacid sodium trimethyl-glycine modification organophilic clay contrasts collection of illustrative plates with commercially available wilkinite TGA, enters the quantity of interlayer in order to analyze the thermostability of original soil and organic ion.As we know from the figure, there is adsorbing the weightlessness of free water in original soil near 56.8 DEG C, and weight loss is 10.01%, 677.7 DEG C of weight losses reach 14.38%, for losing interlayer in conjunction with due to water, after this to 1000 DEG C substantially without weightless, illustrates structure and the stable performance of original soil below 1000 DEG C.By contrast, nonyl (R=9) phenol polyethenoxy ether (n=7) hydroxyl sulfoacid sodium trimethyl-glycine modification organophilic clay only had 4.9% weight loss before 305.4 DEG C, 411.1 DEG C time because the most of organic cation combustion decomposition of interlayer weight loss reaches 9.1%, after this temperature, weightlessness slows down, and is mainly decomposing again of the remaining organic cation of interlayer and resolvent thereof.
[embodiment 5]
Synthesizing of dodecyl phenol polyethenoxy ether (n=20) carboxylic acid sodium trimethyl-glycine modification organophilic clay
1) commercially available 54g sodium bentonite is distributed in 600g water, after high-speed stirring, adopts suspension method to remove impurity, make it to form stable suspension system a;
2) 30g dodecyl phenol polyethenoxy ether (n=20) carboxylic acid sodium type trimethyl-glycine (massfraction is 60%) is mixed with 200g water, form homogeneous system b;
3) under high-speed stirring, b is added drop-wise in a, under normal pressure, 95 DEG C are reacted 2 hours;
4) by the 3rd) the product washing that obtains of step 3 times, then product is dried at 105 DEG C of temperature, pulverized 200 orders, obtain dodecyl phenol polyethenoxy ether (n=20) carboxylic acid sodium trimethyl-glycine modification organophilic clay.
Fig. 7 is that dodecyl phenol polyethenoxy ether (n=20) carboxylic acid sodium trimethyl-glycine modification organophilic clay contrasts collection of illustrative plates with commercially available wilkinite XRD.D (001) value of original soil is 1.23nm, and after modification, existing suitable organic cation enters into original soil interlayer.D (001) the face diffraction peak of organophilic clay moves to little angular direction, due to the long carbon chain lengths of dodecyl phenol polyethenoxy ether (n=20) carboxylic acid sodium trimethyl-glycine and more remarkable compared with nonyl (R=9) phenol polyethenoxy ether (n=7) carboxylic acid sodium type trimethyl-glycine with the steric effect of three-dimensional arrangement, after making its modification, interlamellar spacing obviously increases, and d (001) value reaches 3.29nm.
[embodiment 6]
With [embodiment 5], difference substitutes the properties-correcting agent of dodecyl phenol polyethenoxy ether (n=20) carboxylic acid sodium trimethyl-glycine as organophilic clay using dodecyl (R=12) phenol polyethenoxy ether (n=20) hydroxyl sulfoacid sodium trimethyl-glycine.
Fig. 8 is that dodecyl phenol polyethenoxy ether (n=20) hydroxyl sulfoacid sodium trimethyl-glycine modification organophilic clay contrasts collection of illustrative plates with nonyl (R=9) phenol polyethenoxy ether (n=7) hydroxyl sulfoacid sodium trimethyl-glycine modification organophilic clay TGA.As can be seen from the figure, because the carbon chain lengths that dodecyl phenol polyethenoxy ether (n=20) hydroxyl sulfoacid sodium trimethyl-glycine is long is more remarkable compared with nonyl (R=9) phenol polyethenoxy ether (n=7) hydroxyl sulfoacid sodium trimethyl-glycine, in the time of 387.4 DEG C, dodecyl phenol polyethenoxy ether (n=20) hydroxyl sulfoacid sodium trimethyl-glycine modification organophilic clay weight loss reaches 21.4%.After this temperature, weightlessness slows down, and is mainly decomposing again of the remaining organic cation of interlayer and resolvent thereof.
[embodiment 7～12]
Measure the commercially available white oil of 100mL, joining height stirs in cup, take 2g[embodiment 1～6] in synthetic alkylphenol polyoxyethylene carboxylic acid (sulfonic acid) betaine salt modification organophilic clay, under the condition of 5000r/min, the organophilic clay taking slowly being joined to height stirs in cup, stirring the oily earth mixtures rapidly height being stirred in cup after 30 minutes pours in 100mL tool plug graduated cylinder, cover grinding port plug, leave standstill, and the volume V of upper strata free oil after while recording 24h.The plastic rate of alkylphenol polyoxyethylene carboxylic acid (sulfonic acid) betaine salt modification organophilic clay in white oil, the results are shown in Table shown in 1.
X?=?(100?–?V)/100
Wherein, X is plastic rate, %;
The volume of the free white oil that when V is 24h, separate out on graduated cylinder top, mL.
[comparative example 1]
With [embodiment 7], the above marine products organophilic clay of difference substitutes amyl group (R=5) phenol polyethenoxy ether (n=2) carboxylic acid sodium trimethyl-glycine modification organophilic clay, and all the other are identical, have measured the plastic rate of organophilic clay in white oil, and result is as shown in table 1.
[comparative example 2]
With [embodiment 4], difference is produced organophilic clay with Tianjin and is substituted amyl group (R=5) phenol polyethenoxy ether (n=2) carboxylic acid sodium trimethyl-glycine modification organophilic clay, and all the other are identical, have measured the plastic rate of organophilic clay in white oil, and result is as shown in table 1.
The plastic rate of table 1 modification organophilic clay in white oil
| Title | Plastic rate/% in white oil |
| Amyl group (R=5) phenol polyethenoxy ether (n=2) carboxylic acid sodium trimethyl-glycine modification organophilic clay | 61.0 |
| Nonyl (R=9) phenol polyethenoxy ether (n=7) carboxylic acid potassium trimethyl-glycine modification organophilic clay | 68.0 |
| Dodecyl phenol polyethenoxy ether (n=20) carboxylic acid sodium trimethyl-glycine modification organophilic clay | 76.1 |
| Amyl group (R=5) phenol polyethenoxy ether (n=2) hydroxyl sulfoacid sodium trimethyl-glycine modification organophilic clay | 65.0 |
| Nonyl (R=9) phenol polyethenoxy ether (n=7) hydroxyl sulfoacid sodium trimethyl-glycine modification organophilic clay | 72.1 |
| Dodecyl (R=12) phenol polyethenoxy ether (n=20) hydroxyl sulfoacid sodium trimethyl-glycine modification organophilic clay | 80.2 |
| Commercially available organophilic clay (Shanghai, the place of production) | 50.1 |
| Commercially available organophilic clay (Tianjin, the place of production) | 45.2 |
Claims (7)
1. an organophilic clay for alkylphenol polyoxyethylene carboxylic acid (sulfonic acid) betaine salt modification, comprises following component in mass fraction:
(1) 0.5～30 part of sodium bentonite;
(2) 0.05～20 part of alkylphenol polyoxyethylene carboxylic acid (sulfonic acid) betaine salt;
Wherein, the general molecular formula of component (2) is:
Or
In formula, M is for being selected from basic metal any one, and R is C
1～C
20alkyl, n is the arbitrary integer in 1～30.
2. the organophilic clay of alkylphenol polyoxyethylene carboxylic acid according to claim 1 (sulfonic acid) betaine salt modification, is characterized in that sodium bentonite is commercially available wilkinite.
3. according to the organophilic clay of alkylphenol polyoxyethylene carboxylic acid (sulfonic acid) the betaine salt modification described in claim 1, it is characterized in that basic metal is selected from sodium or potassium.
4. the organophilic clay of alkylphenol polyoxyethylene carboxylic acid according to claim 1 (sulfonic acid) betaine salt modification, is characterized in that R is C
4～C
16alkyl or alkenyl in one.
5. according to the organophilic clay of alkylphenol polyoxyethylene carboxylic acid (sulfonic acid) the betaine salt modification described in claim 1, the span that it is characterized in that the polymerization degree n of Soxylat A 25-7 is 2～20.
6. the preparation method of the organophilic clay of alkylphenol polyoxyethylene carboxylic acid claimed in claim 1 (sulfonic acid) betaine salt modification, comprises the following steps:
1) sodium bentonite of aequum is distributed in water, after high-speed stirring, removes impurity by suspension method, make it to form stable suspension system a;
2) alkylphenol polyoxyethylene carboxylic acid (sulfonic acid) betaine salt of aequum is mixed with water, form homogeneous system b;
3) under high-speed stirring, system b being added drop-wise in system a, is 25～100 DEG C in temperature of reaction, reacts and within 0.5～24 hour, obtain product c under normal pressure; Wherein, the mass ratio of alkylphenol polyoxyethylene carboxylic acid (sulfonic acid) betaine salt and sodium bentonite is 1:1～20;
4) by step 3) the product c that obtains washing, then product c is dried at 80～120 DEG C of temperature, obtain the particulate below granularity 78 μ m, be the organophilic clay of alkylphenol polyoxyethylene carboxylic acid (sulfonic acid) betaine salt modification.
7. according to the preparation method of the organophilic clay of alkylphenol polyoxyethylene carboxylic acid (sulfonic acid) betaine salt described in claim 6, the mass ratio that it is characterized in that alkylphenol polyoxyethylene carboxylic acid (sulfonic acid) betaine salt and sodium bentonite is 1:3～12; Temperature of reaction is 25～95 DEG C; Reaction times is 1～20 hour.
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|---|---|---|---|---|
| CN101870476A (en) * | 2010-05-14 | 2010-10-27 | 淄博联技化工有限公司 | Method for producing temperature-resistant organically modified bentonite |
| CN102277146A (en) * | 2010-06-11 | 2011-12-14 | 中国石油化工股份有限公司 | Composition for improving recovery ratio substantially and preparation method thereof |
| CN102277148A (en) * | 2010-06-11 | 2011-12-14 | 中国石油化工股份有限公司 | Composition for improving recovery ratio of crude oil and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101870476A (en) * | 2010-05-14 | 2010-10-27 | 淄博联技化工有限公司 | Method for producing temperature-resistant organically modified bentonite |
| CN102277146A (en) * | 2010-06-11 | 2011-12-14 | 中国石油化工股份有限公司 | Composition for improving recovery ratio substantially and preparation method thereof |
| CN102277148A (en) * | 2010-06-11 | 2011-12-14 | 中国石油化工股份有限公司 | Composition for improving recovery ratio of crude oil and preparation method thereof |
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