CN108440323A - A kind of star-like polycation based surfactants and its preparation method and application - Google Patents
A kind of star-like polycation based surfactants and its preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of star-like polycation based surfactants and its preparation method and application, which is prepared by following steps：Quantitative trimethylolpropane tris (3 aziridinyl propionic ester) reaction solution is added dropwise in the reaction bulb equipped with long-chain fat primary amine ethanol solution and acidic catalyst and carries out first step aziridine ring-opening reaction；Quantitative chloromethanes (or benzyl chloride) reaction solution is added into reaction solution again and carries out second step quaternary ammonium reaction, products therefrom is a kind of star-like polycation based surfactants.
Description
Technical field
The present invention relates to multi-quaternary ammonium salt cationic surfactant preparing technical field, more particularly to a kind of star-like more sun from
Subbase surfactant and its preparation method and application.
Background technology
Polycationic quaternary ammonium salt surfactant makes it have higher because having multiple hydrophilic radicals and multiple hydrophobic groupings
Table/interfacial activity, lower critical micelle concentration, more excellent bactericidal property, good foaming power and foam stability and its solely
The physical and chemical performances such as special rheological characteristic are widely used in preparing new material, fungicide, inhibit metal erosion, fabric finishing, oil
The fields such as exploitation.Currently, it is cationic Gemini surface active that the research of polycationic quaternary ammonium salt surfactant is most commonly used
Agent, but there is no a kind of star-like polycation based surfactants to meet existing demand.
With the development of petroleum works technology, the drillng operations such as deep-well, extended reach well and horizontal well are more and more, bore and meet ground
Layer becomes increasingly complex, and the highly difficult oil well in part has the spies such as wellbore is big, displacement is big, extended horizontal depth, well track change greatly
Point leads to problems such as mud shale stratum exist and seriously collapses and expand undergauge and serious pulping, this inhibits water-base drilling fluid
More stringent requirements are proposed for ability, and efficient clay stabilizer is to ensure that the key of wellbore stability and drilling fluid inhibition.In recent years
Small molecule quaternary ammonium salt clay stabilizer is gradually taken seriously, small molecule quaternary ammonium salt clay stabilizer easily by clay Preferential adsorption,
It can promote to be dehydrated between clay crystal layer, reduce expansive force, effectively inhibit clay aquation, and can be embedded between clay crystal layer, prevent water
Molecule enters, and reduces the hydration swelling effect of clay, since it is adsorbed securely on clay particle, has effect steady in a long-term.
But existing quaternary ammonium salt clay stabilizer there are dosages it is big, anti-dilative is low and big to formation damage the problems such as, the present invention is to season
Ammonium salt class clay stabilizer molecular structure is redesigned, and a kind of high performance star-like multi-quaternary ammonium salt class clay of synthesis is stablized
Agent.The clay stabilizer can effectively inhibit clay hydration swelling and dispersion migration under extremely low dosage.
Invention content
In order to extend the type of polycationic quaternary ammonium salt surfactant and the quantity of polycationic quaternary ammonium salt, the present invention
React to be formed with independent hub-and-spoke configuration with active amido with the aziridine crosslinker of high activity, be re-introduced into halogenated alkyl object into
Row quaternary ammonium reaction obtains a kind of polycation surfactant with hub-and-spoke configuration.It is an object of the present invention to carry
For a kind of star-like polycation based surfactants.
The second object of the present invention is to provide the preparation method of the surfactant.
In order to achieve the above objectives, the present invention uses following technical scheme：
A kind of star-like polycation based surfactants, structural formula are：
Wherein, R1It is long aliphatic chain, carbon atom number is 12~18 in carbochain；R2For-H or
A kind of preparation method of star-like polycation based surfactants, includes the following steps：
To-three (the 3- aziridinyls of middle addition trimethylolpropane of long-chain fat primary amine ethanol solution and acidic catalyst
Propionic ester) reaction solution progress aziridine ring-opening reaction, 6~8h is reacted at 50~80 DEG C；
Under weak basic condition, chloromethanes is added into above-mentioned reactant or the progress of benzyl chloride reaction solution liquid is quaternary ammoniated anti-
It answers, under nitrogen protection, 50~70 DEG C of 10~16h of reaction；Insoluble matter is removed after reaction, and concentration of reaction solution uses toluene
Column chromatography is isolated and purified with product, is dried under vacuum to constant weight and just obtains product.
In aziridine ring-opening reaction, trimethylolpropane-three (3- aziridinyls propionic ester) and long-chain fat primary amine rub
You are than being 1:3.
In aziridine ring-opening reaction, the acidic catalyst is the phosphate aqueous solution that mass fraction is 85%, is used
Amount is the 1% of raw material gross mass.
In quaternary ammonium reaction, weak basic condition pH=9~10, reaction solution K2CO3It is adjusted to alkalescent.
In quaternary ammonium reaction, the amount of the substance of chloromethanes or benzyl chloride is (the 3- aziridinyls third of trimethylolpropane-three
Acid esters) 6 times.
A kind of star-like polycation based surfactants are in oil-gas mining as the application of clay stabilizer.
Addition as clay stabilizer is the 0.2~1% of gross mass.
The present invention compared with the prior art, has the following advantages：
A kind of star-like polycation based surfactants of the present invention, wherein contain 18 quaternary ammonium salt groups, it can be simultaneously
Multiple spot acts on electronegative clay particle surface, and sphere of action is wide, a kind of efficient clay stabilizer can be used as.
The present invention reacts the star-like surface to be formed and carry active secondary amine with the aziridine crosslinker of high activity with active amido
Activating agent is re-introduced into the quaternary ammonium salt reagent reaction for carrying quaternary ammonium salt, obtains a kind of star-like polycation based surfactants, in order to
Extend the type of polycationic quaternary ammonium salt surfactant and the quantity of polycationic quaternary ammonium salt.
The present invention redesigns quaternary ammonium salt clay stabilizer molecular structure, and synthesis is a kind of high performance star-like more
Quaternary ammonium salt clay stabilizer.The clay stabilizer can effectively inhibit clay hydration swelling and dispersion migration under extremely low dosage.
The star-like clay stabilizer of polycation base multiple spot can be acted on negative simultaneously due to containing multiple quaternary ammonium salt groups in molecule
The clay particle of electricity, degree of absorption is high, to realize the purpose of low dosage, high anti-dilative.
Description of the drawings
Fig. 1 is the chemical structural formula of the present invention；
Fig. 2 is present invention reaction synthetic route chart.
Specific implementation mode
As depicted in figs. 1 and 2, reaction equation of the invention is：
Wherein, R1It is long aliphatic chain, carbon atom number is 12~18 in carbochain；R2For-H or
According to above-mentioned reaction mechanism, a kind of structural formula of star-like polycation based surfactants of the present invention is：
Wherein, R1It is long aliphatic chain, carbon atom number is 12~18 in carbochain；R2For-H or
The step of method for preparing a kind of above-mentioned star-like polycation based surfactants is：
Trimethylolpropane-three is added dropwise in the reaction bulb equipped with long-chain fat primary amine ethanol solution and acidic catalyst
(3- aziridinyls propionic ester) reaction solution carries out first step aziridine ring-opening reaction, wherein (the 3- aziridinyls of hydroxymethyl-propane-three
Propionic ester) and long-chain fat primary amine molar ratio be 1:3,6~8h is reacted at 50~70 DEG C；Again by above-mentioned reaction solution K2CO3It adjusts
To alkalescent (pH=9~10), chloromethanes (or benzyl chloride) reaction solution is added and carries out second step quaternary ammonium reaction, wherein chloromethanes
The amount of the substance of (or benzyl chloride) is 6 times of trimethylolpropane-three (3- aziridinyls propionic ester), under nitrogen protection, 50
~70 DEG C of 10~16h of reaction.Insoluble matter is removed after reaction, and concentration of reaction solution is isolated and purified with toluene column chromatography
Product is dried under vacuum to constant weight and just obtains product.
Technical solution in the embodiment of the present invention is subjected to clear, complete description below.Obviously, described implementation
Example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, the common skill in this field
The every other embodiment that art personnel are obtained without creative efforts belongs to the model that the present invention protects
It encloses.
Embodiment 1
(1) in the dodecyl primary amine ethanol solution (34.69g, wherein containing dodecyl primary for being 80% equipped with mass fraction
Amine 27.75g, 0.15mol) and acidic catalyst (85%H3PO4, 0.50g), 50 DEG C are warming up to, it is 70% that mass fraction, which is added dropwise,
Trimethylolpropane-three (3- aziridinyls propionic ester) ethanol solution (35.42g, wherein (the 3- a word used for translations third containing trimethylolpropane-three
Piperidinyl propionic ester) 21.25g, 0.05mol), time for adding 40min.After being added dropwise, it is warming up to 70 DEG C of reaction 6h.
(2) by above-mentioned reaction solution K2CO3It is adjusted to alkalescent (pH=9~10), under nitrogen protection, mass fraction is added dropwise
For 60% chloromethanes ethanol solution (25.25g, wherein 15.15g containing chloromethanes, 0.30mol), 10h is reacted at 50 DEG C；Reaction
After remove insoluble matter, concentration of reaction solution is isolated and purified with product with toluene column chromatography, and being dried under vacuum to constant weight must produce
Object.
The structural formula of 1 products therefrom of embodiment is：
1H NMR (300MHz, DMSO)：δ 3.94 (s, 6H), 3.63~3.68 (m, 18H), 3.30 (s, 36H), 3.22 (t,
6H), 2.69 (t, 6H), 1.68~1.71 (m, 8H), 1.26~1.29 (s, 54H), 0.83~0.88 (m, 12H) ppm.
13C NMR (300MHz, DMSO)：δ 173.1,65.9,64.4,61.8,58.8~59.1,52.0~52.3,35.7,
31.9,29.3~29.6,26.8,25.4,22.7,14.1,7.3ppm.
Embodiment 2
(1) in the octadecyl primary amine ethanol solution (50.53g, wherein containing octadecyl primary for being 80% equipped with mass fraction
Amine 40.43g, 0.15mol) and acidic catalyst (85%H3PO4, 0.60g), 50 DEG C are warming up to, it is 70% that mass fraction, which is added dropwise,
Trimethylolpropane-three (3- aziridinyls propionic ester) ethanol solution (35.42g, wherein (the 3- a word used for translations third containing trimethylolpropane-three
Piperidinyl propionic ester) 21.25g, 0.05mol), time for adding 40min.After being added dropwise, it is warming up to 50 DEG C of reaction 8h.
(2) by above-mentioned reaction solution K2CO3It is adjusted to alkalescent (pH=9~10), under nitrogen protection, mass fraction is added dropwise
For 80% benzyl chloride ethanol solution (47.48g, wherein chloride containing benzyl 37.98g, 0.30mol), 16h is reacted at 70 DEG C；Reaction
After remove insoluble matter, concentration of reaction solution is isolated and purified with product with toluene column chromatography, is dried under vacuum to constant weight just
Product.
The structural formula of 2 products therefrom of embodiment is：
1H NMR (300MHz, DMSO)：δ 7.16~7.25 (m, 60H), 4.5 (s, 24H), 3.63~3.68 (m, 18H),
3.22 (t, 6H), 2.69 (t, 6H), 1.69~1.71 (m, 8H), 1.26~1.29 (s, 90H), 0.83 (t, 12H) ppm.
13C NMR (300MHz, DMSO)：δ 173.1,125.7~131.6,65.9,60.8~54.6,35.7,22.7~
31.9,14.1,7.1ppm.
Embodiment 3
(3) in the myristyl primary amine ethanol solution (40.03g, wherein containing myristyl primary for being 80% equipped with mass fraction
Amine 32.03g, 0.15mol) and acidic catalyst (85%H3PO4, 0.50g), 50 DEG C are warming up to, it is 70% that mass fraction, which is added dropwise,
Trimethylolpropane-three (3- aziridinyls propionic ester) ethanol solution (35.42g, wherein (the 3- a word used for translations third containing trimethylolpropane-three
Piperidinyl propionic ester) 21.25g, 0.05mol), time for adding 40min.After being added dropwise, it is warming up to 60 DEG C of reaction 7h.
(4) by above-mentioned reaction solution K2CO3It is adjusted to alkalescent (pH=9~10), under nitrogen protection, mass fraction is added dropwise
For 80% benzyl chloride ethanol solution (47.48g, wherein chloride containing benzyl 37.98g, 0.30mol), 12h is reacted at 60 DEG C；Reaction
After remove insoluble matter, concentration of reaction solution is isolated and purified with product with toluene column chromatography, is dried under vacuum to constant weight just
Product.
The structural formula of 3 products therefrom of embodiment is：
Embodiment 4
(1) in the cetyl primary amine ethanol solution (45.29g, wherein containing cetyl primary for being 80% equipped with mass fraction
Amine 36.23g, 0.15mol) and acidic catalyst (85%H3PO4, 0.50g), 50 DEG C are warming up to, it is 70% that mass fraction, which is added dropwise,
Trimethylolpropane-three (3- aziridinyls propionic ester) ethanol solution (35.42g, wherein (the 3- a word used for translations third containing trimethylolpropane-three
Piperidinyl propionic ester) 21.25g, 0.05mol), time for adding 40min.After being added dropwise, it is warming up to 60 DEG C of reaction 7h.
(2) by above-mentioned reaction solution K2CO3It is adjusted to alkalescent (pH=9~10), under nitrogen protection, mass fraction is added dropwise
For 60% chloromethanes ethanol solution (25.25g, wherein 15.15g containing chloromethanes, 0.30mol), 12h is reacted at 60 DEG C；Reaction
After remove insoluble matter, concentration of reaction solution is isolated and purified with product with toluene column chromatography, and being dried under vacuum to constant weight must produce
Object.
The structural formula of 4 products therefrom of embodiment is：
The performance characterization of clay stabilizer
(1) anti-dilative of clay stabilizer and the test of water-fastness rate
Reference standard SY/T 5971-2016《Oil-gas field fracturing is acidified and water filling clay stabilizer method of evaluating performance》
With Q/SH 0053-2010《The requirement of clay stabilizer technology》Middle centrifugal process method, it is molten in clay stabilizer by measuring sodium bentonite
Expansion increment in liquid and distilled water evaluates anti-dilative.Determine the anti-dilative of the clay stabilizer of Examples 1 to 3 in water and
Water-fastness rate.The results are shown in Table 1.
The anti-dilative of 1 clay stabilizer of table and water-fastness rate
As seen from table, for clay stabilizer of the invention under 0.2% dosage, the anti-dilative in riverfrac treatment liquid is high
In 80%, water-fastness rate is more than 90%；For clay stabilizer under 0.5% dosage, the anti-dilative in riverfrac treatment liquid is equal
Higher than 90%；For clay stabilizer under 1.0% dosage, the anti-dilative in riverfrac treatment liquid is above 93%.It compares inorganic
Salt clay stabilizer (potassium chloride and ammonium chloride), under 2.0% dosage, anti-dilative is below 70%.
(2) compatibility is tested
Compatibility observation is carried out to the clay stabilizer and fracturing fluid base fluid and acid solution of Examples 1 to 3, as a result such as table 2
It is shown.
The compatibility of 2 clay stabilizer of table is tested
From table 2 it can be seen that the clay stabilizer of the present invention is mixed with fracturing fluid base fluid and acid solution, no layering, precipitation
It is generated with suspension phenomenon, compatibility is good.
Embodiment 5
(1) equipped with mass fraction be 20% methylamine water solution (23.25g, wherein 4.65g containing methylamine, 0.15mol) and
Acidic catalyst (85%H3PO4, 0.30g), 40 DEG C are warming up to, (the 3- of trimethylolpropane-three that mass fraction is 70% is added dropwise
Aziridinyl propionic ester) aqueous solution (35.42g, wherein contain trimethylolpropane-three (3- aziridinyls propionic ester) 21.25g,
0.05mol), time for adding 40min.After being added dropwise, it is warming up to 70 DEG C of reaction 5h.
(2) by above-mentioned reaction solution K2CO3It is adjusted to alkalescent (pH=9~10), under nitrogen protection, mass fraction is added dropwise
For 60% chloromethanes ethanol solution (25.25g, wherein 15.15g containing chloromethanes, 0.30mol), 10h is reacted at 50 DEG C；Reaction
After remove insoluble matter, concentration of reaction solution is isolated and purified with product with toluene column chromatography, and being dried under vacuum to constant weight must produce
Object.
The structural formula of 5 products therefrom of embodiment is：
1H NMR (300MHz, DMSO)：δ 3.91 (s, 6H), 3.67 (m, 18H), 3.26 (m, 33H), 2.70 (t, 6H),
1.67 (m, 2H), 1.27 (t, 36H), 0.84 (t, 3H) ppm.
13C NMR (300MHz, DMSO)：δ 173.5,66.1,54.1~56.8,49.5,35.7,27.3,23.0,7.9~
8.3ppm。
Embodiment 6
(1) equipped with mass fraction be 70% ethylamine solution (9.54g, wherein 6.75g containing ethamine, 0.15mol) and
Acidic catalyst (85%H3PO4, 0.30g), 50 DEG C are warming up to, (the 3- of trimethylolpropane-three that mass fraction is 70% is added dropwise
Aziridinyl propionic ester) aqueous solution (35.42g, wherein contain trimethylolpropane-three (3- aziridinyls propionic ester) 21.25g,
0.05mol), time for adding 40min.After being added dropwise, it is warming up to 70 DEG C of reaction 7h.
(2) by above-mentioned reaction solution K2CO3It is adjusted to alkalescent (pH=9~10), under nitrogen protection, mass fraction is added dropwise
For 80% benzyl chloride ethanol solution (47.48g, wherein chloride containing benzyl 37.98g, 0.30mol), 16h is reacted at 70 DEG C；Reaction
After remove insoluble matter, concentration of reaction solution is isolated and purified with product with toluene column chromatography, is dried under vacuum to constant weight just
Product.
The structural formula of 6 products therefrom of embodiment is：
1H NMR (300MHz, DMSO)：δ 7.16~7.25 (m, 60H), 4.50 (s, 24H), 3.94 (s, 6H), 3.63~
3.68 (m, 18H), 3.28 (m, 6H), 2.70 (t, 6H), 1.69 (m, 2H), 1.25 (t, 12H), 0.83 (t, 3H) ppm.
13C NMR (300MHz, DMSO)：δ 173.1,125.3~131.6,65.9,60.4,54.2~56.6,35.7,
27.3,23.0,7.7~8.3ppm.
The performance characterization of clay stabilizer
(1) anti-dilative of clay stabilizer and the test of water-fastness rate
Reference standard SY/T 5971-2016《Oil-gas field fracturing is acidified and water filling clay stabilizer method of evaluating performance》
With Q/SH 0053-2010《The requirement of clay stabilizer technology》Middle centrifugal process method, it is molten in clay stabilizer by measuring sodium bentonite
Expansion increment in liquid and distilled water evaluates anti-dilative.Determine the clay stabilizer of embodiment 5 and embodiment 6 in water anti-
Swollen rate and water-fastness rate.The results are shown in Table 3.
The anti-dilative of 3 clay stabilizer of table and water-fastness rate
As seen from table, for clay stabilizer of the invention under 0.2% dosage, the anti-dilative in riverfrac treatment liquid is equal
Higher than 85%, water-fastness rate is more than 90%；Clay stabilizer is under 0.5% dosage, the anti-dilative in riverfrac treatment liquid
It is above 90%, water-fastness rate is more than 90%；Inorganic salts clay stabilizer (potassium chloride and ammonium chloride) is compareed, 2.0%
Dosage under, anti-dilative is below 70%.
(2) compatibility is tested
Compatibility observation is carried out to the clay stabilizer and fracturing fluid base fluid and acid solution of embodiment 1 and embodiment 2, as a result
As shown in table 2.
The compatibility of 4 clay stabilizer of table is tested
From table 4, it can be seen that the clay stabilizer of the present invention is mixed with fracturing fluid base fluid and acid solution, no layering, precipitation
It is generated with suspension phenomenon, compatibility is good.
The above content is it is made for the present invention be further described, and it cannot be said that the present invention specific implementation mode only
It is limited to this, for those of ordinary skill in the art to which the present invention belongs, without departing from the inventive concept of the premise, also
Several simple deduction or replace can be made, the present invention is all shall be regarded as belonging to and determines protection by the claims submitted
Range.
Claims (8)
1. a kind of star-like polycation based surfactants, which is characterized in that structural formula is：
Wherein, R1It is long aliphatic chain, carbon atom number is 12~18 in carbochain；R2For-H or
2. a kind of preparation method of star-like polycation based surfactants as described in claim 1, which is characterized in that including
Following steps：
To (the 3- aziridinyl propionic acid of middle addition trimethylolpropane-three of long-chain fat primary amine ethanol solution and acidic catalyst
Ester) reaction solution progress aziridine ring-opening reaction, 6~8h is reacted at 50~80 DEG C；
Under weak basic condition, chloromethanes is added into above-mentioned reactant or benzyl chloride reaction solution liquid carries out quaternary ammonium reaction,
Under nitrogen protection, 50~70 DEG C of 10~16h of reaction；Insoluble matter, concentration of reaction solution, with toluene column chromatography are removed after reaction
Method is isolated and purified with product, is dried under vacuum to constant weight and just obtains product.
3. a kind of preparation method of star-like polycation based surfactants according to claim 2, which is characterized in that
In aziridine ring-opening reaction, trimethylolpropane-three (3- aziridinyls propionic ester) and long-chain fat primary amine molar ratio are 1:3.
4. a kind of preparation method of star-like polycation based surfactants according to claim 2, it is characterised in that：
In aziridine ring-opening reaction, the acidic catalyst is the phosphate aqueous solution that mass fraction is 85%, and dosage is that raw material is total
The 1% of quality.
5. a kind of preparation method of star-like polycation based surfactants according to claim 2, which is characterized in that
In quaternary ammonium reaction, weak basic condition pH=9~10, reaction solution K2CO3It is adjusted to alkalescent.
6. a kind of preparation method of star-like polycation based surfactants according to claim 2, which is characterized in that
In quaternary ammonium reaction, the amount of the substance of chloromethanes or benzyl chloride is the 6 of trimethylolpropane-three (3- aziridinyls propionic ester)
Times.
7. a kind of star-like polycation based surfactants described in claim 1 are in oil-gas mining as clay stabilizer
Using.
8. a kind of application of the star-like polycation based surfactants according to claim 7 as clay stabilizer,
It is characterized in that, the addition as clay stabilizer is the 0.2~1% of gross mass.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109337664A (en) * | 2018-12-06 | 2019-02-15 | 中国石油化工股份有限公司 | A kind of oligomerization configuration viscoelastic surfactant, synthetic method and viscous acid formula |
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| WO2017132306A1 (en) * | 2016-01-26 | 2017-08-03 | Rhodia Operations | Clay stabilizing agents and methods of use |
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| CN102942493A (en) * | 2012-11-09 | 2013-02-27 | 西南石油大学 | Terquaternary cation surface active agent and preparation method |
| WO2017132306A1 (en) * | 2016-01-26 | 2017-08-03 | Rhodia Operations | Clay stabilizing agents and methods of use |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109337664A (en) * | 2018-12-06 | 2019-02-15 | 中国石油化工股份有限公司 | A kind of oligomerization configuration viscoelastic surfactant, synthetic method and viscous acid formula |
| CN109337664B (en) * | 2018-12-06 | 2021-08-31 | 中国石油化工股份有限公司 | Oligomeric configuration viscoelastic surfactant, synthetic method and thickening acid formula |
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