CN109748994A - Polymer and its preparation method and application with selective water plugging function - Google Patents
Polymer and its preparation method and application with selective water plugging function Download PDFInfo
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Abstract
The present invention relates to the research fields of oil field profile control and water plugging material and promotion High Water Cut Reservoir oil well productivity, disclose a kind of polymer with selective water plugging function, wherein, the polymer is in initiator and in the presence of as the water of solvent, the lotion containing monomer A, monomer B, monomer C and emulsifier is set to carry out polymerization reaction and be made, wherein, the monomer A is acrylamide；The monomer B is fumaric acid；The monomer C is oil-soluble monomer, and the oil-soluble monomer is styrene and/or 2-Propenoic acid, 2-methyl-, octyl ester；The emulsifier includes primary emulsion and/or assistant for emulsifying agent.Polymer prepared by the present invention has the effect of excellent selective water plugging without stifled oily, and resistance to erosion multiple with higher.
Description
Technical field
The present invention relates to the research fields of oil field profile control and water plugging material and promotion High Water Cut Reservoir oil well productivity, specifically
Ground is related to a kind of polymer with selective water plugging function, a kind of side for preparing the polymer with selective water plugging function
Method and the polymer with selective water plugging function being prepared by this method, the polymer with selective water plugging function
The alternatively application of property water shutoff agent.
Background technique
Oilwell water shutoff technique is to optimize a key technique of oil gas field waterflooding extraction achievement.Water layer and oil in stratum
Layer is interweaved together, and heterogeneity is serious, and existing construction technology is difficult for two kinds of reservoirs to be effectively isolated, but oily
Field enterprise is stabilized crude (oil) yield, the composite water cut of oil well is also reduced as far as possible, for this to highly selective with oil/water
Water shutoff agent more stringent requirements are proposed.The water blockoffs systems such as existing water base, oil base, polymer gel, although having centainly
Selectivity, but not only water blockoff was again stifled oily, indoor logistics organizations the result shows that, the oil plugging rate of existing water shutoff agent is all larger than 35%, and
And the temperature-resistant anti-salt performance of system is also poor, the extent of spreading amd application is smaller.Although water-soluble polymer water shutoff agent can select excellent
It is introduced into the higher stratum of water saturation, but the water-soluble polymer water shutoff agent that part is had in the migration of stratum enters
Into oil reservoir, since such water shutoff agent itself is without the ability of voluntarily de-plugging, it is very difficult for discharging it.Oil based cement is stifled
Although aqua also can largely improve oil recovery factor, there is also very big drawbacks, and what it was generally blocked is aqueous
The higher stratum of saturation degree, when oil based cement water shutoff agent is flowed into the stratum of oil mixing with water, even if only being mixed very in oil reservoir
At least part of water flooding, can also react with water flooding makes to the cement solidifies, this illustrates the water blockoff of oil based cement water shutoff agent
There are also be significantly short of selection performance.Polymer gel class water shutoff agent is by means of the lower effectively movably change of volume of grease effect
Change, makes Oil/water Phase Permeability that non-uniform reduction occur, but the processing mode will cause the closure of fluid swivels physics, cause porous
The decline of medium percolation ability, oil well produce oil productive capacity while water is greatly lowered and also reduce, deal with improperly and will cause Liquid output
It is too low, make the crude oil underproduction.
Currently, selective water shutoff agent and Novel technique of in-depth profile control become better and approaching perfection day by day both at home and abroad, in grinding for selective water plugging material
Studying carefully exploitation, construction technology etc. has technically had tremendous development, but as oil field development, oil-layer characteristic and environment are constantly sent out
Changing keeps the contradiction of oil reservoir development more prominent, according to selectivity using water shutoff material for a long time particularly to development late stage
The characteristic of water shutoff material summarizes the experience of oil field actual development, proposes the technology that current selective water shutoff agent must overcome at present
Problem, to research and develop new technology targetedly to adapt to special oil field and improve the water plugging effect of selective system.
In conclusion selective water-plugging used in oilwell water shutoff is mostly by water such as polyacrylamide and its derivatives at present
Soluble polymer generates gel in stratum or frozen glue blocks water flooding, or meets water plastic or solidification envelope with oil base blocking agent
Water blockoff alters channel, but due to its poor selectivity, also will be greatly reduced oleic permeability while water blockoff, causes stifled rear low
Liquid constrains the application of water shutoff in oil well.
Therefore, a kind of novel highly selective water shutoff material is developed, the not stifled oil of the water blockoff of oil reservoir is realized, ultra-high water cut stage is mentioned
High oil well productivity has great importance.
Summary of the invention
The purpose of the invention is to overcome the deficiencies of existing technologies, a kind of polymerization with selective water plugging function is provided
Object and its preparation method and application, that is, a certain amount of water-soluble monomer, oil-soluble monomer and emulsifier are added in aqueous solution,
The emulsion system of stable oil-in-water form is formed after stirring, and initiator is added and is finally synthesizing a kind of water by the way of polymerization
The water shutoff material of base oil insoluble polymer particles type.It is provided by the invention that there is highly selective water shutoff material, it is existing according to oil field
Field demand can be configured to the water shutoff agent of different quality concentration using live water, and water shutoff agent is through injecting in reservoir formation, into water phase
After layer, oil-soluble particle therein can carry out duct effectively to block and then reduce water phase permeability, increase water phase plugging action；
Into after oily phase layer, oil-soluble particle therein be dissolved in crude oil without influence oleic permeability, thus reach selective water plugging and
The effect of oil is not blocked up.
To achieve the goals above, first aspect present invention provides a kind of polymer with selective water plugging function,
Wherein, which is to make in initiator and in the presence of as the water of solvent containing monomer A, monomer B, monomer C and emulsifier
Lotion carry out polymerization reaction and be made, wherein the monomer A be acrylamide；The monomer B is fumaric acid；The monomer C
For oil-soluble monomer, and the oil-soluble monomer is styrene and/or 2-Propenoic acid, 2-methyl-, octyl ester；The emulsifier includes main emulsification
Agent and/or assistant for emulsifying agent.
Preferably, on the basis of the water of 100 parts by weight, the content of the monomer A is 0.4-5 parts by weight, the monomer B's
Content is 0.1-5 parts by weight, and the content of the monomer C is 1-10 parts by weight, and the content of the primary emulsion is 0.5-4.5 weight
Part, the content of the assistant for emulsifying agent is 0-1.5 parts by weight；
More preferably, it is preferable that on the basis of the water of 100 parts by weight, the content of the monomer A is 3.5-4.5 parts by weight,
The content of the monomer B is 2.5-4.5 parts by weight, and the content of the monomer C is 3-4 parts by weight, the content of the primary emulsion
For 2.5-3.5 parts by weight, the content of the assistant for emulsifying agent is 0.6-0.9 parts by weight；
Most preferably, on the basis of the water of 100 parts by weight, the content of the monomer A is 3.8-4.2 parts by weight, the list
The content of body B is 3-4 parts by weight, and the content of the monomer C is 3.3-3.8 parts by weight, and the content of the primary emulsion is 2.8-
3.2 parts by weight, the content of the assistant for emulsifying agent are 0.7-0.8 parts by weight.
Preferably, the resistance to erosion multiple of the polymer is greater than 50PV.
Preferably, the primary emulsion is selected from dodecyl sodium sulfate, lauryl sodium sulfate and dodecyl benzene sulfonic acid
One of sodium is a variety of；Preferably, the primary emulsion is selected from dodecyl sodium sulfate and/or neopelex；
The assistant for emulsifying agent is selected from Span 20, Span 40, Span 60, Span 80, polysorbas20, polysorbate40, polysorbate60 and spits
One of temperature 80 is a variety of；Preferably, the assistant for emulsifying agent is selected from one of Span 20, Span 40 and Tween 80 or more
Kind.
Preferably, the initiator is water soluble starter and/or oil-soluble initiator, and the water soluble starter was
Sulfate-sulphite oxidation-reduction trigger system, the oil-soluble initiator are azodiisobutyronitrile and/or azo two
Isobutyl dimethyl phthalate；
Preferably, the initiator is the composition of water soluble starter and oil-soluble initiator；
Preferably, on the basis of the total content of the monomer A and the monomer B, the content of the persulfate is 0.01-
0.1 weight %, the content of the sulphite are 0.005-0.05 weight %；And
On the basis of the total content of the monomer C, the content of the oil-soluble initiator is 0.01-0.1 weight %.
Second aspect of the present invention provides a kind of preparation method of polymer with selective water plugging function, wherein should
Preparation method the following steps are included:
(1) monomer A, monomer B and water are mixed, forms aqueous solution；
(2) monomer C, emulsifier are mixed with the aqueous solution, forms lotion；
(3) lotion is subjected to polymerization reaction in the presence of initiator；
Wherein, the monomer A is acrylamide；The monomer B is fumaric acid；The monomer C is oil-soluble monomer, and institute
Stating oil-soluble monomer is styrene and/or 2-Propenoic acid, 2-methyl-, octyl ester；The emulsifier includes primary emulsion and/or assistant for emulsifying agent.
Preferably, on the basis of the water of 100 parts by weight, the dosage of the monomer A is 0.4-5 parts by weight, the monomer B's
Dosage is 0.1-5 parts by weight, and the dosage of the monomer C is 1-10 parts by weight, and the dosage of the primary emulsion is 0.5-4.5 weight
Part, the dosage of the assistant for emulsifying agent is 0-1.5 parts by weight；
It is highly preferred that the dosage of the monomer A is 3.5-4.5 parts by weight, the list on the basis of the water of 100 parts by weight
The dosage of body B is 2.5-4.5 parts by weight, and the dosage of the monomer C is 3-4 parts by weight, and the dosage of the primary emulsion is 2.5-
3.5 parts by weight, the dosage of the assistant for emulsifying agent are 0.6-0.9 parts by weight；
Most preferably, on the basis of the water of 100 parts by weight, the dosage of the monomer A is 3.8-4.2 parts by weight, the list
The dosage of body B is 3-4 parts by weight, and the dosage of the monomer C is 3.3-3.8 parts by weight, and the dosage of the primary emulsion is 2.8-
3.2 parts by weight, the dosage of the assistant for emulsifying agent are 0.7-0.8 parts by weight.
Preferably, the resistance to erosion multiple of the polymer is greater than 50PV.
Preferably, the primary emulsion is selected from dodecyl sodium sulfate, lauryl sodium sulfate and dodecyl benzene sulfonic acid
One of sodium is a variety of；Preferably, the primary emulsion is selected from dodecyl sodium sulfate and/or neopelex；
The assistant for emulsifying agent is selected from Span 20, Span 40, Span 60, Span 80, polysorbas20, polysorbate40, polysorbate60 and spits
One of temperature 80 is a variety of；Preferably, the assistant for emulsifying agent is selected from one of Span 20, Span 40 and Tween 80 or more
Kind.
Preferably, the initiator is water soluble starter and/or oil-soluble initiator, and the water soluble starter was
Sulfate-sulphite oxidation-reduction trigger system, the oil-soluble initiator are azodiisobutyronitrile and/or azo two
Isobutyl dimethyl phthalate；
Preferably, the initiator is the composition of water soluble starter and oil-soluble initiator；
Preferably, on the basis of total dosage of the monomer A and the monomer B, the dosage of the persulfate is 0.01-
0.1 weight %, the dosage of the sulphite are 0.005-0.05 weight %；And
On the basis of total dosage of the monomer C, the dosage of the oil-soluble initiator is 0.01-0.1 weight %.
Preferably, in step (1), the pH value of the aqueous solution is 6-10；And in step (3), the polymerization is anti-
The condition answered are as follows: temperature is 40-60 DEG C, and preferably 45-55 DEG C, the time is 6-8 hours, preferably 7-8 hours.
Third aspect present invention provides the polymerization with selective water plugging function that method described above is prepared
Object.
Fourth aspect present invention provides the polymer with selective water plugging function described above, and alternatively property is stifled
The application of aqua.
For the present invention by introducing a kind of oil-soluble polymer beads in the lotion of water base acrylamide copolymer, oil is molten
The polymer beads of property can stable suspersion in water-base emulsion, can be smoothly injected into reservoir formation by high-pressure pump.Oil-soluble
The presence of particle can considerably increase the temperature-resistant anti-salt performance and scour resistance of water blockoff agent material.In the earth formation, work as water shutoff agent
It is influenced, can be deformed by pelagic environment temperature and pressure, a large amount of oil-soluble particle water shutoff agents interaction of aggregation,
Effective closure is formed to the higher blowhole stratum of water saturation, and then substantially reduces the water yield of oil well.Part oil is molten
After property particle water shutoff agent is flowed into oil reservoir, due to itself preferable oil-soluble, just it can be added in crude oil, with underground crude oil one
It rises to return and drains into ground, to significantly improve the oil/water selectivity of water shutoff material, achieve the effect that the not stifled oil of water blockoff, be low oil price
Lower inefficient well creates beneficial synergy and provides behave, improves oil well productivity for ultra-high water cut stage and provides technical support.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
In a first aspect, the present invention provides a kind of polymer with selective water plugging function, wherein the polymer can be with
To gather the lotion containing monomer A, monomer B, monomer C and emulsifier in initiator and in the presence of as the water of solvent
It closes reaction and is made, wherein the monomer A is acrylamide；The monomer B is fumaric acid (FA)；The monomer C is oil-soluble
Monomer, and the oil-soluble monomer is styrene and/or 2-Propenoic acid, 2-methyl-, octyl ester；The emulsifier include primary emulsion and/or
Assistant for emulsifying agent.
In the present invention, the monomer A, the monomer B, the monomer C can be commercially available or using existing
The method of technology synthesizes to obtain.For example, the monomer A, the monomer B, the monomer C that the embodiment of the present invention part uses
It is all from commercially available, wherein monomer A acrylamide is purchased from the commercially available product of Shandong Polymer Bio-Chemicals Co., Ltd.'s production, single
Body B fumaric acid and monomer C styrene and/or 2-Propenoic acid, 2-methyl-, octyl ester are purchased from Beijing chemical reagents corporation commercial product.
According to the present invention, on the basis of the water of 100 parts by weight, the content of the monomer A is 0.4-5 parts by weight, the list
The content of body B is 0.1-5 parts by weight, and the content of the monomer C is 1-10 parts by weight, and the content of the primary emulsion is 0.5-
4.5 parts by weight, the content of the assistant for emulsifying agent are 0-1.5 parts by weight；In the present invention, the monomer A, the monomer B, described
Monomer C, the specific choice of the primary emulsion and the assistant for emulsifying agent and content control can be completed within above range
The present invention, it is, however, preferable that the content of the monomer A is 3.5-4.5 parts by weight, described on the basis of the water of 100 parts by weight
The content of monomer B is 2.5-4.5 parts by weight, and the content of the monomer C is 3-4 parts by weight, and the content of the primary emulsion is
2.5-3.5 parts by weight, when the content of the assistant for emulsifying agent is 0.6-0.9 parts by weight, effect is preferable；It is highly preferred that with 100 weight
On the basis of the water of part, the content of the monomer A is 3.8-4.2 parts by weight, and the content of the monomer B is 3-4 parts by weight, the list
The content of body C is 3.3-3.8 parts by weight, and the content of the primary emulsion is 2.8-3.2 parts by weight, the content of the assistant for emulsifying agent
When for 0.7-0.8 parts by weight, effect is more preferable.
It is further preferred that the total content of the monomer A and the monomer B are 0.5- on the basis of the water of 100 parts by weight
10 weight %, preferably 6.8-8.2 weight %.
Preferably, the resistance to erosion multiple of the polymer is greater than 50PV.
According to the present invention, the primary emulsion can be selected from dodecyl sodium sulfate (SBS), lauryl sodium sulfate
(SDS) and one of neopelex (SDBS) or a variety of；Preferably, the primary emulsion is selected from dodecyl sulphur
One of sour sodium (SBS) and/or neopelex (SDBS) are a variety of；
The assistant for emulsifying agent can be selected from Span 20, Span 40, Span 60, Span 80, polysorbas20, polysorbate40, polysorbate60
With one of Tween 80 or a variety of；Preferably, the assistant for emulsifying agent be selected from one of Span 20, Span 40 and Tween 80 or
It is a variety of.
According to the present invention, the initiator can be water soluble starter and/or oil-soluble initiator, and the water solubility is drawn
Hair agent is persulfate-sulphite oxidation-reduction trigger system, and the oil-soluble initiator can be azodiisobutyronitrile
And/or azo-bis-iso-dimethyl.
Preferably, the initiator is the composition of water soluble starter and oil-soluble initiator；
It is further preferred that on the basis of the total content of the monomer A and the monomer B, the content of the persulfate
For 0.01-0.1 weight %, the content of the sulphite is 0.005-0.05 weight %；It is further preferred that with the monomer
On the basis of the total content of A and the monomer B, the content of the persulfate is 0.025-0.1 weight %, the sulphite
When content is 0.025-0.05 weight %, effect is more preferable；It is further preferred that always containing with the monomer A and monomer B
On the basis of amount, the content of the persulfate is 0.05-0.08 weight %, and the content of the sulphite is 0.03-0.04 weight
When measuring %, effect is best；
On the basis of the total content of the monomer C, the content of the oil-soluble initiator is 0.01-0.1 weight %；It is preferred that
Ground, on the basis of the total content of the monomer C, when the content of the oil-soluble initiator is 0.01-0.05 weight %, effect is more
It is good；It is further preferred that the content of the oil-soluble initiator is 0.02-0.04 weight on the basis of the total content of the monomer C
When measuring %, effect is best.In the present invention, when the oil-soluble initiator can be two isobutyric acid of azodiisobutyronitrile and azo
The ratio of the content of the composition of dimethyl ester, the azodiisobutyronitrile and the azo-bis-iso-dimethyl does not limit specifically
It is fixed, as long as the total content of the azodiisobutyronitrile and the azo-bis-iso-dimethyl is 0.01-0.1 weight %, preferably
For 0.01-0.05 weight %, when more preferably 0.02-0.04.
Second aspect, the present invention provides a kind of preparation methods of polymer with selective water plugging function, wherein should
Preparation method the following steps are included:
(1) monomer A, monomer B and water are mixed, forms aqueous solution；
(2) monomer C, emulsifier are mixed with the aqueous solution, forms lotion；
(3) lotion is subjected to polymerization reaction in the presence of initiator；
Wherein, the monomer A is acrylamide；The monomer B is fumaric acid；The monomer C is oil-soluble monomer, and institute
Stating oil-soluble monomer is styrene and/or 2-Propenoic acid, 2-methyl-, octyl ester；The emulsifier includes primary emulsion and/or assistant for emulsifying agent.
There is polymerization reaction involved in the method for the polymer of selective water plugging function to use for the preparation of the invention
The mode of lotion suspension polymerisation.
The polymerization reaction can also carry out in the presence of protective gas, and the protective gas preferably can be nitrogen.
According to the present invention, on the basis of the water of 100 parts by weight, the dosage of the monomer A is 0.4-5 parts by weight, the list
The dosage of body B is 0.1-5 parts by weight, and the dosage of the monomer C is 1-10 parts by weight, and the dosage of the primary emulsion is 0.5-
4.5 parts by weight, the dosage of the assistant for emulsifying agent are 0-1.5 parts by weight；In the present invention, the monomer A, the monomer B, described
Monomer C, the specific choice of the primary emulsion and the assistant for emulsifying agent and dosage control can be completed within above range
The present invention, it is, however, preferable that the dosage of the monomer A is 3.5-4.5 parts by weight, described on the basis of the water of 100 parts by weight
The dosage of monomer B is 2.5-4.5 parts by weight, and the dosage of the monomer C is 3-4 parts by weight, and the dosage of the primary emulsion is
2.5-3.5 parts by weight, when the dosage of the assistant for emulsifying agent is 0.6-0.9 parts by weight, effect is preferable；It is highly preferred that with 100 weight
On the basis of the water of part, the dosage of the monomer A is 3.8-4.2 parts by weight, and the dosage of the monomer B is 3-4 parts by weight, the list
The dosage of body C is 3.3-3.8 parts by weight, and the dosage of the primary emulsion is 2.8-3.2 parts by weight, the dosage of the assistant for emulsifying agent
When for 0.7-0.8 parts by weight, effect is more preferable.
It is further preferred that on the basis of the water of 100 parts by weight, total dosage of the primary emulsion and the assistant for emulsifying agent
For 1-5 parts by weight, preferably 3-4 parts by weight.
Preferably, the resistance to erosion multiple for the polymer being prepared is greater than 50PV.
According to the present invention, the primary emulsion can be selected from dodecyl sodium sulfate, lauryl sodium sulfate and dodecane
One of base benzene sulfonic acid sodium salt is a variety of；Preferably, the primary emulsion is selected from dodecyl sodium sulfate and/or detergent alkylate
One of sodium sulfonate is a variety of.
The assistant for emulsifying agent can be selected from Span 20, Span 40, Span 60, Span 80, polysorbas20, polysorbate40, polysorbate60
With one of Tween 80 or a variety of；Preferably, the assistant for emulsifying agent be selected from one of Span 20, Span 40 and Tween 80 or
It is a variety of.
According to the present invention, the initiator can be water soluble starter and/or oil-soluble initiator, and the water solubility is drawn
Hair agent can be the oxidation-reduction trigger system being made of persulfate oxidation agent and sulfite reducing agent.In preferable case
Under, on the basis of total dosage of the monomer A and the monomer B, the dosage of the persulfate is 0.01-0.1 weight %, institute
The dosage for stating sulphite is 0.005-0.05 weight %, that is to say, that the dosage of the persulfate is monomer A and monomer B
Total dosage 0.01-0.1 weight %, the dosage of the sulphite is the 0.005-0.05 of total dosage of monomer A and monomer B
Weight %.For example, oxidant in the redox type initiators can for 0.2 weight % persulfate aqueous solution and/
Or 0.2 weight % ammonium persulfate aqueous solution；Reducing agent in the redox type initiators can be the Asia of 0.1 weight %
The aqueous solution of sodium bisulfite of aqueous potassium hydrogen sulfate and/or 0.1 weight %.
Preferably, on the basis of total dosage of the monomer A and the monomer B, the dosage of the persulfate is
0.025-0.1 weight %, when the dosage of the sulphite is 0.025-0.05 weight %, effect is more preferable；Still more preferably
Ground, on the basis of total dosage of the monomer A and the monomer B, the dosage of the persulfate is 0.05-0.08 weight %,
When the dosage of the sulphite is 0.03-0.04 weight %, effect is best.
The oil-soluble initiator can be azodiisobutyronitrile and/or azo-bis-iso-dimethyl；And with the list
On the basis of total dosage of body C, the dosage of the oil-soluble initiator is 0.01-0.1 weight %；Preferably, with the monomer C's
On the basis of total dosage, when the dosage of the oil-soluble initiator is 0.01-0.05 weight %, effect is more preferable；It is further preferred that
On the basis of total dosage of the monomer C, when the dosage of the oil-soluble initiator is 0.02-0.04 weight %, effect is best.
In the present invention, when the oil-soluble initiator can be azodiisobutyronitrile and azo-bis-iso-dimethyl composition,
The ratio of the dosage of the azodiisobutyronitrile and the azo-bis-iso-dimethyl is not particularly limited, as long as the azo two
Total dosage of isobutyronitrile and the azo-bis-iso-dimethyl be 0.01-0.1 weight %, preferably 0.01-0.05 weight %,
When more preferably 0.02-0.04.
It is further preferred that the initiator is the composition of water soluble starter and oil-soluble initiator.
According to the present invention, in step (1), the pH value of the aqueous solution is preferably 6-10, more preferably 7-9.The pH
Value can be obtained by the way that pH adjusting agent is added into mixed system, and the pH adjusting agent can be the various of this field routine
PH adjusting agent, such as can be at least one of sodium hydroxide, sodium carbonate, potassium carbonate and ammonium hydroxide, preferably sodium hydroxide
And/or sodium carbonate.
According to the present invention, in step (3), the condition of the polymerization reaction may include: that temperature is 40-60 DEG C, preferably
It is 45-55 DEG C, the time is 6-8 hours, preferably 7-8 hours.
In the present invention, the environmental condition in the oil field may include: temperature be 40-130 DEG C, preferably 70-110 DEG C,
More preferably 95-110 DEG C；Salinity is 100-200,000mg/L, preferably 10,000-150,000mg/L, more preferably 60,
000-150,000mg/L, most preferably 100,000-150,000mg/L.
A kind of preferred embodiment according to the present invention, the preparation of the polymer with selective water plugging function
Method the following steps are included:
Step 1: monomer A, monomer B and water are added in polymerisation bottle (heat preservation polymerization bottle) and are configured to aqueous solution, is used
The pH value that alkali adjusts the aqueous solution is 6-10；
Step 2: monomer C, emulsifier being added into the aqueous solution of step 1, stirs evenly, and form lotion；
Step 3: in the case where temperature is 40-60 DEG C, after blasting nitrogen 5-60min, being added initiator into the lotion of step 2,
And make it after mixing blasting nitrogen, sealing polymerization 6-8h obtains water base oil-soluble polymers water shutoff material.
Step 4: it uses salinity that water shutoff material is configured to mass concentration for the simulation salt water of 150,000mg/L to be
0.1% aqueous solution, as water shutoff agent.
The third aspect, the present invention provides the polymerizations with selective water plugging function that method described above is prepared
Object.
Fourth aspect, the present invention provides the polymer with selective water plugging function described above, alternatively property is stifled
The application of aqua.
In the above-mentioned polymer with selective water plugging the function alternatively application of property water shutoff agent, specific application side
The technology that method is well known to those skilled in the art.
The present invention synthesizes the aqua type water blockoff material containing oil-soluble polymerization composition granule in a kind of system using the method for polymerization
Material, that is to say, that polymerize in water phase using acrylamide monomers, form water-soluble polymer continuous phase；Oil-soluble list simultaneously
Body is polymerize in emulsification micelle, is formed oil-soluble polymerization composition granule, is changed water shutoff material in oil reservoir by two phase-polymerizations
Achieve the effect that the not stifled oil of water blockoff to improve the oil/water selectivity of water blockoff agent material with water layer different role mechanism.This hair
Bright technical solution obtains oil-soluble polymerization composition granule as raising polymer heat and salt resistance after choosing oil-soluble monomer polymerization
With oil/water selectivity.
The present invention will be described in detail by way of examples below.
Lauryl sodium sulfate (SDS), neopelex (SDBS) and dodecyl sodium sulfate (SBS) Span
20, Span 40 and 80 persulfate of Span and sulphite azodiisobutyronitrile and azo-bis-iso-dimethyl are purchased from traditional Chinese medicines
Chemical reagent Co., Ltd, group.
In following embodiment, the test method being related to is as follows:
Sealing ratiod is on core flow test device according to " drilling fluid bridges plugging material Experimental Method in Laboratory " SY/
Sealing ratiod testing procedure in T5840-2007 carries out.Specifically:
The measurement of water plugging rate: artificial core is packed into core holding unit, is first saturated with water, its pore volume PV and water phase are surveyed
Permeability (Kw1), it is then injected into the water shutoff agent of 1.0PV, after conserving for 24 hours at 95 DEG C, then with after its addition water shutoff agent of aquametry
Permeability (Kw2), Kw2And Kw1Ratio (Kw2/Kw1) it is water plugging rate.
The measurement of oil plugging rate: being packed into core holding unit for artificial core, first with oil saturation, surveys its pore volume PV and oily phase
Permeability (Ko1), it is then injected into the water shutoff agent of 1.0PV, after conserving for 24 hours at 95 DEG C, then with after its addition water shutoff agent of oil measurement
Permeability (Ko2), Ko2And Ko1(Ko2/Ko1) it is oil plugging rate.
The measurement of resistance to erosion multiple: after measuring water plugging rate, continue to inject 50 times of pore volume injecteds (PV) in rock core
Water, while recording the permeability under different PV numbers, and different PV are calculated according to the above-mentioned measuring method about water plugging rate
Water plugging rate under several, the maximum PV number of resistance to erosion multiple injected water when being water plugging rate >=80%.Under normal conditions, it measures
Water plugging rate under 50PV number, the value >=80% illustrate that the material has excellent flushing resistance.
Wherein, artificial core is obtained and tamping the quartz sand of 40-60 mesh in a mold.
Embodiment 1
The present embodiment indicates that the polymer with selective water plugging function of method preparation provided by the invention.
1, weigh 2.9g acrylamide (on the basis of the water of 100 parts by weight, the dosage of monomer A is 0.97 parts by weight) and
The fumaric acid (on the basis of the water of 100 parts by weight, the dosage of monomer B is 0.1 parts by weight) of 0.3g is added in the water of 300mL and stirs
It mixes after completely dissolution, is 6.0 with the pH value that alkali (sodium hydroxide) adjusts the aqueous solution, obtains stable aqueous solution；
2,6.0g styrene (on the basis of the water of 100 parts by weight, the dosage of monomer C is 2 parts by weight), the main cream of 1.5g are weighed
Agent SDBS (on the basis of the water of 100 parts by weight, the dosage of primary emulsion is 0.5 parts by weight) and 1.5g assistant for emulsifying agent Span 20
(on the basis of the water of 100 parts by weight, the dosage of assistant for emulsifying agent is 0.5 parts by weight) is added in above-mentioned solution, after being sufficiently stirred
Form stable lotion；
3, the persulfate aqueous solution 0.15g of 0.2 weight %, the Asia of 0.1 weight % are sequentially added in lotion into step 2
Sodium bisulphate solution 0.15g (on the basis of total dosage 3.2g of the monomer A and monomer B, the use of the persulfate
Amount is 0.01 weight %, and the dosage of the sulphite is 0.005 weight %) and oil-soluble initiator (azodiisobutyronitrile)
0.6mg (on the basis of total dosage 6g of monomer C, the dosage of oil-soluble initiator is 0.01 weight %), after emulsification is sufficiently stirred,
40 DEG C are risen to, causes polymerization and obtains water base oil-soluble polymers in 6 hours.
4, using salinity that water shutoff material is configured to mass concentration for the simulation salt water of 150,000mg/L is 0.1%
Aqueous solution, as DSJ1.
Test result, under conditions of high temperature (95 DEG C) and (salinity 150,000mg/L) with high salt, the water blockoff of the DSJ1
Rate is 94.8%, oil plugging rate 11.6%, and resistance to erosion multiple is greater than 50PV.
Illustrate that the water shutoff material that the present embodiment is prepared has excellent selective shut-off rate and resistance to erosion to oil/water
Property, it is especially remained under high temperature and high salt conditions with preferable oil/water selective shut-off rate.
Embodiment 2
The present embodiment indicates that the polymer with selective water plugging function of method preparation provided by the invention.
1,9.0g acrylamide (on the basis of the water of 100 parts by weight, the dosage of monomer A is 3 parts by weight) and 6.0g are weighed
Fumaric acid (on the basis of the water of 100 parts by weight, the dosage of monomer B is 2 parts by weight) be added in the water of 300mL stir it is abundant
After dissolution, it is 7.0 with the pH value that alkali (sodium carbonate) adjusts the aqueous solution, obtains stable aqueous solution；
2,15.0g styrene (on the basis of the water of 100 parts by weight, the dosage of monomer C is 5 parts by weight), 6.0g master are weighed
Emulsifier SBS (on the basis of the water of 100 parts by weight, the dosage of primary emulsion is 2 parts by weight) and 3.0g assistant for emulsifying agent Span 40
(on the basis of the water of 100 parts by weight, the dosage of assistant for emulsifying agent is 1 parts by weight) is added in above-mentioned solution, and rear shape is sufficiently stirred
At stable lotion；
3, the persulfate aqueous solution 3.75g of 0.2 weight %, 0.1% sulfurous acid are sequentially added in lotion into step 2
(on the basis of total dosage 15g of the monomer A and monomer B, the dosage of the persulfate is hydrogen sodium water solution 3.75g
0.05 weight %, the dosage of the sulphite are 0.025 weight %) and oil-soluble initiator (azo-bis-iso-dimethyl)
7.5mg (on the basis of total dosage 15g of monomer C, the dosage of the oil-soluble initiator is 0.05 weight %), is sufficiently stirred cream
After change, 45 DEG C are risen to, initiation polymerase 17 hour obtains water base oil-soluble polymers.
4, using salinity that water shutoff material is configured to mass concentration for the simulation salt water of 150,000mg/L is 0.1%
Aqueous solution, as DSJ2.
Test result, under conditions of high temperature (95 DEG C) and (salinity 150,000mg/L) with high salt, the water blockoff of the DSJ2
Rate is 98.2%, oil plugging rate 7.9%, and resistance to erosion multiple is greater than 50PV.
Illustrate that the water shutoff material that the present embodiment is prepared has excellent selective shut-off rate and resistance to erosion to oil/water
Property, it is especially remained under high temperature and high salt conditions with preferable oil/water selective shut-off rate.
Embodiment 3
The present embodiment indicates that the polymer with selective water plugging function of method preparation provided by the invention.
1, weigh 15.0g acrylamide (on the basis of the water of 100 parts by weight, the dosage of monomer A is 5 parts by weight) and
The fumaric acid (on the basis of the water of 100 parts by weight, the dosage of monomer B is 5 parts by weight) of 15.0g is added in the water of 300mL and stirs
It mixes after completely dissolution, is 7.0 with the pH value that alkali (sodium hydroxide) adjusts the aqueous solution, obtains stable aqueous solution；
2,30.0g styrene (on the basis of the water of 100 parts by weight, the dosage of monomer C is 10 parts by weight), 10.0g are weighed
Primary emulsion SDS (on the basis of the water of 100 parts by weight, the dosage of primary emulsion is 3.33 parts by weight) and 5.0g assistant for emulsifying agent are spat
Temperature 80 (on the basis of the water of 100 parts by weight, the dosage of assistant for emulsifying agent is 1.67 parts by weight) is added in above-mentioned solution, is sufficiently stirred
Stable lotion is formed after mixing；
3,0.2% persulfate aqueous solution 15.0g, 0.1% sodium hydrogensulfite are sequentially added in lotion into step 2
(on the basis of total dosage 30g of the monomer A and monomer B, the dosage of the persulfate is 0.1 weight to aqueous solution 15.0g
Measure %, the dosage of the sulphite is 0.05 weight %) and oil-soluble initiator 30mg (using total dosage 30g of monomer C as base
Standard, the dosage of the oil-soluble initiator are 0.1 weight %), after emulsification is sufficiently stirred, 60 DEG C are risen to, is caused polymerization 8 hours
To water base oil-soluble polymers.
4, using salinity that water shutoff material is configured to mass concentration for the simulation salt water of 150,000mg/L is 0.1%
Aqueous solution, as DSJ3.
Test result, under conditions of high temperature (95 DEG C) and (salinity 150,000mg/L) with high salt, the water blockoff of the DSJ3
Rate is 99.6%, oil plugging rate 6.1%, and resistance to erosion multiple is greater than 50PV.
Illustrate that the water shutoff material that the present embodiment is prepared has excellent selective shut-off rate and resistance to erosion to oil/water
Property, it is especially remained under high temperature and high salt conditions with preferable oil/water selective shut-off rate.
Embodiment 4
The present embodiment indicates that the polymer with selective water plugging function of method preparation provided by the invention.
1, weigh 10.0g acrylamide (on the basis of the water of 100 parts by weight, the dosage of monomer A is 3.33 parts by weight) and
The fumaric acid (on the basis of the water of 100 parts by weight, the dosage of monomer B is 2.67 parts by weight) of 8.0g is added in the water of 300mL
Stirring after completely dissolution, is 7.0 with the pH value that alkali (sodium carbonate) adjusts the aqueous solution, obtains stable aqueous solution；
2, weighing 12.0g 2-Propenoic acid, 2-methyl-, octyl ester, (on the basis of the water of 100 parts by weight, the dosage of monomer C is 4 weight
Part), 6.0g primary emulsion SDBS (on the basis of the water of 100 parts by weight, the dosage of primary emulsion is 2 parts by weight) and 6.0g help cream
Agent polysorbate40 (on the basis of the water of 100 parts by weight, the dosage of assistant for emulsifying agent is 2 parts by weight) is added in above-mentioned solution, is filled
Stable lotion is formed after dividing stirring；
3,0.2% persulfate aqueous solution 1.8g, 0.1% sodium hydrogensulfite are sequentially added in lotion into step 2
(on the basis of total dosage 18g of the monomer A and monomer B, the dosage of the persulfate is 0.02 weight to aqueous solution 1.8g
% is measured, the dosage of the sulphite is 0.01 weight %) and oil-soluble initiator 6.0mg (is with total dosage 12g of monomer C
Benchmark, the dosage of the oil-soluble initiator are 0.05 weight %), after emulsification is sufficiently stirred, 50 DEG C are risen to, it is small to cause polymerase 17
When obtain water base oil-soluble polymers.
4, using salinity that water shutoff material is configured to mass concentration for the simulation salt water of 150,000mg/L is 0.1%
Aqueous solution, as DSJ4.
Test result, under conditions of high temperature (95 DEG C) and (salinity 150,000mg/L) with high salt, the water blockoff of the DSJ4
Rate is 97.6%, oil plugging rate 5.8%, and resistance to erosion multiple is greater than 50PV.
Illustrate that the water shutoff material that the present embodiment is prepared has excellent selective shut-off rate and resistance to erosion to oil/water
Property, it is especially remained under high temperature and high salt conditions with preferable oil/water selective shut-off rate.
Embodiment 5
The present embodiment indicates that the polymer with selective water plugging function of method preparation provided by the invention.
Have the method for polymer of selective water plugging function identical using with the preparation of implementation 1, except that: this implementation
The usage amount of monomer in example is different, specifically:
The dosage of acrylamide is 12g (on the basis of the water of 100 parts by weight, the dosage of monomer A is 4 parts by weight), rich horse
The dosage of acid is 12g (on the basis of the water of 100 parts by weight, the dosage of monomer B is 4 parts by weight), the dosage of styrene be 6g (with
On the basis of the water of 100 parts by weight, the dosage of monomer C is 2 parts by weight), the dosage of primary emulsion SDBS is 6g (with 100 parts by weight
Water on the basis of, the dosage of primary emulsion is 2 parts by weight) and the dosage of assistant for emulsifying agent Span 20 be 3.0g (with 100 parts by weight
On the basis of water, the dosage of assistant for emulsifying agent is 1 parts by weight)；
And on the basis of total dosage of the monomer A and the monomer B, the dosage of the persulfate is 0.01 weight
% is measured, the dosage of the sulphite is 0.005 weight %；On the basis of total dosage of monomer C, the oil-soluble initiator
Dosage is 0.01 weight %；
Remaining is in the same manner as in Example 1, obtains water base oil-soluble polymers.
Use salinity that water shutoff material is configured to the water that mass concentration is 0.1% for the simulation salt water of 150,000mg/L
Solution, as DSJ5.
Test result: under conditions of high temperature (95 DEG C) and (salinity 150,000mg/L) with high salt, the water blockoff of the DSJ5
Rate is 99.5%, oil plugging rate 8.9%, and resistance to erosion multiple is greater than 60PV, and specifically, resistance to erosion multiple is 60-70PV.
Illustrate that the water shutoff material that the present embodiment is prepared has excellent selective shut-off rate and resistance to erosion to oil/water
Property, it is especially remained under high temperature and high salt conditions with preferable oil/water selective shut-off rate.
Embodiment 6
The present embodiment indicates that the polymer with selective water plugging function of method preparation provided by the invention.
Have the method for polymer of selective water plugging function identical using with the preparation of implementation 1, except that: this implementation
The usage amount of monomer in example is different, specifically:
The dosage of acrylamide is 15g (on the basis of the water of 100 parts by weight, the dosage of monomer A is 5 parts by weight), rich horse
The dosage of acid is 6g (on the basis of the water of 100 parts by weight, the dosage of monomer B is 3 parts by weight), the dosage of styrene be 9g (with
On the basis of the water of 100 parts by weight, the dosage of monomer C is 3 parts by weight), the dosage of primary emulsion SDBS is 9g (with 100 parts by weight
Water on the basis of, the dosage of primary emulsion is 3 parts by weight) and the dosage of assistant for emulsifying agent Span 20 be 9g (with the water of 100 parts by weight
On the basis of, the dosage of assistant for emulsifying agent is 3 parts by weight)；
And on the basis of total dosage of the monomer A and the monomer B, the dosage of the persulfate is 0.1 weight
% is measured, the dosage of the sulphite is 0.05 weight %；On the basis of total dosage of monomer C, the oil-soluble initiator
Dosage is 0.1 weight %；
Remaining is in the same manner as in Example 1, obtains water base oil-soluble polymers.
Use salinity that water shutoff material is configured to the water that mass concentration is 0.1% for the simulation salt water of 150,000mg/L
Solution, as DSJ6.
Test result: under conditions of high temperature (95 DEG C) and (salinity 150,000mg/L) with high salt, the water blockoff of the DSJ6
Rate is 99.6%, oil plugging rate 7.2%, and resistance to erosion multiple is greater than 80PV, and specifically, resistance to erosion multiple is 80-90PV.
Illustrate that the water shutoff material that the present embodiment is prepared has excellent selective shut-off rate and resistance to erosion to oil/water
Property, it is especially remained under high temperature and high salt conditions with preferable oil/water selective shut-off rate.
Embodiment 7
The present embodiment indicates that the polymer with selective water plugging function of method preparation provided by the invention.
Have the method for polymer of selective water plugging function identical using with the preparation of implementation 1, except that: this implementation
The usage amount of monomer in example is different, specifically:
The dosage of acrylamide is 11.4g (on the basis of the water of 100 parts by weight, the dosage of monomer A is 3.8 parts by weight),
The dosage of fumaric acid is 6g (on the basis of the water of 100 parts by weight, the dosage of monomer B is 3 parts by weight), and the dosage of styrene is
9.9g (on the basis of the water of 100 parts by weight, the dosage of monomer C is 3.3 parts by weight), the dosage of primary emulsion SDBS is 8.4g
(on the basis of the water of 100 parts by weight, the dosage of primary emulsion is 2.8 parts by weight) and the dosage of assistant for emulsifying agent Span 20 are 2.1g
(on the basis of the water of 100 parts by weight, the dosage of assistant for emulsifying agent is 0.7 parts by weight).
And on the basis of total dosage of the monomer A and the monomer B, the dosage of the persulfate is 0.05 weight
% is measured, the dosage of the sulphite is 0.03 weight %；On the basis of total dosage of monomer C, the oil-soluble initiator
Dosage is 0.02 weight %；
Remaining is in the same manner as in Example 1, obtains water base oil-soluble polymers.
Use salinity that water shutoff material is configured to the water that mass concentration is 0.1% for the simulation salt water of 150,000mg/L
Solution, as DSJ7.
Test result: under conditions of high temperature (95 DEG C) and (salinity 150,000mg/L) with high salt, the water blockoff of the DSJ7
Rate is 99.1%, oil plugging rate 9.5%, and resistance to erosion multiple is greater than 80PV, and specifically, resistance to erosion multiple is 85-95PV.
Illustrate that the water shutoff material that the present embodiment is prepared has excellent selective shut-off rate and resistance to erosion to oil/water
Property, it is especially remained under high temperature and high salt conditions with preferable oil/water selective shut-off rate.
Embodiment 8
The present embodiment indicates that the polymer with selective water plugging function of method preparation provided by the invention.
Have the method for polymer of selective water plugging function identical using with the preparation of implementation 1, except that: this implementation
The usage amount of monomer in example is different, specifically:
The dosage of acrylamide is 12.6g (on the basis of the water of 100 parts by weight, the dosage of monomer A is 4.2 parts by weight),
The dosage of fumaric acid is 12g (on the basis of the water of 100 parts by weight, the dosage of monomer B is 4 parts by weight), and the dosage of styrene is
11.4g (on the basis of the water of 100 parts by weight, the dosage of monomer C is 3.8 parts by weight), the dosage of primary emulsion SDBS is 9.4g
(on the basis of the water of 100 parts by weight, the dosage of primary emulsion is 3.2 parts by weight) and the dosage of assistant for emulsifying agent Span 20 are 2.4g
(on the basis of the water of 100 parts by weight, the dosage of assistant for emulsifying agent is 0.8 parts by weight)；
And on the basis of total dosage of the monomer A and the monomer B, the dosage of the persulfate is 0.08 weight
% is measured, the dosage of the sulphite is 0.04 weight %；On the basis of total dosage of monomer C, the oil-soluble initiator
Dosage is 0.04 weight %；
Remaining is in the same manner as in Example 1, obtains water base oil-soluble polymers.
Use salinity that water shutoff material is configured to the water that mass concentration is 0.1% for the simulation salt water of 150,000mg/L
Solution, as DSJ8.
Test result: under conditions of high temperature (95 DEG C) and (salinity 150,000mg/L) with high salt, the water blockoff of the DSJ8
Rate is 98.2%, oil plugging rate 18.1%, and resistance to erosion multiple is greater than 80PV, and specifically, resistance to erosion multiple is 85-95PV.
Illustrate that the water shutoff material that the present embodiment is prepared has excellent selective shut-off rate and resistance to erosion to oil/water
Property, it is especially remained under high temperature and high salt conditions with preferable oil/water selective shut-off rate.
Embodiment 9
The present embodiment indicates that the polymer with selective water plugging function of method preparation provided by the invention.
Have the method for polymer of selective water plugging function identical using with the preparation of implementation 1, except that: this implementation
Monomer C in example is styrene and 2-Propenoic acid, 2-methyl-, octyl ester, and the dosage of the styrene and the 2-Propenoic acid, 2-methyl-, octyl ester
Weight ratio is 1:1.
Remaining is in the same manner as in Example 1, obtains water base oil-soluble polymers.
Use salinity that water shutoff material is configured to the water that mass concentration is 0.1% for the simulation salt water of 150,000mg/L
Solution, as DSJ9.
Test result: under conditions of high temperature (95 DEG C) and (salinity 150,000mg/L) with high salt, the water blockoff of the DSJ9
Rate is 95.2%, oil plugging rate 18.5%, and resistance to erosion multiple is greater than 80PV, and specifically, resistance to erosion multiple is 85-95PV.
Illustrate that the water shutoff material that the present embodiment is prepared has excellent selective shut-off rate and resistance to erosion to oil/water
Property, it is especially remained under high temperature and high salt conditions with preferable oil/water selective shut-off rate.
Comparative example 1
Have the method for polymer of selective water plugging function identical using with the preparation of implementation 1, except that: this implementation
The usage amount of monomer in example is different, specifically, the dosage of acrylamide be 18g (on the basis of the water of 100 parts by weight, monomer A
Dosage be 6 parts by weight), the dosage of fumaric acid is that (on the basis of the water of 100 parts by weight, the dosage of monomer B is 6 weight to 18g
Part), the dosage of styrene is 33g (on the basis of the water of 100 parts by weight, the dosage of monomer C is 11 parts by weight), primary emulsion
The dosage of SDBS is 15g (on the basis of the water of 100 parts by weight, the dosage of primary emulsion is 5 parts by weight) and assistant for emulsifying agent Span
20 dosage is 15g (on the basis of the water of 100 parts by weight, the dosage of assistant for emulsifying agent is 5 parts by weight).
Remaining is in the same manner as in Example 1, obtains water base oil-soluble polymers.
Use salinity that water shutoff material is configured to the water that mass concentration is 0.1% for the simulation salt water of 150,000mg/L
Solution, as D1.
Test result: under conditions of high temperature (95 DEG C) and (salinity 150,000mg/L) with high salt, water shutoff material D1
Water plugging rate be 75.3%, oil plugging rate 25.3%, resistance to erosion multiple be 0PV.
Illustrate that the water shutoff material that this comparative example is prepared does not have excellent selective shut-off rate and resistance to erosion to oil/water
Property, do not have preferable oil/water selective shut-off rate especially under high temperature and high salt conditions.
Comparative example 2
Have the method for polymer of selective water plugging function identical using with the preparation of implementation 1, except that: this implementation
The usage amount of monomer in example is different, specifically, the dosage of acrylamide be 0.3g (on the basis of the water of 100 parts by weight, monomer
The dosage of A is 0.1 parts by weight), the dosage of fumaric acid is that (on the basis of the water of 100 parts by weight, the dosage of monomer B is 6 weights to 18g
Measure part), the dosage of styrene is 0.3g (on the basis of the water of 100 parts by weight, the dosage of monomer C is 0.1 parts by weight), main emulsification
The dosage of agent SDBS is 0.9g (on the basis of the water of 100 parts by weight, the dosage of primary emulsion is 0.3 parts by weight) and assistant for emulsifying agent
The dosage of Span 20 is 18g (on the basis of the water of 100 parts by weight, the dosage of assistant for emulsifying agent is 6 parts by weight).
Remaining is in the same manner as in Example 1, obtains water base oil-soluble polymers.
Use salinity that water shutoff material is configured to the water that mass concentration is 0.1% for the simulation salt water of 150,000mg/L
Solution, as D2.
Test result: under conditions of high temperature (95 DEG C) and (salinity 150,000mg/L) with high salt, water shutoff material D2
Water plugging rate be 62.3%, oil plugging rate 120.5%, resistance to erosion multiple be 0PV.
Comparative example 3
Have the method for polymer of selective water plugging function identical using with the preparation of implementation 1, except that: this implementation
Monomer C is added without in example.
Test result: under conditions of high temperature (95 DEG C) and (salinity 150,000mg/L) with high salt, water shutoff material D3
Water plugging rate be 38.5%, oil plugging rate 28.6%, resistance to erosion multiple be 0PV.
Comparative example 4
Have the method for polymer of selective water plugging function identical using with the preparation of implementation 1, except that: this implementation
Monomer B is added without in example.
Test result: under conditions of high temperature (95 DEG C) and (salinity 150,000mg/L) with high salt, water shutoff material D4
Water plugging rate be 48.7%, oil plugging rate 28.4%, resistance to erosion multiple be 0PV.
Illustrate that the water shutoff material that this comparative example is prepared does not have excellent selective shut-off rate and resistance to erosion to oil/water
Property, do not have preferable oil/water selective shut-off rate especially under high temperature and high salt conditions.
Through the foregoing embodiment with comparative example it is found that the present invention by being added water-soluble monomer, oil-soluble in aqueous solution
Monomer and emulsifier form the emulsion system of stable oil-in-water form after stirring, initiator is added, by the way of polymerization,
Caused and polymerize at 40-60 DEG C, is finally synthesizing a kind of corpuscular water shutoff material of water base oil-soluble polymers；And it is water-soluble
The dosage of property monomer, oil-soluble monomer and emulsifier meets within above-mentioned limited range, can complete the present invention, and have
Excellent effect.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Claims (11)
1. a kind of polymer with selective water plugging function, which is characterized in that the polymer is in initiator and as solvent
Water in the presence of, so that lotion containing monomer A, monomer B, monomer C and emulsifier is carried out polymerization reaction and is made, wherein institute
Stating monomer A is acrylamide；The monomer B is fumaric acid；The monomer C is oil-soluble monomer, and the oil-soluble monomer is
Styrene and/or 2-Propenoic acid, 2-methyl-, octyl ester；The emulsifier includes primary emulsion and/or assistant for emulsifying agent.
2. polymer according to claim 1, wherein on the basis of the water of 100 parts by weight, the content of the monomer A is
0.4-5 parts by weight, the content of the monomer B are 0.1-5 parts by weight, and the content of the monomer C is 1-10 parts by weight, the main cream
The content of agent is 0.5-4.5 parts by weight, and the content of the assistant for emulsifying agent is 0-1.5 parts by weight；
Preferably, on the basis of the water of 100 parts by weight, the content of the monomer A is 3.5-4.5 parts by weight, and the monomer B's contains
Amount is 2.5-4.5 parts by weight, and the content of the monomer C is 3-4 parts by weight, and the content of the primary emulsion is 2.5-3.5 weight
Part, the content of the assistant for emulsifying agent is 0.6-0.9 parts by weight；
Preferably, the resistance to erosion multiple of the polymer is greater than 50PV.
3. polymer according to claim 1 or 2, wherein the primary emulsion is selected from dodecyl sodium sulfate, dodecane
One of base sodium sulphate and neopelex are a variety of；Preferably, the primary emulsion is selected from dodecyl sodium sulfonate
Sodium and/or neopelex；
The assistant for emulsifying agent is selected from Span 20, Span 40, Span 60, Span 80, polysorbas20, polysorbate40, polysorbate60 and Tween 80
One of or it is a variety of；Preferably, the assistant for emulsifying agent is selected from one of Span 20, Span 40 and Tween 80 or a variety of.
4. polymer according to claim 1, wherein the initiator is that water soluble starter and/or oil-soluble cause
Agent, the water soluble starter are persulfate-sulphite oxidation-reduction trigger system, and the oil-soluble initiator is
Azodiisobutyronitrile and/or azo-bis-iso-dimethyl；
Preferably, the initiator is the composition of water soluble starter and oil-soluble initiator；
It is further preferred that on the basis of the total content of the monomer A and the monomer B, the content of the persulfate is
0.01-0.1 weight %, the content of the sulphite are 0.005-0.05 weight %；And it is with the total content of the monomer C
Benchmark, the content of the oil-soluble initiator are 0.01-0.1 weight %.
5. a kind of preparation method of the polymer with selective water plugging function, which is characterized in that the preparation method includes following
Step:
(1) monomer A, monomer B and water are mixed, forms aqueous solution；
(2) monomer C, emulsifier are mixed with the aqueous solution, forms lotion；
(3) lotion is subjected to polymerization reaction in the presence of initiator；
Wherein, the monomer A is acrylamide；The monomer B is fumaric acid；The monomer C is oil-soluble monomer, and the oil
Soluble monomers are styrene and/or 2-Propenoic acid, 2-methyl-, octyl ester；The emulsifier includes primary emulsion and/or assistant for emulsifying agent.
6. preparation method according to claim 5, wherein on the basis of the water of 100 parts by weight, the dosage of the monomer A
For 0.4-5 parts by weight, the dosage of the monomer B is 0.1-5 parts by weight, and the dosage of the monomer C is 1-10 parts by weight, the master
The dosage of emulsifier is 0.5-4.5 parts by weight, and the dosage of the assistant for emulsifying agent is 0-1.5 parts by weight；
Preferably, on the basis of the water of 100 parts by weight, the dosage of the monomer A is 3.5-4.5 parts by weight, the use of the monomer B
Amount is 2.5-4.5 parts by weight, and the dosage of the monomer C is 3-4 parts by weight, and the dosage of the primary emulsion is 2.5-3.5 weight
Part, the dosage of the assistant for emulsifying agent is 0.6-0.9 parts by weight；
Preferably, the resistance to erosion multiple of the polymer is greater than 50PV.
7. preparation method according to claim 5, wherein the primary emulsion is selected from dodecyl sodium sulfate, dodecane
One of base sodium sulphate and neopelex are a variety of；Preferably, the primary emulsion is selected from dodecyl sodium sulfonate
Sodium and/or neopelex；
The assistant for emulsifying agent is selected from Span 20, Span 40, Span 60, Span 80, polysorbas20, polysorbate40, polysorbate60 and Tween 80
One of or it is a variety of；Preferably, the assistant for emulsifying agent is selected from one of Span 20, Span 40 and Tween 80 or a variety of.
8. preparation method according to claim 5, wherein the initiator is that water soluble starter and/or oil-soluble draw
Agent is sent out, the water soluble starter is persulfate-sulphite oxidation-reduction trigger system, the oil-soluble initiator
For azodiisobutyronitrile and/or azo-bis-iso-dimethyl；
Preferably, the initiator is the composition of water soluble starter and oil-soluble initiator；
It is further preferred that on the basis of total dosage of the monomer A and the monomer B, the dosage of the persulfate is
0.01-0.1 weight %, the dosage of the sulphite are 0.005-0.05 weight %；And
On the basis of total dosage of the monomer C, the dosage of the oil-soluble initiator is 0.01-0.1 weight %.
9. preparation method according to claim 5, wherein in step (1), the pH value of the aqueous solution is 6-10；With
And in step (3), the condition of the polymerization reaction includes: that temperature is 40-60 DEG C, and preferably 45-55 DEG C, the time is that 6-8 is small
When, preferably 7-8 hours.
10. the polymer with selective water plugging function that method described in any one of claim 5-9 is prepared.
11. alternatively property is stifled for the polymer described in any one of claim 1-4 and 10 with selective water plugging function
The application of aqua.
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| CN1334853A (en) * | 1998-12-23 | 2002-02-06 | 菲利浦石油公司 | Cement composition and process therewith |
| CN1965005A (en) * | 2004-06-07 | 2007-05-16 | 巴斯福股份公司 | Fine-particled amphoteric aqueous polymer dispersion method for production and use thereof |
| WO2013053840A2 (en) * | 2011-10-14 | 2013-04-18 | Basf Se | Finely divided, starch-containing polymer dispersions, processes for their preparation and use as sizes in papermaking |
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