CN114437685A - Degradable dynamic polymer plugging material and preparation method and application thereof - Google Patents

Degradable dynamic polymer plugging material and preparation method and application thereof Download PDF

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CN114437685A
CN114437685A CN202210076076.7A CN202210076076A CN114437685A CN 114437685 A CN114437685 A CN 114437685A CN 202210076076 A CN202210076076 A CN 202210076076A CN 114437685 A CN114437685 A CN 114437685A
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dynamic
polyurea
degradable
particles
plugging
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CN114437685B (en
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王占华
夏和生
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Sichuan University
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
    • C09K8/504—Compositions based on water or polar solvents
    • C09K8/506—Compositions based on water or polar solvents containing organic compounds
    • C09K8/508—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
    • C09K8/5086—Compositions based on water or polar solvents containing organic compounds macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/50—Polyethers having heteroatoms other than oxygen
    • C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
    • C08G18/5024—Polyethers having heteroatoms other than oxygen having nitrogen containing primary and/or secondary amino groups
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
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    • C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
    • C09K2208/08—Fiber-containing well treatment fluids

Abstract

The invention discloses a degradable dynamic polymer plugging material, a preparation method and application thereof, wherein the material comprises the following components: flexible dynamic polyurea particles, rigid dynamic polyurea particles, dynamic polyurea fibers, a tackifier, a weighting agent, and water. According to the degradable dynamic polymer plugging material, the flexible polyurea particles are used as a deformation material, the rigid particles are used as a supporting material, the polyurea fibers are used as a winding material, guanidino urea bonds generated by reaction of guanidino and isocyanate can be subjected to dissociation-association reaction, the dynamic polyurea particles and the fiber materials can be subjected to self-adhesion in a bottom hole crack under high temperature and high pressure, no gap exists between the particles and the fibers, bottom hole plugging in the oil and gas field exploitation process is realized, the plugging effect is good, and plugging of micro-size cracks and large-size cracks can be realized.

Description

Degradable dynamic polymer plugging material and preparation method and application thereof
Technical Field
The invention relates to a plugging material, in particular to a degradable dynamic polymer plugging material and a preparation method and application thereof.
Background
In the process of drilling, with the continuous advance of oil and gas exploration and development engineering, the stratum conditions of drilling and development become more complex, the risk of the encountered downhole accident is increased, and the lost circulation, which is a common and complex downhole accident, usually results in the consumption of a large amount of operation time, the loss of huge materials and drilling fluid, and possibly causes a series of accidents such as blowout, well collapse and the like. The complex well leakage is a troublesome problem, the plugging material for drilling is an essential important component in the leak-proof and plugging of the drilling, and the success rate of the leak-proof and plugging of the drilling almost directly depends on the quality and the application degree of the performance of the plugging material. Therefore, the selection and improvement of the plugging material have very important significance for the smooth operation of oil and gas exploration and development engineering.
At present, the non-selective plugging materials with wider application comprise materials such as epoxy resin, phenolic resin and the like, and as is known, the epoxy resin is widely applied to sealing materials, but is difficult to biodegrade, and is difficult to unblock after a closed space is formed underground and shale oil is extracted, so that underground water flows unsmoothly, and the circulation and balance of the underground water are influenced. Therefore, on the basis of ensuring the strength requirement of the material, a degradation agent needs to be additionally added to degrade or dissolve the material within a certain time, irregular holes are formed in the epoxy resin plugging material, the flowing balance and the permeation of underground water are restored, and the purpose of restoring ecological balance is achieved.
Currently, temporary plugging agents for plugging fractured reservoirs face the following difficulties: (1) the leakage channel is wide, the leakage rate is high, the plugging material easily enters the deep part of the stratum along with the carrier fluid and is difficult to deposit at a crack inlet to form a filter cake barrier layer, so that the plugging effect of solid-phase particles in the drilling fluid and conventional calcium carbonate and oil-soluble resin reservoir protecting agents on the reservoir cracks cannot meet the reservoir protection requirement; (2) a filter cake layer formed by the solid phase large-size particle plugging material is not compact enough, the structure is extremely unstable, and effective plugging cannot be achieved; (3) the cracks can dynamically change under the action of pressure difference, and due to the poor adaptability of the plugging material, the formed filter cake plugging layer has the risk of easy failure, and the requirement of reservoir protection cannot be met.
In order to solve the problems, the intelligent polymer plugging material is widely concerned by people. Common intelligent polymeric lost circulation materials include: shape memory polymer plugging agent, intelligent gel plugging agent, stimulus-response polymer film plugging material and the like. The shape memory plugging material has the advantages of strong bearing capacity, self-adaptive bridging plugging, adjustable activation temperature and the like, is suitable for fractured leakage stratum, but is generally not degradable or incompletely degradable; the intelligent gel plugging material has the advantages of strong self-adaptive capacity, good compatibility, strong scouring resistance, good degradability and the like, and is suitable for plugging fractured and caverned leakage stratum, but the pressure bearing capacity and the temperature resistance capacity are to be improved; the intelligent membrane plugging material has the advantages of good plugging performance while drilling, capability of cooperatively solving the coexistence technical problems of drilling sticking, collapse, oil layer damage and the like, is suitable for high-permeability and microcracked leakage stratum, but the thickness and the strength of the membrane material need to be improved and basically cannot be degraded.
Therefore, a plugging material which has a certain mechanical property and can be degraded needs to be developed to meet the requirements of the plugging material for drilling.
Disclosure of Invention
The invention aims to provide a degradable dynamic polymer plugging material, a preparation method and application thereof, which solve the problems that the existing plugging material is difficult to degrade and the mechanical property is difficult to meet the requirement, and the plugging agent can generate self-adhesion in a bottom hole crack under high temperature and high pressure and can be degraded at a high temperature of a crust crack.
In order to achieve the above object, the present invention provides a degradable dynamic polymer plugging material, comprising: flexible dynamic polyurea particles, rigid dynamic polyurea particles, dynamic polyurea fibers, a tackifier, a weighting agent, and water.
The flexible dynamic polyurea particles are obtained by the following method: the method comprises the steps of stirring and reacting a guanidino compound with a chemical structural formula shown as a formula (1), an isocyanate compound A with a chemical structural formula shown as a formula (2), an isocyanate compound B with a chemical structural formula shown as a formula (3) and an amino-terminated macromolecular chain extender with a chemical structural formula shown as a formula (4) in an organic solvent at room temperature to obtain the flexible dynamic polyurea.
The rigid dynamic polyurea particles are obtained by the following method: and (2) stirring the guanidino compound, the isocyanate compound A and the amino-terminated macromolecular chain extender in an organic solvent for reaction at room temperature to obtain the rigid dynamic polyurea.
The dynamic polyurea fiber is obtained by the following method: stirring the guanidino compound, the isocyanate compound A and the amino-terminated macromolecular chain extender in an organic solvent for reaction at room temperature; and after the reaction is finished, spinning the reaction liquid into a liquid nitrogen frozen normal hexane solution by using an injector, and carrying out freeze drying and crushing to obtain the dynamic polyurea fiber.
Figure BDA0003484090650000031
In the formula (1), R3And R4Each independently selected from H, aromatic ring, or R3And R4To form a five-membered or six-membered heterocyclic ring; r5And R6Each independently selected from H or C1～C5Is a saturated alkane.
Figure BDA0003484090650000032
In the formula (2), R2Is selected from
Figure BDA0003484090650000033
Figure BDA0003484090650000034
Wherein n is3And n4Each independently selected from integers of 0 to 3, n5～n9Each independently selected from 0 or 1, n11An integer selected from 0 to 6, n10Is selected from 0 or 1, and n11And n10Cannot be 0, R simultaneously19～R28Each independently selected from C1～C3Is a saturated alkane.
Figure BDA0003484090650000035
In the formula (3), R7～R9Each independently selected from C1～C6A saturated alkane of,
Figure BDA0003484090650000036
R29～R30Each independently selected from C1～C3Saturated alkanes of (1), n12Is selected from 0 or 1.
Figure BDA0003484090650000041
In the formula (4), R1Is selected from
Figure BDA0003484090650000042
n1And n2The molecular weight of the amino-terminated macromolecular chain extender is determined by the molecular weight of the amino-terminated macromolecular chain extender with the chemical structural formula shown in the formula (4), and the molecular weight of the amino-terminated macromolecular chain extender is 300-4000; wherein R is10～R17Each independently selected from C1～C3Saturated alkanes of (2), R18Is selected from H or C1～C3Is a saturated alkane.
Preferably, the material comprises the following components in parts by weight: 20-40 parts of flexible dynamic polyurea particles, 5-20 parts of rigid dynamic polyurea particles, 3-10 parts of dynamic polyurea fibers, 0.3-2 parts of a tackifier, 20-50 parts of a weighting agent and 100 parts of water; the particle size of the flexible dynamic polyurea particles is 100-300 mu m, the particle size of the rigid dynamic polyurea particles is 100-200 mu m, and the diameter of the dynamic polyurea fibers is 0.3-0.5 mm. The flexible dynamic polyurea particles are too many, the material adaptability is strong, but the mechanical property is relatively poor, the rigid dynamic polyurea particles are too many, the mechanical property of the material is good, but the adaptability is poor, and the mechanical property and the adaptability controlled within the range are good.
Preferably, said R is3And R4Each independently selected from H, a substituted or unsubstituted benzene ring, or R3And R4Constituting a morpholine ring.
Preferably, the amino-terminated macromolecular chain extender is selected from any one or more than two of amino-terminated polypropylene glycol, polyethylene glycol, polytetrahydrofuran, polycaprolactone and polydimethylsiloxane; the guanidine-based compound is any one or more than two of moroxydine, phenyl biguanide, buformin, metformin, biguanide, 1-o-tolylbiguanide, 1- (4-chlorphenyl) biguanide, 1- (4-fluorophenyl) biguanide and 1- (3-fluorophenyl) biguanide.
Preferably, the isocyanate compound a is selected from one or more of naphthalene diisocyanate, toluene diisocyanate, m-phenylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, p-phenylene diisocyanate, dicyclohexylmethane diisocyanate, and dimethylbiphenyl diisocyanate; the isocyanate compound B is selected from one or more of diphenylmethane diisocyanate tripolymer, hexamethylene diisocyanate tripolymer and toluene diisocyanate tripolymer.
Preferably, the viscosity-increasing agent is selected from polyacrylamide or/and xanthan gum; the weighting agent is selected from calcium bromide. Wherein, the polyacrylamide or/and xanthan gum has large molecular weight, and the addition of a small amount of the polyacrylamide or/and xanthan gum can achieve an obvious tackifying effect; the calcium bromide has high solubility in water and good weighting effect.
The invention also aims to provide application of the degradable dynamic polymer plugging material in fracture plugging of oil and gas field exploitation.
It is another object of the present invention to provide flexible dynamic polyurea particles that are the flexible dynamic polyurea particles described in the degradable dynamic polymer lost circulation material.
It is another object of the present invention to provide rigid dynamic polyurea particles that are the rigid dynamic polyurea particles described in the degradable dynamic polymer lost circulation material.
It is another object of the present invention to provide a dynamic polyurea fiber that is the dynamic polyurea fiber described in the degradable dynamic polymer lost circulation material.
The degradable dynamic polymer plugging material, the preparation method and the application thereof solve the problems that the existing plugging material is difficult to degrade and the mechanical property is difficult to meet the requirement, and have the following advantages:
(1) the degradable dynamic polymer plugging material can be used as a plugging agent in the oil field exploitation process, can realize crack plugging, and has the plugging efficiency of more than 95 percent, wherein the flexibility of the polyurea material can be adjusted by adjusting the molecular weight of the macromolecular chain extender, the comprehensive breaking tensile strength of the three polyurea materials can reach 5 MPa-100 MPa, the breaking elongation can reach 3 percent-2000 percent, and the modulus can reach 20 MPa-3 GPa;
(2) according to the degradable dynamic polymer plugging material, the flexible polyurea particles are used as a deformation material, the rigid particles are used as a supporting material, the polyurea fibers are used as a winding material, guanidino urea bonds generated by reaction of guanidino and isocyanate can be subjected to dissociation-association reaction, the dynamic polyurea particles and the fiber materials can be subjected to self-adhesion in a bottom hole crack under high temperature and high pressure, no gap exists between the particles and the fibers, bottom hole plugging in the oil-gas field exploitation process is realized, the plugging effect is good, and plugging of micro-size cracks and large-size cracks can be realized;
(3) according to the degradable dynamic polymer plugging material, due to the existence of the flexible polyurea particles, the dynamic polyurea plugging material can deform under the change of external stress, when the size of a bottom hole crack changes, intelligent plugging can be realized, and the plugging material can plug the crack with the equivalent diameter of 50 micrometers-5 cm;
(4) in the degradable dynamic polymer plugging material, urea bonds generated by the reaction of amino and isocyanate can generate hydrolysis reaction under high temperature and high pressure, but the reaction rate can be controlled, the period is short in the initial stage of oil and gas field exploitation, the urea bond hydrolysis does not influence the plugging effect of the material, after the oil and gas exploitation is finished, the dynamic polyurea plugging material is slowly hydrolyzed at the high temperature of a crust crack, and as the deformation material, the supporting material and the winding material in the plugging agent are all formed by polyurea materials, the plugging material can be completely degraded within a certain time range, the flow balance and the permeation of underground water are recovered, and the purpose of recovering ecological balance is achieved.
Drawings
FIG. 1 is an infrared spectrum of a degradable dynamic polymer plugging material prepared in example 6 of the present invention.
FIG. 2 is an infrared spectrum of polyurea particles prepared according to example 9 of the present invention.
FIG. 3 is an infrared spectrum of a guanidinium urea bond of experimental example 1 of the present invention at different temperatures.
FIG. 4 is a tensile curve of flexible dynamic polyurea particles prepared according to example 1 of the present invention.
FIG. 5 is a tensile curve of rigid dynamic polyurea particles prepared according to example 2 of the present invention.
Fig. 6 is a stress-strain curve of a composite material obtained by hot-pressing the degradable dynamic polymer plugging material of examples 1-3 of the present invention.
FIG. 7 is a hot-press fusion of the flexible dynamic polyurea particles of example 1, the rigid dynamic polyurea particles of example 2, and the polyurea fibers of example 3 of the present invention.
FIG. 8 is a graph of the hydrolysis rate of the materials prepared in examples 1-3 of the present invention after mixing at different temperatures.
FIG. 9 is a graph of the hydrolysis rate of the materials prepared in examples 5-7 of the present invention after mixing at different temperatures.
FIG. 10 shows the hydrolysis rates of composites prepared by hot pressing the degradable dynamic polymer lost circulation materials of examples 1-3 of the present invention at different temperatures.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The preparation method of the flexible dynamic polyurea particles comprises the following steps:
5g of 1-o-tolylbiguanide, 5g of amino-terminated polypropylene glycol (molecular weight: 4000), 5.4g of isophorone diisocyanate and 0.9g of hexamethylene diisocyanate trimer were reacted in DMF (N, N-dimethylformamide) with stirring at room temperature for 30 min.
After the reaction is finished, introducing the mixture into a mold, drying, freezing, crushing and sieving to obtain flexible dynamic polyurea particles with the diameter of 100 microns.
The structure of the amino-terminated polypropylene glycol is as follows:
Figure BDA0003484090650000071
the structure of 1-o-tolylbiguanide is as follows:
Figure BDA0003484090650000072
the structure of isophorone diisocyanate is as follows:
Figure BDA0003484090650000073
the structure of hexamethylene diisocyanate trimer is as follows:
Figure BDA0003484090650000074
example 2
The preparation method of the rigid dynamic polyurea particles comprises the following steps:
5g of 1-o-tolylbiguanide, 5g of amino-terminated polyethylene glycol (molecular weight 300) and 10.7g of 4, 4' -diphenylmethane diisocyanate were reacted in DMF with stirring for 30 min.
After the reaction is finished, introducing the mixture into a mold, drying, freezing, crushing and sieving to obtain rigid dynamic polyurea particles with the diameter of 100 microns.
The structure of the amino-terminated polyethylene glycol is as follows:
Figure BDA0003484090650000075
the structure of 1-o-tolylbiguanide is as follows:
Figure BDA0003484090650000076
the structure of 4, 4' -diphenylmethane diisocyanate is as follows:
Figure BDA0003484090650000081
example 3
A preparation method of the dynamic polyurea fiber comprises the following steps:
Figure BDA0003484090650000082
5g of moroxydine, 5g of amino-terminated polytetrahydrofuran (molecular weight 2000) and 6.9g of isophorone diisocyanate are reacted in dioxane with stirring for 6 h.
After the reaction is finished, spinning the solution into a liquid nitrogen frozen normal hexane solution by using an injector, and freeze-drying and crushing to obtain the dynamic polyurea fiber with the diameter of 0.5 mm.
The structure of the amino-terminated polytetrahydrofuran is as follows:
Figure BDA0003484090650000083
the structure of moroxydine is as follows:
Figure BDA0003484090650000084
the structure of isophorone diisocyanate is as follows:
Figure BDA0003484090650000085
example 4
A degradable dynamic polymer plugging material is prepared by the following steps:
0.5g of polyacrylamide (with a molecular weight of 50 ten thousand as a tackifier), 50g of calcium bromide (as a weighting agent), 25g of the flexible dynamic polyurea particles prepared in example 1, 10g of the rigid dynamic polyurea particles prepared in example 2, and 5g of the dynamic polyurea fibers prepared in example 3 were dispersed in 100g of water, and stirred until the polyacrylamide and the calcium bromide were completely dissolved, to obtain a degradable dynamic polymer plugging material.
Example 5
The preparation method of the flexible dynamic polyurea particles comprises the following steps:
4.1g of buformin, 5g of amino-terminated polydimethylsiloxane (molecular weight 4000), 5.9g of tetramethylm-xylylene diisocyanate and 0.9g of hexamethylene diisocyanate trimer were reacted in tetrahydrofuran with stirring for 30 min.
After the reaction is finished, introducing the mixture into a mold, drying, freezing, crushing and sieving to obtain the flexible dynamic polyurea particles with the diameter of 300 mu m.
The structure of the amino-terminated polydimethylsiloxane is as follows:
Figure BDA0003484090650000091
the structure of buformin is as follows:
Figure BDA0003484090650000092
the structure of tetramethyl m-xylylene diisocyanate is as follows:
Figure BDA0003484090650000093
the structure of hexamethylene diisocyanate trimer is as follows:
Figure BDA0003484090650000094
example 6
The preparation method of the rigid dynamic polyurea particles comprises the following steps:
4.1g of buformin, 5g of amino-terminated polydimethylsiloxane (molecular weight 300) and 10.5g of tetramethylm-xylylene diisocyanate were reacted in tetrahydrofuran with stirring for 30 min.
After the reaction is finished, introducing the mixture into a mold, drying, freezing, crushing and sieving to obtain rigid dynamic polyurea particles with the diameter of 200 mu m.
The structure of the amino-terminated polydimethylsiloxane is as follows:
Figure BDA0003484090650000095
the structure of buformin is as follows:
Figure BDA0003484090650000096
the structure of tetramethyl m-xylylene diisocyanate is as follows:
Figure BDA0003484090650000101
as shown in FIG. 1, the infrared spectrum of the degradable dynamic polymer plugging material prepared in example 6 of the present invention is 1500-1700 cm-1Two characteristic peaks in the wave number range prove that urea bonds exist in the material, and the thickness is 700-1200 cm-1The presence of siloxane groups in the material is evidenced by three characteristic peaks in the wavenumber range, which can demonstrate the successful preparation of the polyurea material of example 6.
Example 7
A preparation method of the dynamic polyurea fiber comprises the following steps:
4.1g of buformin, 5g of amino-terminated polydimethylsiloxane (molecular weight 2000) and 5g of tetramethylm-xylylene diisocyanate were reacted in tetrahydrofuran with stirring for 30 min.
After the reaction is finished, spinning the solution into a liquid nitrogen frozen normal hexane solution by using an injector, and freeze-drying and crushing to obtain the dynamic polyurea fiber with the diameter of 0.3 mm.
The structure of the amino-terminated polydimethylsiloxane is as follows:
Figure BDA0003484090650000102
the structure of buformin is as follows:
Figure BDA0003484090650000103
the structure of tetramethyl m-xylylene diisocyanate is as follows:
Figure BDA0003484090650000104
example 8
A degradable dynamic polymer plugging material is prepared by the following steps:
0.5g of polyacrylamide (having a molecular weight of 50 ten thousand as a tackifier), 50g of calcium bromide (as a weighting agent), 25g of the flexible dynamic polyurea particles prepared in example 5, 10g of the rigid dynamic polyurea particles prepared in example 6, and 5g of the dynamic polyurea fibers prepared in example 7 were dispersed in 49.5g of water, and stirred until the polyacrylamide and the calcium bromide were completely dissolved, to obtain a degradable dynamic polymer plugging material.
Example 9
The preparation method of the polyurea particles comprises the following steps:
0.5g of 1-o-tolylbiguanide and 0.5g of isophorone diisocyanate were reacted in dioxane with stirring for 3 h.
And after the reaction is finished, introducing the mixture into a mold, drying, freezing, crushing and sieving to obtain the rigid dynamic polyurea particles.
The structure of 1-o-tolylbiguanide is as follows:
Figure BDA0003484090650000111
the structure of isophorone diisocyanate is as follows:
Figure BDA0003484090650000112
as shown in FIG. 2, the infrared spectrogram of the polyurea particles prepared in example 9 of the invention is 1450-1750 cm-1Two characteristic peaks in the wavenumber range demonstrate the presence of two different urea linkages in the material, one belonging to guanidinium urea linkages and one belonging to common urea linkages, demonstrating that the polyurea material of example 9 was successfully prepared.
Experimental example 1 dynamic reversibility
0.5g of 1-o-tolylene biguanide and 0.5g of isophorone diisocyanate are stirred in dioxane for reaction for 3 hours, the solution after the reaction is dripped on a potassium bromide sheet to prepare a film, and after the dioxane is volatilized, infrared spectrums of the film material at different temperatures are measured to prove the dynamic reversibility of a guanidiniumsouride bond.
As shown in FIG. 3, which is an infrared spectrum of a guanidinium urea bond of Experimental example 1 of the present invention at various temperatures, it can be seen that at 2250cm, the temperature is increased-1The peak of the isocyanate is obviously increased, which shows that the guanidyl urea bond has dynamic reversibility and can be dissociated at high temperature to generate guanidine groups and isocyanate groups.
Experimental example 2 mechanical Properties
1. Mechanical properties of a single material
As shown in fig. 4, which is a tensile curve of the flexible dynamic polyurea particles prepared in example 1 of the present invention, it can be seen that the flexible dynamic polyurea particles prepared in example 1 have an elongation at break of 430%, a tensile strength at break of 12.8MPa, and good flexibility.
As shown in FIG. 5, which is a tensile curve of the rigid dynamic polyurea particles prepared in example 2 of the present invention, it can be seen that the tensile strength at break of the rigid dynamic polyurea particles prepared in example 2 can reach 83.3MPa, and the modulus can reach 2.3GPa, indicating that the material has good hardness and rigidity.
2. Mechanical properties of hot-pressed composite materials
The materials prepared in examples 1, 2 and 3 were mechanically stirred and mixed uniformly in equal mass ratios (0.5 g each), hot-pressed at pressures of 0MPa, 5MPa and 15MPa, respectively, with the hot-pressing temperature set at 90 ℃, the fusion behavior between particles was observed and the mechanical properties of the hot-pressed materials were measured.
The flexible dynamic polyurea particles of example 1, the rigid dynamic polyurea particles of example 2, and the polyurea fibers of example 3 can self-bond at high temperatures to form a composite material, with the degree of bonding increasing with increasing pressure.
As shown in fig. 6, which is a stress-strain curve of the composite material obtained by hot-pressing the degradable dynamic polymer plugging material of examples 1-3 of the present invention, it can be seen from the graph that the mechanical properties of the composite material are improved as the pressure of the composite material obtained by hot-pressing the material of examples 1-3 is increased.
As shown in fig. 7, the flexible dynamic polyurea particles of example 1, the rigid dynamic polyurea particles of example 2, and the polyurea fibers of example 3 were hot-pressed at 90 ℃ under a pressure of 15MPa, and the solid powder particles could travel through the film material, demonstrating that the flexible dynamic polyurea particles, the rigid dynamic polyurea particles, and the polyurea fibers could be fused.
Experimental example 3 plugging Properties
A glass funnel with the diameter of 2mm is placed in a temperature-controllable closed container, the temperature of the container is set to be 25 ℃, 50 ℃, 70 ℃ and 95 ℃, the degradable dynamic polymer plugging material prepared in example 4 is poured into the glass funnel until no liquid flows down, the weight of the residual liquid is weighed, the plugging efficiency is calculated to evaluate the plugging performance of the plugging agent at different temperatures, and the results are shown in table 1.
Table 1: example 6 plugging efficiency of the prepared plugging material at different temperatures
Figure BDA0003484090650000121
As can be seen from Table 1, after the plugging agent enters the cracks, the plugging material is fused at high temperature and high pressure at the cracks to form a block material, so that plugging is realized, the plugging efficiency is improved along with the increase of temperature within the range of 25-95 ℃, and the plugging efficiency at 95 ℃ can reach 97%.
EXAMPLE 4 hydrolytic Capacity
1. Hydrolytic capacity of mechanically mixed materials
(1) Hydrolysis Capacity of materials prepared in examples 1-3
The flexible dynamic polyurea particles of example 1, the rigid dynamic polyurea particles of example 2, and the polyurea fibers of example 3 were each taken at 5g, mixed well by mechanical stirring, placed in 100mL of water, heated to different times at 25 ℃, 50 ℃, and 80 ℃, and the mass of the solid remaining after the different times was weighed to evaluate the hydrolysis ability of the polyurea material.
As shown in fig. 8, which is the hydrolysis rate of the materials prepared in examples 1 to 3 of the present invention at different temperatures after mixing, it can be seen that the polyurea material has a faster hydrolysis rate and increases with the increase of temperature, and is hydrolyzed at 50 ℃ for 30 days to be substantially completely hydrolyzed, indicating that the plugging agent prepared from the degradable dynamic polymer plugging material of examples 1 to 3 of the present invention can be completely degraded by using it.
(2) Hydrolysis Capacity of materials prepared in examples 5-7
The flexible dynamic polyurea particles of example 5, the rigid dynamic polyurea particles of example 6 and the polyurea fibers of example 7 were mixed in a mass ratio of 1: 1: 1. 2: 1: 1. 3: 1: 1. 3: 2: 1, placing the mixture in water at 90 ℃, and weighing the mass of the residual solid at intervals to evaluate the hydrolysis capacity of the polyurea material.
As shown in fig. 9, the hydrolysis rates of the materials prepared in examples 5 to 7 of the present invention at different temperatures after mixing were shown to be excellent, the hydrolysis rate reached 90% or more after 21 days, the hydrolysis rate could be adjusted by adjusting the ratio between the polyurea particles and the fibers and the monomer molecular structure of the prepared polyurea material, and the self-adaptive adjustability was strong.
2. Hydrolytic capability of hot-pressed composite material
5g of the flexible dynamic polyurea particles prepared in example 1, 2g of the rigid dynamic polyurea particles prepared in example 2 and 1g of the dynamic polyurea fibers prepared in example 3 were mechanically stirred and mixed uniformly, hot-pressed at 20MPa and 90 ℃ for 30min, and the hot-pressed material was put in water at 25 ℃, 50 ℃ and 80 ℃, and the mass of the solid remaining after different times was weighed to evaluate the hydrolysis ability of the composite material.
As shown in fig. 10, the hydrolysis rates of the composite materials prepared by hot-pressing the degradable dynamic polymer plugging materials of examples 1 to 3 of the present invention at different temperatures are shown, and it can be seen that the polyurea material still has good hydrolysis performance after hot-press molding, the hydrolysis capacity increases with the increase of the temperature, the hydrolysis rate reaches more than 80% after 30 days of hydrolysis at 50 ℃, and the hydrolysis rate reaches 100% basically after 30 days of hydrolysis at 80 ℃, which indicates that when the material is used as a plugging agent, even if a crack has a huge pressure, the polyurea material still has good hydrolysis performance after extrusion molding in the crack, and can realize complete degradation.
While the present invention has been described in detail with reference to the preferred embodiments, it should be understood that the above description should not be taken as limiting the invention. Various modifications and alterations to this invention will become apparent to those skilled in the art upon reading the foregoing description. Accordingly, the scope of the invention should be determined from the following claims.

Claims (10)

1. A degradable dynamic polymer plugging material, comprising: flexible dynamic polyurea particles, rigid dynamic polyurea particles, dynamic polyurea fibers, a tackifier, a weighting agent and water;
the flexible dynamic polyurea particles are obtained by the following method:
the method comprises the following steps of (1) stirring and reacting a guanidino compound with a chemical structural formula shown in a formula (1), an isocyanate compound A with a chemical structural formula shown in a formula (2), an isocyanate compound B with a chemical structural formula shown in a formula (3) and an amino-terminated macromolecular chain extender with a chemical structural formula shown in a formula (4) in an organic solvent at room temperature to obtain flexible dynamic polyurea;
the rigid dynamic polyurea particles are obtained by the following method:
stirring the guanidyl compound, the isocyanate compound A and the amino-terminated macromolecular chain extender in an organic solvent for reaction at room temperature to obtain rigid dynamic polyurea;
the dynamic polyurea fiber is obtained by the following method:
stirring the guanidino compound, the isocyanate compound A and the amino-terminated macromolecular chain extender in an organic solvent for reaction at room temperature; after the reaction is finished, spinning the reaction liquid into a liquid nitrogen frozen normal hexane solution by using an injector, and carrying out freeze drying and crushing to obtain dynamic polyurea fibers;
Figure FDA0003484090640000011
in the formula (1), R3And R4Each independently selected from H, aromatic ring, or R3And R4To form a five-membered or six-membered heterocyclic ring; r5And R6Each independently selected from H or C1～C5Saturated alkanes of (a);
Figure FDA0003484090640000012
in the formula (2), R2Is selected from
Figure FDA0003484090640000013
Figure FDA0003484090640000021
Wherein the content of the first and second substances,n3and n4Each independently selected from integers of 0 to 3, n5～n9Each independently selected from 0 or 1, n11An integer selected from 0 to 6, n10Is selected from 0 or 1, and n11And n10Cannot be 0, R simultaneously19～R28Each independently selected from C1～C3Saturated alkanes of (a);
Figure FDA0003484090640000022
in the formula (3), R7～R9Each independently selected from C1～C6A saturated alkane of,
Figure FDA0003484090640000023
R29～R30Each independently selected from C1～C3Saturated alkanes of (1), n12Is selected from 0 or 1;
Figure FDA0003484090640000024
in the formula (4), R1Is selected from
Figure FDA0003484090640000025
n1And n2The molecular weight of the amino-terminated macromolecular chain extender is determined by the molecular weight of the amino-terminated macromolecular chain extender with the chemical structural formula shown in the formula (4), and the molecular weight of the amino-terminated macromolecular chain extender is 300-4000; wherein R is10～R17Each independently selected from C1～C3Saturated alkanes of (2), R18Is selected from H or C1～C3Is a saturated alkane.
2. The degradable dynamic polymer plugging material of claim 1, wherein the material comprises the following components in parts by weight: 20-40 parts of flexible dynamic polyurea particles, 5-20 parts of rigid dynamic polyurea particles, 3-10 parts of dynamic polyurea fibers, 0.3-2 parts of a tackifier, 20-50 parts of a weighting agent and 100 parts of water; the particle size of the flexible dynamic polyurea particles is 100-300 mu m, the particle size of the rigid dynamic polyurea particles is 100-200 mu m, and the diameter of the dynamic polyurea fibers is 0.3-0.5 mm.
3. The degradable dynamic polymer plugging material of claim 1, wherein R is3And R4Each independently selected from H, a substituted or unsubstituted phenyl ring, or R3And R4Constituting a morpholine ring.
4. The degradable dynamic polymer plugging material of claim 1, wherein the amino-terminated macromolecular chain extender is selected from one or more of amino-terminated polypropylene glycol, polyethylene glycol, polytetrahydrofuran, polycaprolactone and polydimethylsiloxane; the guanidine-based compound is any one or more than two of moroxydine, phenyl biguanide, buformin, metformin, biguanide, 1-o-tolylbiguanide, 1- (4-chlorphenyl) biguanide, 1- (4-fluorophenyl) biguanide and 1- (3-fluorophenyl) biguanide.
5. The degradable dynamic polymer plugging material of claim 1, wherein the isocyanate compound a is selected from one or more of naphthalene diisocyanate, toluene diisocyanate, m-phenylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, p-phenylene diisocyanate, dicyclohexylmethane diisocyanate, and dimethylbiphenyl diisocyanate; the isocyanate compound B is selected from one or more of diphenylmethane diisocyanate tripolymer, hexamethylene diisocyanate tripolymer and toluene diisocyanate tripolymer.
6. The degradable dynamic polymer plugging material of claim 1, wherein the viscosifying agent is selected from polyacrylamide or/and xanthan gum; the weighting agent is selected from calcium bromide.
7. Use of the degradable dynamic polymer plugging material of any one of claims 1-6 in plugging fractures in oil and gas field production.
8. A flexible dynamic polyurea particle characterized in that it is a flexible dynamic polyurea particle as claimed in claim 1.
9. A rigid dynamic polyurea particle characterized in that it is a rigid dynamic polyurea particle as claimed in claim 1.
10. A dynamic polyurea fiber characterized in that it is the dynamic polyurea fiber as claimed in claim 1.
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