CN111592866B - High-adhesion plugging material and preparation method thereof - Google Patents
High-adhesion plugging material and preparation method thereof Download PDFInfo
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- CN111592866B CN111592866B CN202010499789.5A CN202010499789A CN111592866B CN 111592866 B CN111592866 B CN 111592866B CN 202010499789 A CN202010499789 A CN 202010499789A CN 111592866 B CN111592866 B CN 111592866B
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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
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- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/42—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells
- C09K8/426—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells for plugging
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Abstract
The application provides a high-adhesion plugging material, uses unsaturated polyester as the main raw material, and long chain carboxylic acid modified titanate coupling agent is as coupling agent acid, can strengthen the compatibility of rock soil to unsaturated polyester in the pit, prevents to separate out on the rock soil top layer when using as the plugging agent, and the long chain oiliness group of introduction can effectively reduce the solubility of coupling agent in water, extension life. Meanwhile, the addition ratio of the curing agent and the accelerator in the plugging material is adjusted, so that the crosslinking curing time of the plugging material can be adjusted within a certain time range, the plugging material is flowable liquid before crosslinking, and is a solid material with good mechanical property and high temperature resistance after crosslinking, so that the plugging material is suitable for permanently plugging underground pores and cracks. Meanwhile, the application also provides a preparation method of the high-adhesion plugging material, and the method is simple, convenient and easy to implement, good in effect and high in application value.
Description
Technical Field
The application relates to the technical field of oilfield chemical products, in particular to a high-adhesion plugging material and a preparation method thereof.
Background
The demand of the domestic and foreign society for crude oil resources is increasing day by day, the exploitation efficiency of crude oil is increased under the prior art, and the method has great significance for relieving the situation of shortage of crude oil resources in China. At present, most of domestic oil fields are exploited for decades, the water content of crude oil is increasing day by day, and partial oil wells are exploited even by a water injection fracturing technology, so that the development of cracks of underground well layers is increased. The water content of the oil field rises, the water injection utilization rate is low, and the water content of the oil layer of primary and secondary oil extraction development is higher, which is a problem to be solved urgently in the current oil field exploitation. The water-blocking profile control technology is a commonly used technology for improving the oil recovery efficiency, and the working principle is to use a specific blocking material to block a high permeable formation and adjust the water absorption profile of a water injection layer section, so that the water content of produced oil is reduced. After the chemical plugging agent is injected into a reservoir, crosslinking and curing can be carried out under the conditions of certain formation temperature, pressure and the like, so that a permeable fracture is plugged, and the subsequent displacement process is facilitated. The chemical water shutoff profile control resin system is cheap and easy to obtain, has excellent performance and adjustable and controllable cross-linking time, and is widely applied to the field of oilfield plugging. The unsaturated polyester is a high molecular compound containing unsaturated double bonds and generated by the condensation polymerization reaction of dibasic acid and dihydric alcohol, and can generate copolymerization crosslinking reaction with a vinyl monomer to form a three-dimensional crosslinking, high-strength, insoluble and infusible thermosetting polymer material, so that the unsaturated polyester can be used for plugging oil reservoir cracks.
When plugging operation is carried out, the adhesion capability of the plugging agent to underground rock soil is of great importance to the final plugging effect. The underground environment is complex and changeable, the attachment capacity of the plugging material to rock soil can be gradually reduced until the plugging material falls off, and the plugging effect is reduced or fails. If a small amount of coupling agent capable of improving the adhesion capability of the plugging material to rock soil is added, the plugging effect can be enhanced, wherein the common coupling agent is titanate coupling agent. Titanate coupling agents can be broadly classified into four categories according to their structure: the single alkoxy type, the single alkoxy pyrophosphate type, the integrated type and the coordination type have better coupling effect in a resin filler system, can form a bridging effect on the surfaces of organic resin and inorganic materials, and obviously enhances the adhesion capability. In the prior art, a high-strength multifunctional plugging agent is disclosed, wherein a structure forming agent comprises unsaturated polyester and vinyl resin, a curing agent comprises peroxide, a peroxide compound and an azo compound, and an interface adhesive, a diluent and a nano filler are added. When the mixed liquid gel is injected into a target plugging layer, the mixed liquid gel is solidified to form the high-strength multifunctional plugging agent, and the high-strength multifunctional plugging agent has stable performance, good residence property, large adhesive force, high elastic modulus and high compressive strength.
However, the compatibility between the coupling agent commonly used in the current market and the unsaturated polyester in the commonly used plugging agent is not ideal, so that the coupling performance between the resin and rock soil cannot meet the expected requirement, and the requirement of the plugging agent on high adhesion of the plugging material cannot be met.
Disclosure of Invention
The application provides a high-adhesion plugging material and a preparation method thereof, which aim to solve the problem that the requirements of a plugging agent on the coupling property and the high adhesion of the plugging material cannot be met due to the fact that the compatibility of the coupling agent and unsaturated polyester in a common plugging agent is not ideal in the prior art.
The technical scheme adopted by the application for solving the technical problems is as follows:
a high-adhesion plugging material comprises the following raw materials in parts by weight:
60-95 parts of unsaturated polyester, 5-25 parts of curing agent, 0.5-5 parts of accelerator and 0.5-5 parts of long-chain carboxylic acid modified titanate coupling agent.
Optionally, the long-chain carboxylic acid modified titanate coupling agent is prepared by the reaction of a water-soluble titanate coupling agent containing hydroxyl functional groups and a long-chain carboxylic acid, and the long-chain carboxylic acid modified titanate coupling agent has the following chemical structure:
wherein: r is 1 And R 2 Is alkyl substituted by O and N or heteroaryl substituted by O and N, the value range of N is 1 to 5, and the value range of m is 9 to 24.
Optionally, the unsaturated polyester is an unsaturated linear thermosetting resin prepared by condensation polymerization of dibasic acid or anhydride and dihydric alcohol, and comprises one or more of o-phenyl unsaturated polyester, m-phenyl unsaturated polyester, bisphenol A unsaturated polyester and vinyl resin.
Optionally, the curing agent is one or more of styrene, vinyl toluene, methyl methacrylate, cumene hydroperoxide, dicumyl peroxide, methyl ethyl ketone peroxide, benzoyl peroxide, tert-butyl perbenzoate, dibenzoyl peroxide, or tert-butyl perbenzoate.
Optionally, the promoter is one or more of tertiary amine N, N '-dimethylaniline, N' -diethylaniline, metal salt cobalt octoate, cobalt naphthenate and mercaptan dodecyl mercaptan.
A high-adhesion plugging material comprises the following raw materials in parts by weight:
70 parts of unsaturated polyester, 25 parts of methyl ethyl ketone peroxide, 4 parts of N, N' -dimethylaniline and 1 part of long-chain carboxylic acid modified titanate coupling agent.
A high-adhesion plugging material comprises the following raw materials in parts by weight:
70 parts of unsaturated polyester, 25 parts of styrene, 4 parts of cobalt naphthenate and 1 part of long-chain carboxylic acid modified titanate coupling agent.
A high-adhesion plugging material comprises the following raw materials in parts by weight:
70 parts of unsaturated polyester, 25 parts of styrene, 8 parts of cobalt naphthenate and 1 part of long-chain carboxylic acid modified titanate coupling agent.
A high-adhesion plugging material comprises the following raw materials in parts by weight:
70 parts of unsaturated polyester, 20 parts of methyl methacrylate, 5 parts of N, N' -dimethylaniline and 2 parts of long-chain carboxylic acid modified titanate coupling agent.
A method for preparing a highly adherent plugging material, the method comprising the steps of:
mixing unsaturated polyester and long-chain carboxylic acid modified titanate coupling agent, and uniformly stirring to obtain a mixture;
adding a curing agent into the uniformly stirred mixture, and uniformly stirring;
adding an accelerant into the mixture after the curing agent is added, and uniformly stirring to obtain a crude material;
and sealing the coarse material, and placing the sealed coarse material in an oven, setting the temperature of the oven to be 40-150 ℃, and reacting for 2-20h to obtain the high-adhesion plugging material.
The technical scheme provided by the application comprises the following beneficial technical effects:
the high-adhesion plugging material provided by the application takes unsaturated polyester as a main raw material, and takes a long-chain carboxylic acid modified titanate coupling agent as a coupling agent acid, so that the compatibility of underground rock and soil to the unsaturated polyester can be enhanced, the situation that the coupling agent is separated out on the surface layer of the rock and soil when the plugging agent is used is prevented, and the introduced long-chain oily group can effectively reduce the solubility of the coupling agent in water and prolong the service life. Meanwhile, the addition ratio of the curing agent and the accelerator in the plugging material is adjusted, so that the crosslinking curing time of the plugging material can be adjusted within a certain time range, the plugging material is flowable liquid before crosslinking, and is a solid material with good mechanical property and high temperature resistance after crosslinking, so that the plugging material is suitable for permanently plugging underground pores and cracks. Meanwhile, the application also provides a preparation method of the high-adhesion plugging material, and the method is simple, convenient and easy to implement, good in effect and high in application value. The high-adhesion plugging material and the preparation method thereof solve the problem that the requirements of the plugging agent on the coupling property and the high adhesion property of the plugging material cannot be met due to the fact that the compatibility of the coupling agent and unsaturated polyester in a common plugging agent is not ideal in the prior art.
Drawings
In order to more clearly describe the technical solution of the present application, the drawings required to be used in the embodiments will be briefly described below, and it is obvious for those skilled in the art to obtain other drawings without inventive labor.
FIG. 1 is a flow chart of a method for preparing a highly adhesive plugging material according to an embodiment of the present disclosure;
FIG. 2 is a graph of mechanical property data for examples 1-4 and comparative examples.
Detailed Description
In order to make those skilled in the art better understand the technical solutions in the present application, the technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application; it is to be understood that the embodiments described are only a few embodiments of the present application 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 application.
According to the technical scheme, the existing coupling agent is modified, long-carbon-chain carboxylic acid is introduced into hydroxyl of the coupling agent, the long-chain carboxylic acid modified titanate coupling agent is prepared, the compatibility of underground rock and soil to unsaturated polyester is enhanced, and the phenomenon that the long-chain carboxylic acid modified titanate coupling agent is separated out on the surface layer of the rock and soil when the long-chain carboxylic acid modified titanate coupling agent is used as a blocking agent is prevented. Meanwhile, the introduced long-chain oily group can effectively reduce the solubility of the coupling agent in water and prolong the service life.
The preparation method of the long-chain carboxylic acid modified titanate coupling agent comprises the following steps: in the modification process of the titanate coupling agent, the coupling agent is a water-soluble titanate coupling agent containing hydroxyl functional groups, and the modifier is long carbon chain carboxylic acid, such as stearic acid, and is introduced into the titanate coupling agent through esterification reaction. During the reaction, the reaction temperature is set to 80 ℃, the pH value is 5, and a proper amount of each reactant is added and stirred for 8 hours to obtain the four-arm long-chain carboxylic acid modified titanate coupling agent product.
The high-adhesion blocking agent in the technical scheme is prepared by taking the long-chain carboxylic acid modified titanate coupling agent product prepared by the method as a raw material, and simultaneously comprises the following raw materials in parts by weight:
60-95 parts of unsaturated polyester, 5-20 parts of curing agent and 0.5-5 parts of accelerator, wherein the addition amount of the long-chain carboxylic acid modified titanate coupling agent is 0.5-5 parts. Meanwhile, the addition ratio of the curing agent and the accelerator in the plugging material is adjusted, so that the crosslinking curing time of the plugging material can be adjusted within a certain time range, the plugging material is flowable liquid before crosslinking, and is a solid material with good mechanical property and high temperature resistance after crosslinking, so that the plugging material is suitable for permanently plugging underground pores and cracks.
Alternatively, the long chain carboxylic acid modified titanate coupling agent is prepared by the reaction of a water soluble titanate coupling agent containing hydroxyl functional groups and a long chain carboxylic acid, the long chain carboxylic acid modified titanate coupling agent having the following chemical structure:
wherein: r is 1 And R 2 Is alkyl substituted by O and N or heteroaryl substituted by O and N, the value range of N is 1 to 5, and the value range of m is 9 to 24.
The unsaturated polyester is unsaturated linear thermosetting resin prepared by polycondensation of dibasic acid or anhydride and dihydric alcohol, and comprises one or more of o-phenyl unsaturated polyester, m-phenyl unsaturated polyester, bisphenol A unsaturated polyester and vinyl resin.
The curing agent is one or more of styrene, vinyl toluene, methyl methacrylate, cumene hydroperoxide, dicumyl peroxide, methyl ethyl ketone peroxide, benzoyl peroxide, tert-butyl perbenzoate, dibenzoyl peroxide or tert-butyl perbenzoate.
The accelerant is one or more of tertiary amine N, N '-dimethylaniline, N' -diethylaniline, metal salt cobalt octoate, cobalt naphthenate and mercaptan dodecyl mercaptan.
Referring to fig. 1, as shown in fig. 1, the technical solution of the present application further provides a method for preparing a high adhesion plugging material, which includes the following steps:
s1: mixing unsaturated polyester and long-chain carboxylic acid modified titanate coupling agent, and uniformly stirring to obtain a mixture;
s2: adding a curing agent into the uniformly stirred mixture, and uniformly stirring;
s3: adding an accelerant into the mixture after the curing agent is added, and uniformly stirring to obtain a crude material;
s4: and sealing the coarse material, and placing the sealed coarse material in an oven, setting the temperature of the oven to be 40-150 ℃, and reacting for 2-20h to obtain the high-adhesion plugging material.
The technical solution in the present application is further explained and illustrated by several examples below.
Example 1
A high-adhesion plugging material comprises the following raw materials in parts by weight:
and is prepared by the following method:
(1) Mixing unsaturated polyester and long-chain carboxylic acid modified titanate coupling agent, and uniformly stirring to obtain a mixture;
(2) Adding methyl ethyl ketone peroxide into the uniformly stirred mixture, and uniformly stirring;
(3) Adding N, N' -dimethylaniline into the mixture added with the methyl ethyl ketone peroxide, and uniformly stirring to obtain a crude material;
(4) And sealing the coarse material, placing the sealed coarse material in a drying oven, setting the temperature of the drying oven to be 60 ℃, and reacting for 8 hours to obtain a finished product of the plugging material with high adhesion.
Example 2
A high-adhesion blocking material comprises the following raw materials in parts by weight:
and is prepared by the following method:
(1) Mixing unsaturated polyester and long-chain carboxylic acid modified titanate coupling agent, and uniformly stirring to obtain a mixture;
(2) Adding styrene into the uniformly stirred mixture, and uniformly stirring;
(3) Adding cobalt naphthenate into the mixture after adding styrene, and uniformly stirring to obtain a crude material;
(4) And sealing the coarse material, placing the sealed coarse material in a drying oven, setting the temperature of the drying oven to be 60 ℃, and reacting for 8 hours to obtain a finished product of the plugging material with high adhesion.
Example 3
A high-adhesion plugging material comprises the following raw materials in parts by weight:
and is prepared by the following method:
(1) Mixing unsaturated polyester and long-chain carboxylic acid modified titanate coupling agent, and uniformly stirring to obtain a mixture;
(2) Adding styrene into the uniformly stirred mixture, and uniformly stirring;
(3) Adding cobalt naphthenate into the mixture after adding styrene, and uniformly stirring to obtain a crude material;
(4) And sealing the coarse material, placing the sealed coarse material in a drying oven, setting the temperature of the drying oven to be 60 ℃, and reacting for 8 hours to obtain a finished product of the plugging material with high adhesion.
Example 4
A high-adhesion plugging material comprises the following raw materials in parts by weight:
and is prepared by the following method:
(1) Mixing unsaturated polyester and long-chain carboxylic acid modified titanate coupling agent, and uniformly stirring to obtain a mixture;
(2) Adding methyl methacrylate into the uniformly stirred mixture, and uniformly stirring;
(3) Adding N, N' -dimethylaniline into the mixture after the methyl methacrylate is added, and uniformly stirring to obtain a crude material;
(4) And sealing the coarse material, placing the sealed coarse material in a drying oven, setting the temperature of the drying oven to be 60 ℃, and reacting for 8 hours to obtain a finished product of the plugging material with high adhesion.
Comparative example
The plugging material without long-chain carboxylic acid modified titanate coupling agent is used as a comparative example and comprises the following raw materials in parts by weight:
70 parts by weight of unsaturated polyester;
20 parts by weight of methyl methacrylate;
5 parts by weight of N, N' -dimethylaniline;
and is prepared by the following method:
(1) Mixing unsaturated polyester and methyl methacrylate, and stirring uniformly;
(2) Adding N, N' -dimethylaniline and stirring uniformly;
(3) And sealing the materials, and placing the materials in an oven at the temperature of 60 ℃ for reaction for 8 hours to obtain the plugging material in the comparative example.
The finished plugging materials prepared in the above embodiments and comparative examples are all liquid cross-linking type plugging materials, which are flowable liquids before cross-linking and solid materials with good mechanical properties and high temperature resistance after cross-linking, and are suitable for permanent plugging of downhole pores and cracks. The following functional tests were performed on the finished products made in examples 1-4 above and comparative example:
start of cure time test: the inversion method is adopted to determine that the finished plugging material materials in the examples 1-4 and the comparative example after being uniformly mixed are filled into a 20mL sample bottle and heated and cured at the temperature of 60-80 ℃, the bottle is taken out after a period of time, and the bottle is inverted, and the curing time is the beginning time when the materials cannot flow.
And (3) testing the compression performance: the plugging material finished products of examples 1 to 4 and comparative example after uniform stirring were left to stand for a period of time (no air bubbles were available), then injected into a compression mold, subsequently cured at 60 ℃, and after 10 hours, the cured compression specimens were taken out and subjected to compression testing. The resulting compressed specimens were cylindrical specimens 12mm in diameter and about 30mm in height. The compression test adopts a Zwick/Roell Z020 universal material testing machine, the force sensing type is 20KN, the preloading force is 3N, the elastic modulus speed is 1mm/min, and the testing temperature is room temperature. At least 5 bars were tested in parallel for each sample and the results averaged. The mechanical properties of the cured plugging materials of examples 1 to 4 and comparative examples were measured by compression testing.
Adhesion performance test: the finished plugging material systems of examples 1-4 and comparative examples were used as adhesives to characterize the adhesion properties to geotechnical substances by their cementitious strength between two cores.
A rod-shaped core, 15cm long and 2.5cm in diameter, was used, with both ends of the core being selected as gluing zones. In the preparation of the bonded samples, the finished plugging material systems of examples 1-4 and comparative examples were selected to bond two cores. The cured bond area was then tested for axial tensile strength after curing in an oven at 60 ℃ for 8 h. The axial stretching is carried out by using a Zwick/Roell Z020 universal material testing machine, and the temperature for measuring the mechanical property is room temperature. Multiple parallel samples were tested simultaneously at each time, and the location of core fracture and the magnitude of the tensile force at final fracture were observed and recorded.
And (3) rheological property testing: the viscosity was measured using an RS6000 rotational rheometer manufactured by HAAKE, germany. The dynamic viscosity of the finished plugging material systems of examples 1 to 4 and comparative examples was measured using the double cylinder method at room temperature, taking into account the viscosity number of the resin system, just before curing.
And (4) analyzing results:
as shown in the following table, table 1 shows the results of the test of the initial curing time and the mechanical properties of the samples of examples 1 to 4 and comparative example. FIG. 2 is a graph of the mechanical properties of examples 1-4 and comparative examples under the test conditions. The relative error of the results of the mechanical property parallel experiment measurement is not more than 0.5 percent, and the arithmetic mean value is taken as the result. According to the results of mechanical property tests shown in table 1 and fig. 2, the compressive strength of each example sample is equivalent to that of the comparative example, which shows that the mechanical properties of the plugging material are not damaged by the addition of the long carbon chain carboxylic acid modified titanate coupling agent. The difference between examples 2 and 3 is only the amount of the accelerator, and the data of mechanical properties show that the compressive strength and the elastic modulus of the two are equivalent, which indicates that the mass ratio of the accelerator is changed in a certain region and does not affect the performance after crosslinking and curing. Therefore, the high-adhesion plugging material can be compounded with common oil well fillers for use, and the mechanical property of the compound can meet the use requirement of the underground environment, thereby playing a good plugging role.
TABLE 1 test results of initial curing time and compression Properties of examples and comparative examples
| Sample(s) | Onset of curing time (h) | Compressive strength (MPa) | Modulus of elasticity (MPa) |
| Example 1 | 2.5 | 79.1 | 333 |
| Example 2 | 3 | 61.0 | 397 |
| Example 3 | 1.5 | 66.9 | 401 |
| Example 4 | 3 | 79.3 | 501 |
| Comparative example | 3 | 74.3 | 486 |
As shown in the table 1, it can be seen from the result of the initial curing time that the cross-linking curing time of the plugging material is related to the proportions of the unsaturated polyester, the curing agent, the accelerator, the long carbon chain carboxylic acid modified titanate coupling agent and other components, and the curing time can be adjusted within the range of 2-10 h by changing the distribution ratio of the components, so that the plugging material can meet the use requirements of wells with different depths. By comparing the curing start times of examples 2 and 3, it can be found that the increase of the accelerator ratio can significantly increase the rate of crosslinking curing, thereby realizing adjustable plugging time and being applicable to plugging effects of different well conditions.
Table 2 shows the results of the dynamic viscosity test of the samples of examples 1 to 4 and comparative example immediately after the start of curing. Since the viscosity hardly changes as the shear rate varies from 1 to 200r/s, the viscosity data at a shear rate of 100r/s was selected as the viscosity of the resin system.
Table 2 test results of dynamic viscosity of examples and comparative examples
It can be seen from table 2 above that the viscosity of the plugging material is mainly related to the matrix resin when it is not cured, and the viscosity of the plugging material does not change with the change of the shear strength, and shows the flow behavior of a typical newtonian fluid in a period of time when it starts to cure, the flow performance is good, and the pumping is convenient. Finally, the time of reaching the appointed position is estimated in advance, and the plugging material can be ensured to play a plugging role in the proper position.
Table 3 shows the results of testing the adhesion after curing for examples 1-4 and comparative examples. Comparative example 1 broke at the junction of the two cores when subjected to stretching, while examples 1-4 broke inside the core, indicating that the adhesion of the resin system to the core even exceeded the strength of the core itself after addition of the carboxylic acid-modified coupling agent, clearly indicating good adhesion.
Table 3 test results of adhesion of examples and comparative examples
As can be seen from the data in table 3, the differences in adhesion between examples 1 to 4, to which the long carbon chain carboxylic acid-modified titanate coupling agent was added, and the comparative examples, to which the carboxylic acid-modified coupling agent was not added, were significant, and the adhesion of the samples to metal (tinplate) was enhanced by 50% or more by the addition of the long carbon chain carboxylic acid-modified titanate coupling agent. The organic functional group in the titanate coupling agent modified by the long carbon chain carboxylic acid has higher affinity with resin, and can form a bridging chain with the surface of an inorganic material to enhance the adhesive force between the organic functional group and the resin. From the comparison of examples 2 and 3, it was found that the adhesion ability of the resin to rock and soil substances is slightly increased when the amount of the long carbon chain carboxylic acid modified titanate coupling agent is slightly increased, and when a plugging material having a stronger adhesion ability is required, the amount of the long carbon chain carboxylic acid modified titanate coupling agent can be slightly increased to improve the adhesion effect.
In conclusion, the high-adhesion plugging material provided by the application takes unsaturated polyester as a main raw material and the long-chain carboxylic acid modified titanate coupling agent as coupling agent acid, so that the compatibility of underground rock and soil to the unsaturated polyester can be enhanced, the rock and soil surface layer is prevented from being separated out when the plugging material is used as a plugging agent, and the introduced long-chain oily group can effectively reduce the solubility of the coupling agent in water and prolong the service life. Meanwhile, the addition ratio of the curing agent and the accelerator in the plugging material is adjusted, so that the crosslinking curing time of the plugging material can be adjusted within a certain time range, the plugging material is flowable liquid before crosslinking, and is a solid material with good mechanical property and high temperature resistance after crosslinking, so that the plugging material is suitable for permanently plugging underground pores and cracks. Meanwhile, the application also provides a preparation method of the high-adhesion plugging material, and the method is simple, convenient and easy to implement, good in effect and high in application value. The high-adhesion plugging material and the preparation method thereof solve the problem that the requirements of the plugging agent on the coupling property and the high adhesion of the plugging material cannot be met due to the fact that the compatibility of the coupling agent and unsaturated polyester in a common plugging agent is not ideal in the prior art.
It should be noted that the terms "comprises", "comprising" or any other variation thereof are intended to cover a non-exclusive inclusion, so that an article or apparatus including a series of elements includes not only those elements but also other elements not explicitly listed or inherent to such a process, method, article or apparatus. Without further limitation, an element defined by the phrases "comprising a," "8230," "8230," or "comprising" does not exclude the presence of additional like elements in a process, method, article, or apparatus that comprises the element.
The previous description is only an example of the present application, and is provided to enable any person skilled in the art to understand or implement the present application. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the application. Thus, the present application is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
It will be understood that the present application is not limited to what has been described above and shown in the accompanying drawings, and that various modifications and changes can be made without departing from the scope thereof. The scope of the application is limited only by the appended claims.
Claims (6)
1. The high-adhesion plugging material is characterized by comprising the following raw materials in parts by weight:
60-95 parts of unsaturated polyester, 5-25 parts of curing agent, 0.5-5 parts of accelerator and 0.5-5 parts of long-chain carboxylic acid modified titanate coupling agent;
wherein the unsaturated polyester is unsaturated linear thermosetting resin prepared by condensation polymerization of dibasic acid or anhydride and dihydric alcohol, and comprises one or more of o-benzene unsaturated polyester, m-benzene unsaturated polyester and bisphenol A unsaturated polyester;
the curing agent is one or more of styrene, vinyl toluene, methyl methacrylate, cumene hydroperoxide, dicumyl peroxide, methyl ethyl ketone peroxide, benzoyl peroxide and tert-butyl peroxybenzoate;
the accelerant is one or more of N, N '-dimethylaniline, N' -diethylaniline, cobalt octoate, cobalt naphthenate and dodecyl mercaptan;
the long-chain carboxylic acid modified titanate coupling agent is prepared by the reaction of a water-soluble titanate coupling agent containing hydroxyl functional groups and long-chain carboxylic acid; the long chain carboxylic acid modified titanate coupling agent has the following chemical structure:
wherein: r is 1 And R 2 Is alkyl substituted by O and N or heteroaryl substituted by O and N, the value range of N is 1 to 5, and the value range of m is 9 to 24.
2. The highly adhesive plugging material according to claim 1, wherein the plugging material comprises the following raw materials in parts by weight:
70 parts of unsaturated polyester, 25 parts of methyl ethyl ketone peroxide, 4 parts of N, N' -dimethylaniline and 1 part of long-chain carboxylic acid modified titanate coupling agent.
3. The highly adhesive plugging material according to claim 1, wherein the plugging material comprises the following raw materials in parts by weight:
70 parts of unsaturated polyester, 25 parts of styrene, 4 parts of cobalt naphthenate and 1 part of long-chain carboxylic acid modified titanate coupling agent.
4. The highly adherent plugging material of claim 1, wherein the plugging material comprises the following raw materials in parts by weight:
70 parts of unsaturated polyester, 25 parts of styrene, 8 parts of cobalt naphthenate and 1 part of long-chain carboxylic acid modified titanate coupling agent.
5. The highly adherent plugging material of claim 1, wherein the plugging material comprises the following raw materials in parts by weight:
70 parts of unsaturated polyester, 20 parts of methyl methacrylate, 5 parts of N, N' -dimethylaniline and 2 parts of long-chain carboxylic acid modified titanate coupling agent.
6. A method for producing a highly adhesive plugging material according to any of claims 1 to 5, comprising the steps of:
mixing unsaturated polyester and long-chain carboxylic acid modified titanate coupling agent, and uniformly stirring to obtain a mixture;
adding a curing agent into the uniformly stirred mixture, and uniformly stirring;
adding an accelerant into the mixture after the curing agent is added, and uniformly stirring to obtain a crude material;
sealing the coarse material, placing the sealed coarse material in a drying oven, setting the temperature of the drying oven to be 40-150 ℃, and reacting for 2-20h to obtain the high-adhesion plugging material;
wherein the unsaturated polyester is unsaturated linear thermosetting resin prepared by condensation polymerization of dibasic acid or anhydride and dihydric alcohol, and comprises one or more of o-benzene unsaturated polyester, m-benzene unsaturated polyester and bisphenol A unsaturated polyester;
the curing agent is one or more of styrene, vinyl toluene, methyl methacrylate, cumene hydroperoxide, dicumyl peroxide, methyl ethyl ketone peroxide, benzoyl peroxide and tert-butyl peroxybenzoate;
the accelerant is one or more of N, N '-dimethylaniline, N' -diethylaniline, cobalt octoate, cobalt naphthenate and dodecyl mercaptan;
the long-chain carboxylic acid modified titanate coupling agent is prepared by the reaction of a water-soluble titanate coupling agent containing hydroxyl functional groups and long-chain carboxylic acid; the long chain carboxylic acid modified titanate coupling agent has the following chemical structure:
wherein: r is 1 And R 2 Is alkyl substituted by O and N or heteroaryl substituted by O and N, the value range of N is 1 to 5, and the value range of m is 9 to 24.
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