CN106432708B - A kind of multi-branch polyether amine and its preparation method and application - Google Patents
A kind of multi-branch polyether amine and its preparation method and application Download PDFInfo
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Abstract
The present invention provides a kind of multi-branch polyether amine, have the structure shown in Formulas I；In Formulas I, m is that 1~16, n is that 1~2, o is 0~4.The present invention provides a kind of preparation method of multi-branch polyether amine described in above-mentioned technical proposal, including：Glycerine, glycol compound, water and acidic catalyst are reacted, obtain intermediate product；The intermediate product and chloro epoxides, alkali compounds, organic amine are reacted, obtain multi-branch polyether amine.Multi-branch polyether amine provided by the invention has preferable shale inhibition and clay aquation dispersion performance.In addition, multi-branch polyether amine provided by the invention has preferable greasy property, and no biotoxicity.Multi-branch polyether amine provided by the invention can be applied in drilling fluid, suitable for more demanding strong retraction mud shale, containing the caving grounds such as mud stone and shale gas Horizontal Well Drilling well construction.
Description
Technical field
The present invention relates to polyetheramine technical fields more particularly to a kind of multi-branch polyether amine and its preparation method and application.
Background technology
Polyetheramine is that a kind of main chain is polyether structure, and end active functional group is the polymer of amido, and polyetheramine is in polyureas
The various fields such as spraying, large-scale composite material preparation and epoxy curing agent are widely applied, in recent years polyetheramine
Start to apply in drilling fluid, show preferable rejection and environmental-protecting performance, and the molecular structure of polyetheramine uniqueness
Clay interlayer can be embedded in well, is bound tightly together clay layer, so as to effectively inhibit point of clay and landwaste
It dissipates；Polyetheramine inhibition is lasting, is conducive to wellbore stability and reservoir protection, can be separately as drilling fluid inhibitor or anti-sloughing agent
It uses, polyetheramine drilling fluid system can also be formed.
The main method for preparing polyetheramine in the prior art adds including polyethers catalysis reduction hydroamination method, the catalysis of polyethers nitrile
Hydrogen method and leaving group method, wherein polyethers catalysis reduction hydroamination method and polyethers catalytic hydrogenation of nitriles method are preparing the mistake of polyetheramine
High temperature and pressure is needed in journey, catalytic hydrogenation, reduction amination, process conditions are harsh, and reaction step is more, and post processing is complicated；And it leaves away
Functional group method prepares that polyethers amine reaction step is cumbersome, and sintetics yield is relatively low.The preparation side for the polyetheramine that the prior art provides
Method not only complex process, is awkward, and the rejection for the polyetheramine being prepared and clay aquation dispersiveness need
It improves, to better meet the use demand of drilling fluid.
Therefore, it is badly in need of a kind of rejection and the preferable polyethers amine product of clay aquation dispersiveness currently on the market.
The content of the invention
In view of this, it is an object of the invention to provide a kind of multi-branch polyether amine and its preparation method and application, this hairs
The multi-branch polyether amine of bright offer has preferable shale inhibition and clay aquation dispersiveness.
The present invention provides a kind of multi-branch polyether amine, have the structure shown in Formulas I：
In Formulas I, m is 1~16；N is that 1~2, o is 0~4.
Preferably, in the Formulas I, m is 5~10.
Multi-branch polyether amine provided by the invention has preferable shale inhibition can be with clay aquation dispersiveness.Experiment knot
Fruit shows the shale primary recovery ＞ 95% for the multi-branch polyether aqueous solution provided by the invention that mass concentration is 1%, shale
Relative recovery ＞ 98%, clay relative inhibition ＞ 95%.
In addition, multi-branch polyether amine provided by the invention has preferable lubricity, and no biotoxicity.Experimental result
Show the extreme boundary lubrication coefficient ＜ 0.1 for the multi-branch polyether amine aqueous solution provided by the invention that mass concentration is 1%.
The present invention provides a kind of preparation method of multi-branch polyether amine described in above-mentioned technical proposal, including：
Glycerine, glycol compound, water and acidic catalyst are reacted, obtain intermediate product, the glycols
Compound includes ethylene glycol or polyethylene glycol；
The intermediate product and chloro epoxides, alkali compounds, organic amine are reacted, obtain multi-branch polyether
Amine, the chloro epoxides include epoxychloropropane or 1,2- epoxy chloro-butane, and the organic amine includes ethylenediamine, diethyl
Alkene triamine, triethylene tetramine, tetraethylenepentamine or pentaethylene hexamine.
Preferably, the glycerine, glycol compound, water, acidic catalyst, chloro epoxides, alkali compounds
Mass ratio with organic amine is 10:(8~14):(30~60):(0.8~1.5):(5~15):(0.8~1.2):(10~20).
Preferably, the glycol compound is polyethylene glycol.
Preferably, the acidic catalyst is hydrochloric acid, sulfuric acid, phosphoric acid, tartaric acid, oxalic acid, p-methyl benzenesulfonic acid, dodecyl
Benzene sulfonic acid, sulfamic acid or phosphotungstic acid.
Preferably, the chloro epoxides is epoxychloropropane.
Preferably, the alkali compounds is sodium hydroxide, potassium hydroxide or barium hydroxide.
Preferably, the organic amine is diethylenetriamine, triethylene tetramine, tetraethylenepentamine or pentaethylene hexamine.
The multi-branch polyether amine that method provided by the invention is prepared has preferable shale inhibition energy and clay water
Change dispersion performance.In addition, the multi-branch polyether amine that method provided by the invention is prepared has preferable greasy property, and
No biotoxicity.In addition, the preparation method of multi-branch polyether amine provided by the invention is simple for process, reaction condition is mild, is convenient for
Operation.
The present invention provides a kind of application of multi-branch polyether amine in drilling fluid, the multi-branch polyether amine is above-mentioned skill
The multi-branch polyether amine that the method described in multi-branch polyether amine or above-mentioned technical proposal described in art scheme is prepared.
In the present invention, the multi-branch polyether amine has preferable shale inhibition energy and clay aquation dispersion performance,
But also there is preferable greasy property, this multi-branch polyether amine can be applied in drilling fluid, this is added in drilling fluid
Kind multi-branch polyether amine can make drilling fluid have preferable rejection, dispersion performance and greasy property, be applicable in drilling fluid
In more demanding strong retraction mud shale, containing the caving grounds such as mud stone and shale gas Horizontal Well Drilling well construction.
Specific embodiment
The technical solution in the embodiment of the present invention will be clearly and completely described below, it is clear that described implementation
Example is only part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is common
Technical staff's all other embodiments obtained without making creative work belong to the model that the present invention protects
It encloses.
The present invention provides a kind of multi-branch polyether amine, have the structure shown in Formulas I：
In Formulas I, m is 1~16；N is that 1~2, o is 0~4.
In an embodiment of the present invention, the m in the Formulas I is 5~10；In other examples, the m in the Formulas I
For 6~8.In an embodiment of the present invention, the number-average molecular weight of the multi-branch polyether amine is 550~3500；Other real
It applies in example, the number-average molecular weight of the multi-branch polyether amine is 1000~3000；In a further embodiment, it is described hyper-branched poly-
The number-average molecular weight of ether amines is 1500~2500.Multi-branch polyether amine provided by the invention has preferable shale inhibition and sticks
Native aquation dispersion performance.In addition, multi-branch polyether amine provided by the invention has preferable lubricity, and no biotoxicity.
The present invention provides a kind of preparation method of multi-branch polyether amine described in above-mentioned technical proposal, including：
Glycerine, glycol compound, water and acidic catalyst are reacted, obtain intermediate product, the glycols
Compound includes ethylene glycol or polyethylene glycol；
The intermediate product and chloro epoxides, alkali compounds, organic amine are reacted, obtain multi-branch polyether
Amine；The chloro epoxides includes epoxychloropropane or 1,2- epoxy chloro-butane, and the organic amine includes ethylenediamine, diethyl
Alkene triamine, triethylene tetramine, tetraethylenepentamine or pentaethylene hexamine.
In an embodiment of the present invention, the glycerine, glycol compound, water and the temperature of acidic catalyst reaction are
90 DEG C~140 DEG C；In other examples, the glycerine, glycol compound, water and the temperature of acidic catalyst reaction
For 100 DEG C~120 DEG C.In an embodiment of the present invention, the glycerine, glycol compound, water and acidic catalyst reaction
Time for 2 it is small when~4 it is small when；In other examples, the glycerine, glycol compound, water and acidic catalyst
The time of reaction for 2.5 it is small when~3.5 it is small when.It in an embodiment of the present invention, can be under conditions of stirring by glycerine, two
Alcohol compound, water and acidic catalyst are reacted.
After obtaining intermediate product, the present invention by the intermediate product and chloro epoxides, alkali compounds, organic amine into
Row reaction, obtains multi-branch polyether amine.In an embodiment of the present invention, the intermediate product and chloro epoxides, alkalization
Close object, the temperature of organic amine reaction is 40 DEG C~60 DEG C；In other examples, the intermediate product and chloro epoxidation
Object, alkali compounds, the temperature of organic amine reaction are 45 DEG C~55 DEG C.In an embodiment of the present invention, the intermediate product and
Chloro epoxides, alkali compounds, organic amine reaction time for 0.5 it is small when~2 it is small when；In other examples, institute
State intermediate product and chloro epoxides, alkali compounds, organic amine reaction time for 1 it is small when~1.5 it is small when.In the present invention
Embodiment in, intermediate product and chloro epoxides, alkali compounds, organic amine can be carried out under conditions of stirring anti-
It should.
In an embodiment of the present invention, the intermediate product and chloro epoxides, alkali compounds, organic amine have reacted
Obtained reaction product is dried and removed water, obtains multi-branch polyether amine by Cheng Hou.
In the present invention, the glycol compound includes ethylene glycol or polyethylene glycol.In an embodiment of the present invention, institute
The number-average molecular weight for stating polyethylene glycol is 400~800；In other examples, the number-average molecular weight of the polyethylene glycol is
500~700；In a further embodiment, the number-average molecular weight of the polyethylene glycol is 550~650.In the embodiment of the present invention
In, the acidic catalyst can be hydrochloric acid, sulfuric acid, phosphoric acid, tartaric acid, oxalic acid, p-methyl benzenesulfonic acid, dodecyl benzene sulfonic acid,
Sulfamic acid or phosphotungstic acid.In the present invention, the chloro epoxides is epoxychloropropane or 1,2- epoxy chloro-butane；
In the embodiment of the present invention, the chloro epoxides is epoxychloropropane.In an embodiment of the present invention, the alkaline chemical combination
Object is sodium hydroxide, potassium hydroxide or barium hydroxide.In the present invention, the organic amine includes ethylenediamine, diethylenetriamine, three
Ethylene tetramine, tetraethylenepentamine or pentaethylene hexamine；In an embodiment of the present invention, the organic amine include diethylenetriamine,
Triethylene tetramine, tetraethylenepentamine or pentaethylene hexamine.
In an embodiment of the present invention, the glycerine, glycol compound, water, acidic catalyst, chloro epoxidation
The mass ratio of object, alkali compounds and organic amine is 10:(8~14):(30~60):(0.8~1.5):(5~15):(0.8~
1.2):(10~20)；In other examples, the glycerine, glycol compound, water, acidic catalyst, chloro epoxy
The mass ratio of compound, alkali compounds and organic amine is 10:(9~12):(40~50):(1~1.4):(8~12):(0.9~
1.1):(12~18)；In a further embodiment, the glycerine, glycol compound, water, acidic catalyst, chloro epoxy
The mass ratio of compound, alkali compounds and organic amine is 10:(10~11):(42~48):(1.1~1.3):(10~11):1:
(14~16).
In the present invention, the multi-branch polyether amine is consistent with the multi-branch polyether amine described in above-mentioned technical proposal, herein
It repeats no more.
The multi-branch polyether amine that method provided by the invention is prepared has preferable shale inhibition energy and clay water
Change dispersion performance.In addition, the multi-branch polyether amine that method provided by the invention is prepared has preferable greasy property, and
No biotoxicity.In addition, the preparation method of multi-branch polyether amine provided by the invention is simple for process, reaction condition is mild, is convenient for
Operation.
The present invention provides a kind of application of multi-branch polyether amine in drilling fluid, the multi-branch polyether amine is above-mentioned skill
The multi-branch polyether amine that the method described in multi-branch polyether amine or above-mentioned technical proposal described in art scheme is prepared.
In the present invention, the multi-branch polyether amine is consistent with multi-branch polyether amine described in above-mentioned technical proposal, herein not
It repeats again.In the present invention, the multi-branch polyether amine has preferable shale inhibition energy and clay aquation dispersion performance, and
And also there is preferable greasy property, this multi-branch polyether amine can be applied in drilling fluid, be added in drilling fluid this
Multi-branch polyether amine can make drilling fluid have preferable rejection, dispersion performance and greasy property, be suitable for drilling fluid
More demanding strong retraction mud shale, containing the caving grounds such as mud stone and shale gas Horizontal Well Drilling well construction.
Multi-branch polyether amine provided by the invention is configured to the multi-branch polyether amine aqueous solution that mass concentration is 1%,
When high temperature rolling 16 is small at 150 DEG C, by the following method, its shale primary recovery and shale relative recovery are tested：
By above-mentioned mass concentration be 1% multi-branch polyether amine aqueous solution under 7000 revs/min of speed high-speed stirred
After 5min, pour into spare in ageing can；The landwaste of 2.0mm~5.0mm is taken to dry 4h at 103 DEG C, is down to room temperature；Weigh G0g
The multi-branch polyether amine aqueous solution that landwaste is put into ageing can with above-mentioned mass concentration is 1% rolls 16h at 150 DEG C, after cooling
It takes out, recycling landwaste is sieved with aperture 0.42mm, the dry 4h at 103 DEG C is down to room temperature weighing recycling landwaste quality and is denoted as G1；So
Overweight recycling landwaste will be claimed to be put into clear water at 150 DEG C afterwards and rolled 16h, taken out after cooling, sieved back with aperture 0.42mm
Landwaste is received, the dry 4h at 103 DEG C is cooled to room temperature weighing recycling landwaste quality, is denoted as G2；Page is calculated according to following formula
Rock primary recovery, shale secondary returning yield and shale relative recovery：
Shale primary recovery=G1/G0× 100%；
Shale secondary returning yield=G2/G0× 100%；
Shale relative recovery=shale secondary returning yield/shale primary recovery × 100%；
Result of calculation is the multi-branch polyether amine aqueous solution provided by the invention that mass concentration is 1% high temperature at 150 DEG C
Roll 16h, shale primary recovery ＞ 95%, shale relative recovery ＞ 98%.
Clay relative inhibition is tested by the following method, and specific method is：
Accurate 2 parts of distilled water for measuring 350mL, is put into height and stirs in cup, and the anhydrous carbon of 1.75g is added in portion thereto
Sour sodium, into another, addition quality is that the multi-branch polyether aqueous amine that the above-mentioned mass concentration of distillation water quality 1.5% is 1% is molten
The natrium carbonicum calcinatum of liquid and 1.75g makes it all dissolve；
The calcium bentonite of 35g is weighed, high stirring cup high speed stirring 10min is added in, is fitted into high temperature aging tank, in 150
DEG C high temperature rolls 16h；Room temperature is down in taking-up；
Above-mentioned calcium Peng Run soil with the above-mentioned distilled water containing natrium carbonicum calcinatum is mixed, obtains the first mixed liquor；It will be above-mentioned
Calcium bentonite is mixed with the above-mentioned distilled water containing multi-branch polyether amine aqueous solution, obtains the second mixed liquor；Described first is mixed
It closes liquid and the second mixed liquor and stirs 5min with homogenizer respectively, its viscosity is tested using rotational viscometer, according to following public affairs
Formula calculates clay relative inhibition：
In formula：
B-clay relative inhibition, %；
The mixed liquor rotary viscosities of Ф-first metering rotating speed stablizes reading when being 100r/min；
Ф1- the second mixed liquor rotary viscosity metering rotating speed stablizes reading when being 100r/min.
Test result, which is that mass concentration is that the clay of 1% multi-branch polyether amine aqueous solution provided by the invention is opposite, to be pressed down
Rate ＞ 95% processed.
By the following method, the multi-branch polyether amine aqueous solution extreme pressure at room temperature that above-mentioned mass concentration is 1% is tested
Lubricating coefficient：
Using the extreme boundary lubrication instrument for the EP models that Zhengzhou north and south Instrument Design Co., Ltd provides, setting instrument is in 300r/
15min is operated under min, it is 60r/min then to adjust rotating speed；
Sliding block in instrument is immersed in the multi-branch polyether amine aqueous solution that above-mentioned mass concentration is 1%, adjust torque spanner
It is worth for 16.95N/m, apparatus working 5min, instrument when reading the multi-branch polyether amine aqueous solution immersion sliding block that mass concentration is 1%
The numerical value of upper display, extreme boundary lubrication coefficient calculation formula are：
In above formula：K is extreme boundary lubrication coefficient；
X is to be shown when the multi-branch polyether amine aqueous solution provided by the invention that mass concentration is 1% impregnates sliding block on instrument
Numerical value.
Test result is that mass concentration is the extreme boundary lubrication system of 1% multi-branch polyether amine aqueous solution provided by the invention
Number ＜ 0.1.
Raw material used in following embodiment of the present invention is commercial goods.
Embodiment 1
The hydrochloric acid of the glycerine of 10g, the ethylene glycol of 8g, the water of 30g, 0.8g are added in stirring and condensation reflux unit
Four-hole boiling flask in, react 2.0h at 90 DEG C of temperature, obtain intermediate product；
The epoxychloropropane of 5g, the sodium hydroxide of 0.8g, the ethylenediamine of 10g are added in into above-mentioned intermediate product, in temperature
0.5h is reacted at 40 DEG C, obtained reaction product is dried and is removed water, obtains multi-branch polyether amine, yield 92.18%.
The multi-branch polyether amine that the embodiment of the present invention 1 is prepared has the structure shown in formula 1：
In formula 1, m 1, n 1, o 0.
According to the method described in above-mentioned technical proposal, the multi-branch polyether amine that the test embodiment of the present invention 1 is prepared exists
Shale primary recovery, shale relative recovery, clay relative inhibition and extreme boundary lubrication system when rolling 16 is small at 150 DEG C
Number；Test result is as shown in table 1, and table 1 is the multi-branch polyether amine the performance test results that the embodiment of the present invention is prepared.
Embodiment 2
The number-average molecular weight of the glycerine of 10g, 9g are added in into band for 400 polyethylene glycol, the water of 35g, the sulfuric acid of 0.9g
In the four-hole boiling flask for having stirring and condensation reflux unit, 3.0h is reacted at 100 DEG C of temperature, obtains intermediate product；
1,2- epoxies chlorobutane, the potassium hydroxide of 0.9g, the divinyl three of 11g of 6g is added in into above-mentioned intermediate product
Amine reacts 1.0h under temperature 45 C, and obtained reaction product is dried and is removed water, obtains multi-branch polyether amine, yield is
92.43%.
The multi-branch polyether amine that the embodiment of the present invention 2 is prepared has the structure shown in formula 2：
In formula 2, m is 9~10, n 2, o 1.
According to the method described in above-mentioned technical proposal, the multi-branch polyether amine that the test embodiment of the present invention 2 is prepared exists
Shale primary recovery, shale relative recovery, clay relative inhibition and extreme boundary lubrication system when rolling 16 is small at 150 DEG C
Number；Test result is as shown in table 1.
Embodiment 3
The number-average molecular weight of the glycerine of 10g, 10g are added in into band for 600 polyethylene glycol, the water of 40g, the phosphoric acid of 1.0g
In the four-hole boiling flask for having stirring and condensation reflux unit, 4.0h is reacted at 110 DEG C of temperature, obtains intermediate product；
The epoxychloropropane of 7g, the barium hydroxide of 1.0g, the triethylene tetramine of 12g are added in into above-mentioned intermediate product,
1.5h is reacted under temperature 50 C, obtained reaction product is dried and is removed water, obtains multi-branch polyether amine, yield 92.56%.
The multi-branch polyether amine that the embodiment of the present invention 3 is prepared has the structure shown in formula 3：
In formula 3, m is 12~13, n 1, o 2.
According to the method described in above-mentioned technical proposal, the multi-branch polyether amine that the test embodiment of the present invention 3 is prepared exists
Shale primary recovery, shale relative recovery, clay relative inhibition and extreme boundary lubrication system when rolling 16 is small at 150 DEG C
Number；Test result is as shown in table 1.
Embodiment 4
The number-average molecular weight of the glycerine of 10g, 11g are added in for 800 polyethylene glycol, the water of 45g, the tartaric acid of 1.1g
In four-hole boiling flask with stirring and condensation reflux unit, 2.0h is reacted at 120 DEG C of temperature, obtains intermediate product；
1,2- epoxies chlorobutane, the sodium hydroxide of 1.1g, four ethylene five of 13g of 8g are added in into above-mentioned intermediate product
Amine reacts 2.0h at 55 DEG C of temperature, and obtained reaction product is dried and is removed water, obtains multi-branch polyether amine, yield is
92.28%.
The multi-branch polyether amine that the embodiment of the present invention 4 is prepared has the structure shown in formula 4：
In formula 4, m is 15~16, n 2, o 3.
According to the method described in above-mentioned technical proposal, the multi-branch polyether amine that the test embodiment of the present invention 4 is prepared exists
Shale primary recovery, shale relative recovery, clay relative inhibition and extreme boundary lubrication system when rolling 16 is small at 150 DEG C
Number；Test result is as shown in table 1.
Embodiment 5
The oxalic acid of the glycerine of 10g, the ethylene glycol of 12g, the water of 50g, 1.2g are added in stirring and condensing reflux dress
In the four-hole boiling flask put, 3.0h is reacted at 130 DEG C of temperature, obtains intermediate product；
The epoxychloropropane of 9g, the potassium hydroxide of 1.2g, the pentaethylene hexamine of 14g are added in into above-mentioned intermediate product,
0.5h is reacted under temperature 60 C, obtained reaction product is dried and is removed water, obtains multi-branch polyether amine, yield 92.37%.
The multi-branch polyether amine that the embodiment of the present invention 5 is prepared has the structure shown in formula 5：
In formula 5, m 1, n 1, o 4.
According to the method described in above-mentioned technical proposal, the multi-branch polyether amine that the test embodiment of the present invention 5 is prepared exists
Shale primary recovery, shale relative recovery, clay relative inhibition and extreme boundary lubrication system when rolling 16 is small at 150 DEG C
Number；Test result is as shown in table 1.
Embodiment 6
By polyethylene glycol that the number-average molecular weight of the glycerine of 10g, 13g are 400, the water of 55g, 1.3g p-methyl benzenesulfonic acid
It adds in the four-hole boiling flask with stirring and condensation reflux unit, reacts 4.0h at 140 DEG C of temperature, obtain intermediate product；
1,2- epoxies chlorobutane, the barium hydroxide of 1.2g, the divinyl three of 15g of 11g is added in into above-mentioned intermediate product
Amine reacts 1h at 40 DEG C of temperature, and obtained reaction product is dried and is removed water, obtains multi-branch polyether amine, yield is
95.29%.
The multi-branch polyether amine that the embodiment of the present invention 6 is prepared has the structure shown in formula 6：
In formula 6, m is 9~10, n 2, o 1.
According to the method described in above-mentioned technical proposal, the multi-branch polyether amine that the test embodiment of the present invention 6 is prepared exists
Shale primary recovery, shale relative recovery, clay relative inhibition and extreme boundary lubrication system when rolling 16 is small at 150 DEG C
Number；Test result is as shown in table 1.
Embodiment 7
By polyethylene glycol that the number-average molecular weight of the glycerine of 10g, 14g are 600, the water of 60g, 1.4g detergent alkylate
Sulfonic acid is added in the four-hole boiling flask with stirring and condensation reflux unit, is reacted 2.0h at 140 DEG C of temperature, is obtained intermediate production
Object；
The epoxychloropropane of 12g, the sodium hydroxide of 1.2g, the triethylene tetramine of 16g are added in into above-mentioned intermediate product,
2h is reacted under temperature 45 C, obtained reaction product is dried and is removed water, obtains multi-branch polyether amine, yield 92.57%.
The multi-branch polyether amine that the embodiment of the present invention 7 is prepared has the structure shown in formula 7：
In formula 7, m is 12~13, n 1, o 2.
According to the method described in above-mentioned technical proposal, the multi-branch polyether amine that the test embodiment of the present invention 7 is prepared exists
Shale primary recovery, shale relative recovery, clay relative inhibition and extreme boundary lubrication system when rolling 16 is small at 150 DEG C
Number；Test result is as shown in table 1.
Embodiment 8
Polyethylene glycol, the water of 60g, the sulfamic acid of 1.5g that the number-average molecular weight of the glycerine of 10g, 14g are 600 are added
Enter in the four-hole boiling flask with stirring and condensation reflux unit, react 3.0h at 140 DEG C of temperature, obtain intermediate product；
1,2- epoxies chlorobutane, the sodium hydroxide of 1.2g, four ethylene five of 18g of 14g are added in into above-mentioned intermediate product
Amine reacts 2.0h under temperature 50 C, and obtained reaction product is dried and is removed water, obtains multi-branch polyether amine, yield is
92.25%.
The multi-branch polyether amine that the embodiment of the present invention 8 is prepared has the structure shown in formula 8：
In formula 8, m is 12~13, n 2, o 3.
According to the method described in above-mentioned technical proposal, the multi-branch polyether amine that the test embodiment of the present invention 8 is prepared exists
Shale primary recovery, shale relative recovery, clay relative inhibition and extreme boundary lubrication system when rolling 16 is small at 150 DEG C
Number；Test result is as shown in table 1.
Embodiment 9
The number-average molecular weight of the glycerine of 10g, 14g are added in for 600 polyethylene glycol, the water of 60g, the phosphotungstic acid of 1.5g
In four-hole boiling flask with stirring and condensation reflux unit, 4.0h is reacted at 140 DEG C of temperature, obtains intermediate product；
1,2- epoxies chlorobutane, the sodium hydroxide of 1.2g, five ethylene six of 20g of 15g are added in into above-mentioned intermediate product
Amine reacts 2.0h under temperature 60 C, and obtained reaction product is dried and is removed water, obtains multi-branch polyether amine, yield is
93.49%.
The multi-branch polyether amine that the embodiment of the present invention 9 is prepared has the structure shown in formula 9：
In formula 9, m is 12~13, n 2, o 4.
According to the method described in above-mentioned technical proposal, the multi-branch polyether amine that the test embodiment of the present invention 9 is prepared exists
Shale primary recovery, shale relative recovery, clay relative inhibition and extreme boundary lubrication system when rolling 16 is small at 150 DEG C
Number；Test result is as shown in table 1.
The multi-branch polyether amine the performance test results that 1 embodiment of the present invention of table is prepared
As shown in Table 1, the multi-branch polyether amine aqueous solution provided in an embodiment of the present invention that mass concentration is 1% is at 150 DEG C
High temperature rolls 16h, shale primary recovery ＞ 95%, shale relative recovery ＞ 98%；Clay relative inhibition is 100%,
Extreme boundary lubrication coefficient ＜ 0.1.The multi-branch polyether amine that the embodiment of the present invention is prepared has preferable shale inhibition energy, sticks
Native aquation dispersion performance and greasy property.
As seen from the above embodiment, the present invention provides a kind of multi-branch polyether amine, there is the structure shown in Formulas I；Formulas I
In, m is that 1~16, n is that 1~2, o is 0~4.The present invention provides a kind of systems of multi-branch polyether amine described in above-mentioned technical proposal
Preparation Method, including：Glycerine, glycol compound, water and acidic catalyst are reacted, obtain intermediate product；By described in
Intermediate product and chloro epoxides, alkali compounds, organic amine are reacted, and obtain multi-branch polyether amine.The present invention provides
Multi-branch polyether amine have preferable shale inhibition and clay aquation dispersion performance.It is in addition, provided by the invention hyper-branched
Polyetheramine has preferable greasy property, and no biotoxicity.In addition, the preparation side of multi-branch polyether amine provided by the invention
Method is simple for process, and reaction condition is mild, easy to operation.
Claims (10)
1. a kind of multi-branch polyether amine has the structure shown in Formulas I：
In Formulas I, m is 1~16；N is that 1~2, o is 0~4.
2. multi-branch polyether amine according to claim 1, which is characterized in that in the Formulas I, m is 5~10.
3. a kind of preparation method of the multi-branch polyether amine of claim 1 or 2, including：
Glycerine, glycol compound, water and acidic catalyst are reacted, obtain intermediate product, the glycols chemical combination
Object is ethylene glycol or polyethylene glycol；
The intermediate product and chloro epoxides, alkali compounds, organic amine are reacted, obtain multi-branch polyether amine,
The chloro epoxides includes epoxychloropropane or 1,2- epoxy chloro-butanes；
The organic amine includes ethylenediamine, diethylenetriamine, triethylene tetramine, tetraethylenepentamine or pentaethylene hexamine.
4. according to the method described in claim 3, it is characterized in that, the glycerine, glycol compound, water, acidic catalyst
Agent, chloro epoxides, the mass ratio of alkali compounds and organic amine are 10:(8~14):(30~60):(0.8~1.5):(5
~15):(0.8~1.2):(10~20).
5. according to the method described in claim 3, it is characterized in that, the glycol compound is polyethylene glycol.
6. according to the method described in claim 3, it is characterized in that, the acidic catalyst is hydrochloric acid, sulfuric acid, phosphoric acid, winestone
Acid, oxalic acid, p-methyl benzenesulfonic acid, dodecyl benzene sulfonic acid, sulfamic acid or phosphotungstic acid.
7. according to the method described in claim 3, it is characterized in that, the chloro epoxides is epoxychloropropane.
8. according to the method described in claim 3, it is characterized in that, the alkali compounds for sodium hydroxide, potassium hydroxide or
Barium hydroxide.
9. according to the method described in claim 3, it is characterized in that, the organic amine is diethylenetriamine, triethylene tetramine, four
Five amine of ethylene or pentaethylene hexamine.
10. a kind of application of multi-branch polyether amine in drilling fluid, the multi-branch polyether amine is described in claim 1 or 2
The multi-branch polyether amine that method in multi-branch polyether amine or claim 3~9 described in any one is prepared.
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| EP3385299B1 (en) * | 2015-12-03 | 2020-11-04 | China Petroleum & Chemical Corporation | Amine polymer and preparation method and use thereof. |
| CN108727562B (en) * | 2017-04-24 | 2020-11-13 | 中国石油化工股份有限公司 | Epoxy resin curing agent, epoxy resin curing method and epoxy resin cured product obtained by epoxy resin curing method |
| CN108728059B (en) * | 2017-04-24 | 2021-01-08 | 中国石油化工股份有限公司 | Drilling fluid composition and preparation method thereof |
| CN107090281A (en) * | 2017-05-05 | 2017-08-25 | 辽宁石油化工大学 | A kind of preparation method of drilling fluid mobile phase |
| CN109694473B (en) * | 2017-10-23 | 2021-06-15 | 中石化石油工程技术服务有限公司 | Polyether amine shale inhibitor for drilling fluid, preparation method of polyether amine shale inhibitor and drilling fluid |
| CN110699051B (en) * | 2018-07-09 | 2022-07-08 | 中石化石油工程技术服务有限公司 | Biomass base oil and preparation method thereof |
| CN111718698B (en) * | 2020-07-22 | 2022-04-19 | 西南石油大学 | Hyperbranched polyetheramine environment-friendly shale inhibitor, preparation method thereof and water-based drilling fluid |
| CN111662194B (en) * | 2020-07-22 | 2022-03-08 | 西南石油大学 | Environment-friendly ether amine shale inhibitor and water-based drilling fluid thereof |
| CN113528100B (en) * | 2020-12-28 | 2023-01-17 | 中国石油化工集团有限公司 | Near-well-wall stable polyamine shale inhibitor, and preparation method and application thereof |
| CN115838337A (en) * | 2022-11-23 | 2023-03-24 | 广州天润新材料科技有限公司 | Polyhydroxy branched polyether amine and preparation method and application thereof |
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