CN106866506B - The salt cationic of heterocyclic quaternary ammonium containing N prevents swollen clay stabilizer and its synthetic method - Google Patents
The salt cationic of heterocyclic quaternary ammonium containing N prevents swollen clay stabilizer and its synthetic method Download PDFInfo
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- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
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Abstract
The invention belongs to oil field development technical fields, swollen clay stabilizer and its synthetic method are prevented more particularly to the salt cationic of heterocyclic quaternary ammonium containing N, the clay stabilizer is to be reacted to generate dodecyl naphthalene anhydride half ester with n-dodecanol by naphthalene anhydride, then with N, N- dimethylamino chloromethanes generates intermediate by solution polymerization, finally generation is reacted with 2- bromo methyl cycloheptapyridine again, wherein naphthalene anhydride, n-dodecanol, N, the molar ratio of N- dimethylamino chloromethanes and 2- bromo methyl cycloheptapyridine is 1:1~1.6:1.1~1.5:0.8~1.7, preferably 1:1.1:1.2:1.5.The feature that the raw material sources of clay stabilizer of the invention are extensive, synthesis technology is simple, dosage is few, oil reservoir conformability is strong；Clay stabilizer heat-resistant salt-resistant performance of the invention is good, and energy heatproof reaches 220 DEG C, and resistance to salinity reaches 220000mg/L, and has good compatibility；Clay stabilizer of the invention can be adsorbed onto surface of clay strongly, be not easily decomposed, and clay stabilizer validity period is long, and anti-dilative is high, and anti-dilative reaches 98% or more.
Description
Technical field
The present invention relates to field of petroleum exploitation, and in particular to the salt cationic of heterocyclic quaternary ammonium containing N prevent swollen clay stabilizer and
Its synthetic method.
Background technique
Contain a certain amount of clay mineral in stratum, mainly there is kaolinite, montmorillonite, illite and chlorite etc..These
Clay encounters water or water-based material in water filling, acidification, fracturing process will generate expansion, and then further (such as you are de- for dispersion
Stone, chlorite) or direct fine particle for dispersing (such as kaolinite, illite) at diameter less than 10 μm.Under normal circumstances, from
Upper layer is to lower layer, and smectite content is reduced in oil-bearing reservoir, and illite content increases, and kaolinite disappears in certain depth, green mud
Stone is mainly distributed on deep layer.These clay minerals mostly form layer structure by oxygen-octahedron and alumina octahedral, wherein covering de-
Stone presss from both sides one layer of alumina octahedral by two layers of oxygen-octahedron and forms, and interlayer surface is oxygen layer, and connecting forces are weak, is contacted when with water
When, water can enter between crystal layer, and the exchangeable cations on face crystal layer surface dissociates diffusion in water, form diffusion electric double layer, make
Laminated structure surface is negatively charged, mutually exclusive between crystal layer, and electronegative laminated structure voluntarily separates, and generates expansion, therefore covers de-
Stone category expanded clay mineral, clay swell can cause in-place permeability to reduce.Kaolinite, illite and chlorite or because of interlayer
It easily forms hydrogen bond, be coupled closely, water is not easily accessible interlayer, or because of cation exchange capacity very little, water will not cause to expand, generally
Ground category non-expansion type clay mineral.In the case where formation fluid washes away, non-swelling clay is dispersed into flaky particles and migrates, into ground
Layer hole, blocks venturi, reduces in-place permeability.
In order to protect the permeability of hydrocarbon formations, it is necessary to using clay stabilizer i.e.: anti-soil adhesion swelling agent (expansion-resisting agent) and
Anti-soil adhesion fine migration agent (anti-migration agent).
With the exploitation in oil field, clay stabilizer using more and more extensive, type is more and more, according to different structures
And the different developments in this respect of used chemicals can substantially be divided into 3 stages: (1) 50-60 later period in age, it is main
Stablize clay with inorganic salts；(2) seventies stablizes clay with inorganic multicore polymer and cationic surfactant；
(3) research and experiment for stablizing clay with cationic organic polymer have mainly been carried out after the eighties.
Cation of the cationic active agent due to that can dissociate surface-active in water, can be adsorbed on clay particle
The negative electrical charge that surface of clay is neutralized on surface, so can be used as expansion-resisting agent.But cationic active agent makees anti-clayswelling agent Shi Yiyu
Several anion chemical agent reactions generate precipitating, such as petroleum sulfonate or to improve the partial hydrolysis polypropylene that recovery ratio uses
Amide and some biopolymers.Its is maximum the disadvantage is that can make the wettability of reservoir becomes oil-wet, can make the phase of water
To permeability decrease.
Patent ZL201310118314.7 " a kind of low molecular weight clay stabilizer preparation method " is with the ammonium salt containing carbon carbon
It polymerize in aqueous solution with 2- acrylamide-2-methylpro panesulfonic acid for raw material and is prepared, polymer number-average molecular weight is lower than 5
Ten thousand.Sulfonic acid group is introduced in the polymer stabilizer, increases the water solubility and heat-resisting property of polymer.It in water can be same
When with multiple clay particles formed multiple spot absorption, after absorption, clay particle surface formed one layer of absorption protective film, prevent from gluing
The expansion and migration of soil particle.But the stabilizer is easy to be adsorbed onto rock surface, reduces in-place permeability, or directly by stratum
The shortcomings that blocking, while the heat-resistant salt-resistant performance of the clay stabilizer is poor, limits its scope of application.
Summary of the invention
The present invention is directed to the deficiency of currently available technology, the first purpose be to provide it is a kind of oil drilling, complete well, production,
Play the role of preventing the salt cationic of heterocyclic quaternary ammonium containing N of clay swell protection reservoir from preventing swollen glue in exploitation, pressure break and water filling
Soil stabilizer can keep stabilization not decompose, be applicable to oil under the conditions of 220 DEG C and salinity are 220000mg/L
Field exploitation high temperature high salinity reservoir prevents the swollen clay stabilizer used, and the stabilizer is simple, low in cost with preparation process, matches
Good, oil reservoir the adaptable and high anti-dilative feature of 5 property；The second purpose provides the salt cationic of heterocyclic quaternary ammonium containing N and prevents swollen glue
The synthetic method of soil stabilizer.
One of the objects of the present invention is to provide the salt cationics of heterocyclic quaternary ammonium containing N to prevent swollen clay stabilizer, and the clay is steady
Determining agent is to be reacted to generate dodecyl naphthalene anhydride half ester with n-dodecanol by naphthalene anhydride, and then with N, N- dimethylamino chloromethanes passes through molten
Liquid polymerization reaction generates intermediate, finally reacts generation with 2- bromo methyl cycloheptapyridine again, molecular formula is as follows:
The molar ratio of the naphthalene anhydride, n-dodecanol, N, N- dimethylamino chloromethanes and 2- bromo methyl cycloheptapyridine be 1:1~
1.6:1.1~1.5:0.8~1.7, preferably 1:1.1:1.2:1.5.
It is another object of the present invention to provide the synthesis sides that the salt cationic of heterocyclic quaternary ammonium containing N prevents swollen clay stabilizer
Method, the synthetic method of the clay stabilizer specifically includes the following steps:
(1) naphthalene anhydride of aforementioned proportion and n-dodecanol are added to four-hole boiling flask, are heated to 75~85 DEG C, stirring rate is
300~400rpm, reaction time are 0.5~1.5h, and normal heptane is then added, and the reaction time is 3~8h, are then cooled to room
Temperature stirs 10~25min, obtains half ester solution of dodecyl naphthalene anhydride；
(2) N of aforementioned proportion, N- dimethylamino chloromethanes, while stirring are added in above-mentioned half ester solution of dodecyl naphthalene anhydride
Side reaction is mixed, stirring rate is 400~500rpm, and the reaction time is 5~8h, is then heated to 75~85 DEG C, while stirring instead
It answers, stirring rate is 200~300rpm, and the reaction time is 10~15h, is filtered after the reaction time, is washed with the petroleum ether of heat
Filter residue collects filtrate, with the dry 15~30h of anhydrous magnesium sulfate, normal heptane is removed under reduced pressure, obtains brown yellow oil liquid；
(3) the 2- bromo methyl cycloheptapyridine of above-mentioned brown yellow oil liquid and aforementioned proportion is added to equipped with blender and condensation
In the flask of pipe, then butanone is added thereto, under the protection of nitrogen at 50~80 DEG C reaction 10~for 24 hours, stirring rate is
400~500rpm, to the reaction time after, be cooled to room temperature, obtain crude product；
(4) above-mentioned crude product is evaporated under reduced pressure and removes solvent, obtained yellow and stick shape liquid, crossed silica gel column chromatography, point
Eluant, eluent is not made with petroleum ether and ether and washes off impurity, and again with methanol elutes to obtain faint yellow viscous shape liquid, and as of the invention is viscous
Soil stabilizer.
The dosage of the normal heptane is 15~25 times of naphthalene anhydride quality, and the dosage of the butanone is the 25 of naphthalene anhydride quality
~35 times.
The reaction equation is as follows:
It is provided by the invention to prevent swollen clay stabilizer, belong to cationic surface active agent, contains a naphthylene group one
A heterocycle polar group, and quaternary ammonium N ion dissociates the cation for generating high positive electricity price in water, it can be with multiple clay particle shapes
It is adsorbed at multiple spot, after absorption, forms one layer of adsorbed film on the surface of clay particle, prevent the expansion and migration of clay particle.This
The clay anti-expension stabilizer provided is invented since molecular weight is moderate, molecule, which does not need curling, to combine closely with clay, salt resistance
It has excellent performance, effectively raises service efficiency；And there are two benzene radicals for tool on molecule, have certain rigid structure,
Effectively increase the heat-resisting property of molecule.In addition, the present invention is since with Long carbon chain hydrophobic grouping, freedom of movement is bigger,
The thus dispersion migration significant effect of the hydration swelling to control clay and mineral microparticle.
The present invention is had the following advantages and beneficial effects: compared with prior art
(1) raw material sources of clay stabilizer of the invention are extensive, and synthesis technology is simple, low in cost；
(2) dosage of clay stabilizer of the invention is few, and oil reservoir conformability is strong, can meet the needs of oil field development；
(3) clay stabilizer heat-resistant salt-resistant performance of the invention is good, and energy heatproof reaches 220 DEG C, and resistance to salinity reaches
220000mg/L, and there is good compatibility；
(4) what clay stabilizer of the invention can be strong is adsorbed onto surface of clay, is not easily decomposed, clay stabilizer validity period
Long, anti-dilative is high, and anti-dilative reaches 98% or more.
Specific embodiment
The present invention is described in further detail below with reference to specific embodiment, and referring to data.It should be understood that these embodiments
It is of the invention solely for the purpose of illustration, rather than limit the scope of the invention in any way.
Embodiment 1: clay stabilizer C1And preparation method thereof
(1) clay stabilizer C1Composition, component and molecular formula it is as follows:
Clay stabilizer C1By naphthalene anhydride, n-dodecanol, N, N- dimethylamino chloromethanes and 2- bromo methyl cycloheptapyridine according to mole
Than reacting to obtain for 1:1:1.1:0.8 ratio, molecular formula is as follows:
(2) clay stabilizer C1Synthetic method it is as follows:
1. the n-dodecanol of the naphthalene anhydride of 1mol and 1mol is added to four-hole boiling flask, 75 DEG C are heated to, stirring rate is
Then 2972.7g normal heptane is added in 300rpm, reaction time 0.5h, reaction time 5h is then cooled to room temperature, stirs
15min obtains half ester solution of dodecyl naphthalene anhydride；
2. the N of 1.1mol is added in above-mentioned half ester solution of dodecyl naphthalene anhydride, N- dimethylamino chloromethanes, while stirring
Reaction, stirring rate 400rpm, reaction time 5h are then heated to 75 DEG C, react while stirring, and stirring rate is
200rpm, reaction time 10h, is filtered after the reaction time, with the petroleum ether filter wash slag of heat, filtrate is collected, with anhydrous sulphur
The dry 15h of sour magnesium, is removed under reduced pressure normal heptane, obtains brown yellow oil liquid；
3. being added to the 2- bromo methyl cycloheptapyridine of above-mentioned brown yellow oil liquid and 0.8mol equipped with blender and condenser pipe
Flask in, then thereto be added 4954.5g butanone, 10h is reacted at 50 DEG C under the protection of nitrogen, stirring rate is
430rpm, to the reaction time after, be cooled to room temperature, obtain crude product；
4. above-mentioned crude product is evaporated under reduced pressure and removes solvent, obtains yellow and stick shape liquid, crossed silica gel column chromatography, respectively
Eluant, eluent is made with petroleum ether and ether and washes off impurity, and again with methanol elutes to obtain faint yellow viscous shape liquid, clay as of the invention
Stabilizer C1。
Embodiment 2: clay stabilizer C2And preparation method thereof
(1) clay stabilizer C2Composition, component and molecular formula it is as follows:
Clay stabilizer C2By naphthalene anhydride, n-dodecanol, N, N- dimethylamino chloromethanes and 2- bromo methyl cycloheptapyridine according to mole
Than reacting to obtain for 1:1.1:1.2:1.5 ratio, molecular formula is as follows:
(2) clay stabilizer C2Synthetic method it is as follows:
1. the n-dodecanol of the naphthalene anhydride of 1mol and 1.1mol is added to four-hole boiling flask, 78 DEG C are heated to, stirring rate is
Then 3256.3g normal heptane is added in 400rpm, reaction time 0.6h, reaction time 6h is then cooled to room temperature, stirs
18min obtains half ester solution of dodecyl naphthalene anhydride；
2. the N of 1.2mol is added in above-mentioned half ester solution of dodecyl naphthalene anhydride, N- dimethylamino chloromethanes, while stirring
Reaction, stirring rate 500rpm, reaction time 6h are then heated to 85 DEG C, react while stirring, and stirring rate is
270rpm, reaction time 12h, is filtered after the reaction time, with the petroleum ether filter wash slag of heat, filtrate is collected, with anhydrous sulphur
The dry 20h of sour magnesium, is removed under reduced pressure normal heptane, obtains brown yellow oil liquid；
3. being added to the 2- bromo methyl cycloheptapyridine of above-mentioned brown yellow oil liquid and 1.5mol equipped with blender and condenser pipe
Flask in, then thereto be added 6242.3g butanone, 12h is reacted at 60 DEG C under the protection of nitrogen, stirring rate is
480rpm, to the reaction time after, be cooled to room temperature, obtain crude product；
4. above-mentioned crude product is evaporated under reduced pressure and removes solvent, obtains yellow and stick shape liquid, crossed silica gel column chromatography, respectively
Eluant, eluent is made with petroleum ether and ether and washes off impurity, and again with methanol elutes to obtain faint yellow viscous shape liquid, clay as of the invention
Stabilizer C2。
Embodiment 3: clay stabilizer C3And preparation method thereof
(1) clay stabilizer C3Composition, component and molecular formula it is as follows:
Clay stabilizer C3By naphthalene anhydride, n-dodecanol, N, N- dimethylamino chloromethanes and 2- bromo methyl cycloheptapyridine according to mole
Than reacting to obtain for 1:1.3:1.3:1.2 ratio, molecular formula is as follows:
(2) clay stabilizer C3Synthetic method it is as follows:
1. the n-dodecanol of the naphthalene anhydride of 1mol and 1.3mol is added to four-hole boiling flask, 80 DEG C are heated to, stirring rate is
Then 3954.5g normal heptane is added in 330rpm, reaction time 0.8h, reaction time 7h is then cooled to room temperature, stirs
21min obtains half ester solution of dodecyl naphthalene anhydride；
2. the N of 1.3mol is added in above-mentioned half ester solution of dodecyl naphthalene anhydride, N- dimethylamino chloromethanes, while stirring
Reaction, stirring rate 420rpm, reaction time 7h are then heated to 78 DEG C, react while stirring, and stirring rate is
220rpm, reaction time 13h, is filtered after the reaction time, with the petroleum ether filter wash slag of heat, filtrate is collected, with anhydrous sulphur
The dry 25h of sour magnesium, is removed under reduced pressure normal heptane, obtains brown yellow oil liquid；
3. being added to the 2- bromo methyl cycloheptapyridine of above-mentioned brown yellow oil liquid and 1.2mol equipped with blender and condenser pipe
Flask in, then thereto be added 789.6g butanone, 16h is reacted at 65 DEG C under the protection of nitrogen, stirring rate is
450rpm, to the reaction time after, be cooled to room temperature, obtain crude product；
4. above-mentioned crude product is evaporated under reduced pressure and removes solvent, obtains yellow and stick shape liquid, crossed silica gel column chromatography, respectively
Eluant, eluent is made with petroleum ether and ether and washes off impurity, and again with methanol elutes to obtain faint yellow viscous shape liquid, clay as of the invention
Stabilizer C3。
Embodiment 4: clay stabilizer C4And preparation method thereof
(1) clay stabilizer C4Composition, component and molecular formula it is as follows:
Clay stabilizer C4By naphthalene anhydride, n-dodecanol, N, N- dimethylamino chloromethanes and 2- bromo methyl cycloheptapyridine according to mole
Than reacting to obtain for 1:1.5:1.4:1.0 ratio, molecular formula is as follows:
(2) clay stabilizer C4Synthetic method it is as follows:
1. the n-dodecanol of the naphthalene anhydride of 1mol and 1.5mol is added to four-hole boiling flask, 82 DEG C are heated to, stirring rate is
Then 4365.8g normal heptane is added in 360rpm, reaction time 1.0h, reaction time 3h is then cooled to room temperature, stirs
10min obtains half ester solution of dodecyl naphthalene anhydride；
2. the N of 1.4mol is added in above-mentioned half ester solution of dodecyl naphthalene anhydride, N- dimethylamino chloromethanes, while stirring
Reaction, stirring rate 450rpm, reaction time 6h are then heated to 80 DEG C, react while stirring, and stirring rate is
250rpm, reaction time 11h, is filtered after the reaction time, with the petroleum ether filter wash slag of heat, filtrate is collected, with anhydrous sulphur
The dry 22h of sour magnesium, is removed under reduced pressure normal heptane, obtains brown yellow oil liquid；
3. being added to the 2- bromo methyl cycloheptapyridine of above-mentioned brown yellow oil liquid and 1.0mol equipped with blender and condenser pipe
Flask in, then thereto be added 5237.5g butanone, 20h is reacted at 70 DEG C under the protection of nitrogen, stirring rate is
400rpm, to the reaction time after, be cooled to room temperature, obtain crude product；
4. above-mentioned crude product is evaporated under reduced pressure and removes solvent, obtains yellow and stick shape liquid, crossed silica gel column chromatography, respectively
Eluant, eluent is made with petroleum ether and ether and washes off impurity, and again with methanol elutes to obtain faint yellow viscous shape liquid, clay as of the invention
Stabilizer C4。
Embodiment 5: clay stabilizer C5And preparation method thereof
(1) clay stabilizer C5Composition, component and molecular formula it is as follows:
Clay stabilizer C5By naphthalene anhydride, n-dodecanol, N, N- dimethylamino chloromethanes and 2- bromo methyl cycloheptapyridine according to mole
Than reacting to obtain for 1:1.6:1.5:1.7 ratio, molecular formula is as follows:
(2) clay stabilizer C5Synthetic method it is as follows:
1. the n-dodecanol of the naphthalene anhydride of 1mol and 1.6mol is added to four-hole boiling flask, 85 DEG C are heated to, stirring rate is
Then 4954.5g normal heptane is added in 380rpm, reaction time 1.5h, reaction time 8h is then cooled to room temperature, stirs
25min obtains half ester solution of dodecyl naphthalene anhydride；
2. the N of 1.5mol is added in above-mentioned half ester solution of dodecyl naphthalene anhydride, N- dimethylamino chloromethanes, while stirring
Reaction, stirring rate 480rpm, reaction time 8h are then heated to 82 DEG C, react while stirring, and stirring rate is
300rpm, reaction time 15h, is filtered after the reaction time, with the petroleum ether filter wash slag of heat, filtrate is collected, with anhydrous sulphur
The dry 30h of sour magnesium, is removed under reduced pressure normal heptane, obtains brown yellow oil liquid；
3. being added to the 2- bromo methyl cycloheptapyridine of above-mentioned brown yellow oil liquid and 1.7mol equipped with blender and condenser pipe
Flask in, then thereto be added 6936.3g butanone, reacted for 24 hours at 80 DEG C under the protection of nitrogen, stirring rate is
500rpm, to the reaction time after, be cooled to room temperature, obtain crude product；
4. above-mentioned crude product is evaporated under reduced pressure and removes solvent, obtains yellow and stick shape liquid, crossed silica gel column chromatography, respectively
Eluant, eluent is made with petroleum ether and ether and washes off impurity, and again with methanol elutes to obtain faint yellow viscous shape liquid, clay as of the invention
Stabilizer C5。
Embodiment 6
The above-mentioned C of 5.00g is accurately weighed respectively1~C5Clay stabilizer sample is dissolved in 995.00g distilled water, stirring
30min forms homogeneous solution, for use.
Embodiment 7
Having rated product in temperature according to " SY/T5971-94 fills the water clay stabilizer method of evaluating performance " is 220 DEG C
Anti-dilative and validity period under the conditions of being 220000mg/L with salinity.Clay stabilization agent solution used in this experiment is embodiment 6
Middle matched solution, test result are shown in Table 1.
1 clay stabilizer C of table1~C5Evaluation result
| Product | Anti-dilative, % |
| C1 | 98.7 |
| C2 | 99.5 |
| C3 | 98.3 |
| C4 | 98.6 |
| C5 | 99.0 |
As it can be seen from table 1 clay stabilizer C1~C5Anti-dilative be all larger than 98.0%, wherein clay stabilizer C2's
Anti-dilative highest, reaches 99.5%.Illustrate that the clay stabilizer of the invention developed is 220 DEG C in temperature and salinity is
There is the good ability for preventing bentonite hydration swelling under the conditions of 220000mg/L.
Embodiment 8
Reference standard " SY-T 5613-2000 mud shale physicochemical property test method " evaluates sample and inhibits Shale Hydration point
Scattered ability.Rock sample used is Gudao area of Shengli Oilfield landwaste, washes 10min with 3% dioxygen, then dries.200mL is being taken respectively
20-30 mesh landwaste 50g is added in the prepared clay stabilization agent solution of embodiment 6, and clear water is used in heat rolling afterwards for 24 hours at a temperature of 220 DEG C
It cleans, sieves with 100 mesh sieve, 6h is dried at a temperature of 220 DEG C, weighing calculates primary recovery, the results are shown in Table 2.
2 landwaste rolling rate of recovery test result of table
As can be seen from Table 2, clay stabilizer C1~C5A rolling rate of recovery be all larger than 97.0%, wherein clay stabilizer
C2A rolling rate of recovery highest, reach 98.7%.Test result shows clay stabilizer product prepared by the present invention 220
DEG C heat rolling after still with it is very strong inhibition Shale Hydration dispersion ability.
Embodiment 9
The linear dilatancy experiment of sample is carried out according to China National Petroleum professional standard evaluation SY/T6335-1997.Institute
It is NP-3 shale expansion tester with instrument.Weigh second level bentonite (the diameter 0.01- that 5.00g dries 10h at 220 DEG C
0.05mm), tabletting (pressure 10MPa, time 5min) is made on press machine.Tabletting is put into shale expansion instrument, addition is matched
The certain density stabiliser solution (matched solution in embodiment 6) made, the expansion of mud shale tabletting after measurement test solution impregnates
Rate.The expansion rate of mud shale tabletting is smaller, illustrates that the ability of the inhibition hydration and expansion of clay of product is stronger；It is on the contrary then poorer.It is real
Test that the results are shown in Table 3.
3 linear expansion rate experimental test result of table
| Product | Reduced rate of the 16h with respect to clear water, % |
| C1 | 22.3 |
| C2 | 20.3 |
| C3 | 22.0 |
| C4 | 21.2 |
| C5 | 22.5 |
Seen from table 3, clay stabilizer C1~C516h is below 23% with respect to the reduced rate of clear water, wherein clay stabilization
Agent C216h is minimum with respect to the reduced rate of clear water, reaches 20.3%, illustrates that clay stabilizer product prepared by the present invention can be effective
The hydration swelling of ground inhibition clay.
Claims (6)
1. the salt cationic of heterocyclic quaternary ammonium containing N prevents swollen clay stabilizer, which is characterized in that the clay stabilizer is by naphthalene anhydride
Generation dodecyl naphthalene anhydride half ester is reacted with n-dodecanol, then with N, it is raw that N- dimethylamino chloromethanes passes through solution polymerization
At intermediate, generation finally is reacted with 2- bromo methyl cycloheptapyridine again, molecular formula is as follows:
2. the salt cationic of heterocyclic quaternary ammonium containing N according to claim 1 prevents the synthetic method of swollen clay stabilizer, feature
Be, the synthetic method specifically includes the following steps:
1. naphthalene anhydride and n-dodecanol are added to four-hole boiling flask, 75~85 DEG C are heated to, stirring rate is 300~400rpm, instead
It is 0.5~1.5h between seasonable, normal heptane is then added, the reaction time is 3~8h, then it is cooled to room temperature, stirring 10~
25min obtains half ester solution of dodecyl naphthalene anhydride；
2. N is added in above-mentioned half ester solution of dodecyl naphthalene anhydride, N- dimethylamino chloromethanes reacts while stirring, stirring speed
Rate is 400~500rpm, and the reaction time is 5~8h, is then heated to 75~85 DEG C, reacts while stirring, stirring rate 200
~300rpm, reaction time are 10~15h, are filtered after the reaction time, with the petroleum ether filter wash slag of heat, collect filtrate, use
Anhydrous magnesium sulfate dries 15~30h, and normal heptane is removed under reduced pressure, obtains brown yellow oil liquid；
3. above-mentioned brown yellow oil liquid and 2- bromo methyl cycloheptapyridine are added in the flask equipped with blender and condenser pipe, then to
Butanone is wherein added, under the protection of nitrogen at 50~80 DEG C reaction 10~for 24 hours, stirring rate be 400~500rpm, to anti-
After between seasonable, it is cooled to room temperature, obtains crude product；
4. above-mentioned crude product is evaporated under reduced pressure and removes solvent, obtains yellow and stick shape liquid, crossed silica gel column chromatography, use stone respectively
Oily ether and ether make eluant, eluent and wash off impurity, and again with methanol elutes to obtain faint yellow viscous shape liquid, as clay stabilizer.
3. the salt cationic of heterocyclic quaternary ammonium containing N according to claim 2 prevents the synthetic method of swollen clay stabilizer, feature
It is, the naphthalene anhydride, n-dodecanol, N, the molar ratio of N- dimethylamino chloromethanes and 2- bromo methyl cycloheptapyridine is 1:1~1.6:
1.1~1.5:0.8~1.7.
4. the salt cationic of heterocyclic quaternary ammonium containing N according to claim 3 prevents the synthetic method of swollen clay stabilizer, feature
It is, the naphthalene anhydride, n-dodecanol, N, the molar ratio of N- dimethylamino chloromethanes and 2- bromo methyl cycloheptapyridine is 1:1.1:1.2:
1.5。
5. the salt cationic of heterocyclic quaternary ammonium containing N according to claim 2 prevents the synthetic method of swollen clay stabilizer, feature
It is, the dosage of the normal heptane is 15~25 times of naphthalene anhydride quality.
6. the salt cationic of heterocyclic quaternary ammonium containing N according to claim 2 prevents the synthetic method of swollen clay stabilizer, feature
It is, the dosage of the butanone is 25~35 times of naphthalene anhydride quality.
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