CN111500231B - Casing pipe repairing material with high adhesion to metal and preparation method thereof - Google Patents
Casing pipe repairing material with high adhesion to metal and preparation method thereof Download PDFInfo
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- CN111500231B CN111500231B CN202010500662.0A CN202010500662A CN111500231B CN 111500231 B CN111500231 B CN 111500231B CN 202010500662 A CN202010500662 A CN 202010500662A CN 111500231 B CN111500231 B CN 111500231B
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- 239000000463 material Substances 0.000 title claims abstract description 106
- 239000002184 metal Substances 0.000 title claims abstract description 56
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 238000006263 metalation reaction Methods 0.000 title description 2
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 49
- 239000007849 furan resin Substances 0.000 claims abstract description 43
- 230000008439 repair process Effects 0.000 claims abstract description 32
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 28
- 150000004756 silanes Chemical class 0.000 claims abstract description 28
- 239000002994 raw material Substances 0.000 claims abstract description 25
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 25
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- 230000001070 adhesive effect Effects 0.000 claims abstract description 8
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 claims description 48
- 238000003756 stirring Methods 0.000 claims description 25
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 22
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- JOBBTVPTPXRUBP-UHFFFAOYSA-N [3-(3-sulfanylpropanoyloxy)-2,2-bis(3-sulfanylpropanoyloxymethyl)propyl] 3-sulfanylpropanoate Chemical compound SCCC(=O)OCC(COC(=O)CCS)(COC(=O)CCS)COC(=O)CCS JOBBTVPTPXRUBP-UHFFFAOYSA-N 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
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- 239000013058 crude material Substances 0.000 claims description 7
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- 239000012258 stirred mixture Substances 0.000 claims description 7
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- CSKNSYBAZOQPLR-UHFFFAOYSA-N benzenesulfonyl chloride Chemical compound ClS(=O)(=O)C1=CC=CC=C1 CSKNSYBAZOQPLR-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- IMQFZQVZKBIPCQ-UHFFFAOYSA-N 2,2-bis(3-sulfanylpropanoyloxymethyl)butyl 3-sulfanylpropanoate Chemical compound SCCC(=O)OCC(CC)(COC(=O)CCS)COC(=O)CCS IMQFZQVZKBIPCQ-UHFFFAOYSA-N 0.000 claims description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Substances O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 3
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- 238000004519 manufacturing process Methods 0.000 claims description 3
- RUDUCNPHDIMQCY-UHFFFAOYSA-N [3-(2-sulfanylacetyl)oxy-2,2-bis[(2-sulfanylacetyl)oxymethyl]propyl] 2-sulfanylacetate Chemical compound SCC(=O)OCC(COC(=O)CS)(COC(=O)CS)COC(=O)CS RUDUCNPHDIMQCY-UHFFFAOYSA-N 0.000 claims description 2
- 230000001464 adherent effect Effects 0.000 claims 2
- 238000000034 method Methods 0.000 abstract description 32
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- 230000000694 effects Effects 0.000 abstract description 15
- 239000003208 petroleum Substances 0.000 abstract description 8
- 238000004132 cross linking Methods 0.000 abstract description 7
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- CHTHALBTIRVDBM-UHFFFAOYSA-N furan-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)O1 CHTHALBTIRVDBM-UHFFFAOYSA-N 0.000 description 4
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- 238000005259 measurement Methods 0.000 description 3
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- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide Substances CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 description 2
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
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- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 description 1
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- BPTCFZZYVLNLHK-UHFFFAOYSA-N formaldehyde;furan;urea Chemical compound O=C.NC(N)=O.C=1C=COC=1 BPTCFZZYVLNLHK-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The application provides a casing pipe repair material with high adhesion to metal, which comprises the following raw materials in parts by weight: 60-95 parts of furan resin; 5-15 parts of a curing agent; 0.5-5 parts of a crosslinking agent; 0.5-5 parts of furan modified silane coupling agent. The application adopts the furan-modified silane coupling agent, improves the compatibility between the coupling agent and furan resin, thereby enhancing the adhesive capacity of the repair material and the metal surface, improving the repair effect, changing the crosslinking density and activity of a system by changing the proportion of the curing agent and the crosslinking agent, realizing the controllability of the curing time within a certain time range, and solving the problem that the prepared casing repair material cannot meet the actual use requirement on the adhesion of the metal petroleum casing because the common coupling agent and the furan resin have poor compatibility in the prior art. The application also provides a preparation method of the casing pipe repairing 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 functional polymers and oilfield chemical products, in particular to a casing repairing material with high adhesion to metal and a preparation method thereof.
Background
The petroleum casing pipe is one kind of important petroleum exploiting equipment and is used mainly in the well drilling process and after well completion to support well wall and ensure the normal operation of the well. In the long-term development process of oil and gas wells, due to factors such as plastic deformation of underground rock stratums, perforation misshooting, corrosion, casing abrasion and the like, the service life of the casing is greatly shorter than expected, and the normal production of the oil field is seriously influenced.
The currently common casing pipe repairing technologies are mainly divided into cement repairing, expansion pipe repairing and chemical repairing technologies. The thermosetting resin used in the chemical repair technology is heated to generate a chemical curing reaction, is heated and is not melted or dissolved, has excellent mechanical property, good chemical stability and long service time, and is widely applied to the field of casing repair. Furan resin is a thermosetting resin tree produced from furfuryl alcohol having a furan ring and furfural as raw materials. The prior art discloses a chemical sealing agent, which comprises the main components of phenolic resin and epoxy resin. The casing repairing material can be used for repairing and reinforcing operations after casing damage and deformation in oilfield development, and the production capacity of an oil-water well is recovered. The compressive strength of the cured sample can reach 13-87 MPa.
The adhesion performance of the thermosetting resin to the casing material is crucial to the repairing effect, and factors such as underground rock formation creep, formation temperature and pressure can cause the casing repairing material to gradually loosen and fall off. The conventional thermosetting resins have poor adhesion to metals and require modification for improving adhesion. Coupling agents are commonly used to improve the interfacial properties between two or more substances, where a silane coupling agent is a modified coupling agent containing an organofunctional group and a siloxy group, the siloxy group being reactive with inorganic substances and the organofunctional group being reactive with or compatible with organic substances. The selection of a proper silane coupling agent can enhance the adhesion of the repair material to metal, and simultaneously, the improvement of compatibility can also improve the service performance of the material. However, the compatibility of the common coupling agent and furan resin is not good, so that the adhesion of the prepared casing repairing material to the metal petroleum casing cannot meet the requirement of practical use.
Disclosure of Invention
The application provides a casing pipe repairing material with high adhesion to metal and a preparation method thereof, and aims to solve the problem that in the prior art, the adhesion of the prepared casing pipe repairing material to a metal petroleum casing pipe cannot meet the actual use requirement due to poor compatibility of a common coupling agent and furan resin.
The technical scheme adopted by the application for solving the technical problems is as follows:
a casing pipe repairing material with high adhesion to metal comprises the following raw materials in parts by weight:
60-95 parts of furan resin; 5-15 parts of a curing agent; 0.5-5 parts of a crosslinking agent; 0.5-5 parts of furan modified silane coupling agent.
Optionally, the furan-modified silane coupling agent is prepared by the reaction of furan ring dicarboxylic acid and an amino-containing silane coupling agent, and the furan-modified silane coupling agent has the following chemical structure:
wherein R is1Is alkyl containing 1-3 carbon atoms, and the value range of n is 1-5.
Optionally, the furan resin is a resin produced by using furfuryl alcohol and furfural of furan rings as raw materials, and comprises one or more of furfuryl alcohol resin, furfural resin, furfuryl ketone-formaldehyde resin and urea formaldehyde furan resin.
Optionally, the curing agent is one or more of benzene sulfonyl chloride, p-toluene sulfonyl chloride, ethyl sulfate, phosphoric acid and p-toluene sulfonic acid.
Optionally, the cross-linking agent is one or more of trimethylolpropane tri (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate), and pentaerythritol tetrakis (3-mercaptopropionate).
A casing pipe repairing material with high adhesion to metal comprises the following raw materials in parts by weight:
84 parts of furfuryl alcohol furan resin; 10 parts of ethyl sulfate; 4 parts of tetra (3-mercaptopropionic acid) pentaerythritol ester; 2 parts of furan modified silane coupling agent.
A casing pipe repairing material with high adhesion to metal comprises the following raw materials in parts by weight:
85 parts of furfuryl alcohol furan resin; 10 parts of benzenesulfonyl chloride; 4 parts of trimethylolpropane tris (3-mercaptopropionate); 1 part of furan modified silane coupling agent.
A casing pipe repairing material with high adhesion to metal comprises the following raw materials in parts by weight:
85 parts of furfuryl alcohol furan resin; 10 parts of p-toluenesulfonic acid; 4 parts of trimethylolpropane tris (3-mercaptopropionate); 1 part of furan modified silane coupling agent.
A casing pipe repairing material with high adhesion to metal comprises the following raw materials in parts by weight:
85 parts of urea-formaldehyde furan resin; 10 parts of p-toluenesulfonic acid; 4 parts of tetra (3-mercaptopropionic acid) pentaerythritol ester; 1 part of furan modified silane coupling agent.
A method for preparing a casing repair material having high adhesion to metals, the method comprising the steps of:
mixing furan resin and a furan-modified silane coupling agent, and uniformly stirring to obtain a mixture;
adding a curing agent into the uniformly stirred mixture, and uniformly stirring;
adding a cross-linking agent into the mixture after the curing agent is added, and uniformly stirring to obtain a crude material;
and sealing the coarse material, placing the sealed coarse material in an oven, setting the temperature of the oven to be 50-100 ℃, and reacting for 2-20h to obtain the casing repairing material with high adhesion to metal.
The technical scheme provided by the application comprises the following beneficial technical effects:
the application provides a casing pipe repair material with high adhesion to metal, which comprises the following raw materials in parts by weight: 60-95 parts of furan resin; 5-15 parts of a curing agent; 0.5-5 parts of a crosslinking agent; 0.5-5 parts of furan modified silane coupling agent. The method has the advantages that the furan-modified silane coupling agent replaces the traditional coupling agent, the compatibility between the coupling agent and furan resin can be improved, the adhesion capability of the repairing material and the metal surface is enhanced, the repairing effect is improved, the crosslinking density and the activity of a system are changed by changing the proportion of the curing agent and the crosslinking agent, the controllability of the curing time within a certain time range is realized, and the problem that the prepared casing repairing material cannot meet the requirement of practical use on the adhesion of a metal petroleum casing due to the poor compatibility of the common coupling agent and the furan resin in the prior art is solved. The application also provides a preparation method of the casing pipe repairing material with high adhesion to metal, and the method is simple, convenient and easy to implement, good in effect and high in application value.
Drawings
In order to more clearly explain the technical solution of the present application, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious to those skilled in the art that other drawings can be obtained according to the drawings without any creative effort.
FIG. 1 is a flow chart of a method for preparing a casing repair material with high adhesion to metal according to an embodiment of the present disclosure;
FIG. 2 is a graph showing mechanical properties of examples 1 to 4 and comparative examples 1 and 2 under a curing condition of 80 ℃.
Detailed Description
In order to make the technical solutions in the present application better understood by those skilled in the art, 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.
In the technical scheme of the application, the existing coupling agent is modified, and 2, 5-furandicarboxylic acid is connected to the amino group of the coupling agent through reaction, so that the compatibility of the coupling agent with resin is enhanced, and a better coupling effect is achieved.
The technical scheme of the application adopts an in-situ curing method to repair the casing, and has higher application value. The in-situ curing method is a non-extraction casing pipe repairing process and generally comprises a turning method and a pulling-in method according to different construction processes. When the composite hose is applied, the fiber reinforced composite hose is used as a carrier, impregnated with synthetic resin and then pulled or overturned to be lined in a cleaned pipeline to be repaired. Because the flexibility of the composite hose is extremely strong, the lining pipe can be always tightly attached to the inner wall of the pipeline to be repaired under the action of pressure, and a composite pipeline with high integrity is formed after curing. The lining hose material of the turnover method is generally made of flexible polymer material as a framework, and a water-resisting film is covered on the outer layer of the material. Under the action of water pressure and air pressure, the lining material reversely rotates to enter the inner wall of the pipeline, after the completion, under the action of the temperature of hot water, the resin is solidified, and the lining material forms a hard inner wall of the pipeline. The method is convenient, low in cost and smooth in pipe wall, and is very suitable for the occasion of repairing the damaged casing pipe.
The preparation method of the furan-modified silane coupling agent comprises the following steps: in the modification process of the silane coupling agent, the coupling agent is a silane coupling agent containing amino, the modifying agent is 2, 5-furandicarboxylic acid, and can be directly reacted or added with acyl chloride or a condensing agent EDCI (1- (3-dimethylaminopropyl) -3-ethylcarbodiimide)/DCC (dicyclohexylcarbodiimide) and the like, and the solvent is ethanol solution. And during reaction, the temperature is 80 ℃, and a proper amount of each reactant and a condensing agent are added and stirred for 4 hours to obtain the linear furan ring-containing modified silane coupling agent.
The furan-modified silane coupling agent product prepared by the method is used as a raw material to prepare the casing pipe repairing material with high metal adhesion in the technical scheme of the application, and simultaneously comprises the following raw materials in parts by weight:
60-95 parts of furan resin; 5-15 parts of a curing agent; 0.5-5 parts of a crosslinking agent; the addition amount of the furan-modified silane coupling agent is 0.5-5 parts. According to the technical scheme, the furan-modified silane coupling agent is used for replacing the traditional coupling agent, the compatibility between the coupling agent and furan resin can be improved, the adhesion capability of the repairing material and the metal surface is enhanced, the repairing effect is improved, the crosslinking density and the activity of a system are changed by changing the proportion of the curing agent and the crosslinking agent, the controllability of the curing time within a certain time range is realized, and the problem that the prepared casing repairing material cannot meet the actual use requirement on the adhesion of a metal petroleum casing due to the poor compatibility of the common coupling agent and the furan resin in the prior art is solved.
Further, the furan-modified silane coupling agent is prepared by the reaction of furan ring dicarboxylic acid and an amino-containing silane coupling agent, and has the following chemical structure:
wherein R is1Is alkyl containing 1-3 carbon atoms, and the value range of n is 1-5.
The furan resin is produced by taking furfuryl alcohol and furfural of furan rings as raw materials, and comprises one or more of furfuryl alcohol resin, furfural resin, furfuryl ketone-formaldehyde resin and urea-formaldehyde furan resin.
The curing agent is one or more of benzene sulfonyl chloride, p-toluene sulfonyl chloride, ethyl sulfate, phosphoric acid and p-toluene sulfonic acid.
The cross-linking agent is one or more of trimethylolpropane tri (3-mercaptopropionic acid) ester, pentaerythritol tetra (2-mercaptoacetic acid) ester and pentaerythritol tetra (3-mercaptopropionate).
Referring to fig. 1, as shown in fig. 1, the present application further provides a method for preparing a casing repairing material with high adhesion to metal, including the following steps:
s1: mixing furan resin and a furan-modified silane coupling agent, and uniformly stirring to obtain a mixture;
s2: adding a curing agent into the uniformly stirred mixture, and uniformly stirring;
s3: adding a cross-linking agent into the mixture after the curing agent is added, and uniformly stirring to obtain a crude material;
s4: and sealing the coarse material, placing the sealed coarse material in an oven, setting the temperature of the oven to be 50-100 ℃, and reacting for 2-20h to obtain the casing repairing material with high adhesion to metal.
The technical solution in the present application is further explained and illustrated by several examples below.
Example 1
A casing pipe repairing material with high adhesion to metal comprises the following raw materials in parts by weight:
and is prepared by the following method:
(1) mixing furfuryl alcohol furan resin and a furan-modified silane coupling agent, and uniformly stirring to obtain a mixture;
(2) adding ethyl sulfate into the uniformly stirred mixture, and uniformly stirring;
(3) adding pentaerythritol tetrakis (3-mercaptopropionate) into the mixture after the curing agent is added, and uniformly stirring to obtain a crude material;
(4) and sealing the coarse material, placing the sealed coarse material in an oven, setting the temperature of the oven to 80 ℃, and reacting for 12 hours to obtain the casing repairing material with high adhesion to metal.
Example 2
A casing pipe repairing material with high adhesion to metal comprises the following raw materials in parts by weight:
and is prepared by the following method:
(1) mixing furfuryl alcohol furan resin and a furan-modified silane coupling agent, and uniformly stirring to obtain a mixture;
(2) adding benzene sulfonyl chloride into the uniformly stirred mixture, and uniformly stirring;
(3) adding trimethylolpropane tris (3-mercaptopropionic acid) ester into the mixture after the curing agent is added, and uniformly stirring to obtain a crude material;
(4) and sealing the coarse material, placing the sealed coarse material in an oven, setting the temperature of the oven to 80 ℃, and reacting for 12 hours to obtain the casing repairing material with high adhesion to metal.
Example 3
A casing pipe repairing material with high adhesion to metal comprises the following raw materials in parts by weight:
and is prepared by the following method:
(1) mixing furfuryl alcohol furan resin and a furan-modified silane coupling agent, and uniformly stirring to obtain a mixture;
(2) adding p-toluenesulfonic acid into the uniformly stirred mixture, and uniformly stirring;
(3) adding trimethylolpropane tris (3-mercaptopropionic acid) ester into the mixture after the curing agent is added, and uniformly stirring to obtain a crude material;
(4) and sealing the coarse material, placing the sealed coarse material in an oven, setting the temperature of the oven to 80 ℃, and reacting for 12 hours to obtain the casing repairing material with high adhesion to metal.
Example 4
A casing pipe repairing material with high adhesion to metal comprises the following raw materials in parts by weight:
and is prepared by the following method:
(1) mixing urea-formaldehyde furan resin and a furan-modified silane coupling agent, and uniformly stirring to obtain a mixture;
(2) adding p-toluenesulfonic acid into the uniformly stirred mixture, and uniformly stirring;
(3) adding pentaerythritol tetrakis (3-mercaptopropionate) into the mixture after the curing agent is added, and uniformly stirring to obtain a crude material;
(4) and sealing the coarse material, placing the sealed coarse material in an oven, setting the temperature of the oven to 80 ℃, and reacting for 12 hours to obtain the casing repairing material with high adhesion to metal.
Comparative example 1
The casing pipe repair material prepared by adding no furan modified silane coupling agent is taken as a comparative example and comprises the following raw materials in parts by weight:
89 parts by weight of furfuryl alcohol furan resin;
10 parts of ethyl sulfate;
1 part by weight of pentaerythritol tetrakis (3-mercaptopropionate);
and is prepared by the following method:
(1) mixing furfuryl alcohol furan resin and ethyl sulfate, and stirring uniformly;
(2) adding pentaerythritol tetrakis (3-mercaptopropionate) and stirring uniformly;
(3) and sealing the materials, placing the materials in an oven at the temperature of 80 ℃ and reacting for 12 hours to obtain the casing repairing material in the comparative example 1.
Comparative example 2
The casing pipe repair material prepared by adding no furan modified silane coupling agent is taken as a comparative example and comprises the following raw materials in parts by weight:
89 parts by weight of urea-formaldehyde furan resin;
10 parts by weight of p-toluenesulfonic acid;
1 part by weight of pentaerythritol tetrakis (3-mercaptopropionate);
and is prepared by the following method:
(1) mixing urea-formaldehyde furan resin and p-toluenesulfonic acid, and uniformly stirring;
(2) adding pentaerythritol tetrakis (3-mercaptopropionate) and stirring uniformly;
(3) and sealing the materials, placing the materials in an oven at the temperature of 80 ℃ and reacting for 12 hours to obtain the casing repairing material in the comparative example 2.
The following functional tests were performed on the finished products prepared in examples 1 to 4 and comparative examples 1 to 2 above:
start of cure time test: the method is determined by adopting an inversion method, namely the finished sleeve repairing material materials in the examples 1-4 and the comparative examples 1-2 after being uniformly mixed are filled into a 20mL sample bottle and are heated and cured at the temperature of 60-80 ℃, the bottle is taken out after a period of time and is inverted, and the curing starting time is determined when the materials can not flow.
And (3) testing mechanical properties: the finished sleeve repair material materials in examples 1-4 and comparative examples 1-2 after being uniformly stirred were allowed to stand for a period of time (no air bubbles were present), then injected into a compression mold, subsequently cured at 80 ℃, and after 12 hours, the cured compression sample strips were taken out and subjected to compression testing. The resulting specimens were cylindrical, 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 finished casing repair material materials of examples 1-4 and comparative examples 1-2 were measured by compression testing.
Adhesion performance test: the adhesion properties to metal-textured sleeves were characterized by determining the bond strength as an adhesive to two tinplate pieces using the finished sleeve repair material systems of examples 1-4 and comparative examples 1-2. A 10cm by 2cm frosted iron piece was used, and a 2cm by 2cm area was defined at the end of each iron piece as an adhesive area. When preparing the bonded sample, the finished casing pipe repair material system in examples 1-4 and comparative examples 1-2 is selected to bond two iron sheets. Then, the obtained product was placed in an oven at 80 ℃ for 12 hours to be cured, and the cured bonding area was tested for the axial tensile strength. The temperature at which the mechanical property measurement was performed was room temperature. A plurality of parallel samples are simultaneously tested each time, and an average value is taken when the bonding performance is calculated.
The rheological property test method comprises the following steps:
the viscosity was measured using an RS6000 rotational rheometer manufactured by HAAKE, germany. The dynamic viscosity of the finished casing repair material systems in examples 1-4 and comparative examples 1-2 was measured using the double cylinder method at room temperature just before curing, taking into account the viscosity number of the material system.
And (4) analyzing results:
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 examples 1 to 2. FIG. 1 is a graph showing mechanical property curves of examples 1 to 4 and comparative examples 1 to 2 under test conditions. The relative error of the measurement result of the mechanical property parallel experiment is not more than 0.5 percent, and the arithmetic mean value is taken as the result. As shown in Table 1 and FIG. 1, the compressive strength of the samples of the examples is slightly improved compared with the comparative examples, and the elastic modulus of the samples is not obviously changed, which indicates that the mechanical properties of the casing pipe repairing material are not obviously damaged by adding the modified silane coupling agent containing furan rings, and even the crosslinking density can be slightly increased due to the coupling performance, the mechanical properties can be slightly improved. The above results show that the mechanical properties of the casing pipe repairing material with high metal adhesion can meet the use requirements of a certain underground environment, and a good casing pipe repairing effect can be achieved.
TABLE 1 test results of initial curing time and mechanical properties of examples and comparative examples
As shown in table 1, it can be seen from the result of the initial curing time that the crosslinking curing time of the casing pipe repair material is closely related to the ratio of the furan resin, the curing agent, the crosslinking agent, the furan modified coupling agent and other components, and by changing the distribution ratio of the components, the curing time can be adjusted within the range of 2-20h, and the casing pipe repair material can be suitable for use requirements under different conditions.
Table 2 shows the results of dynamic viscosity measurements at the very beginning of curing for the samples of examples 1 to 4 and comparative examples 1 to 2. 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
From the above table 2, it can be seen that the viscosity of the casing pipe repairing material is mainly related to the matrix resin when the casing pipe repairing material is not cured obviously, and the casing pipe repairing material shows a fixed value which is not changed with the added components, and the viscosity of the casing pipe repairing material does not change with the change of the shear strength, shows the flowing character of the typical newtonian fluid within a period of time when the casing pipe repairing material starts to be cured, has good flowing performance, and is easily immersed into a hose used for in-situ curing during actual use, and is subjected to crosslinking curing under corresponding conditions of temperature, pressure and the like.
Table 3 below shows the results of testing the adhesion after curing of the samples of examples 1 to 4 and comparative examples 1 to 2.
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 force are significant between examples 1-4, to which the furan-modified silane coupling agent was added, and comparative examples 1-2, to which the furan-modified silane coupling agent was not added, and the adhesion force of the sample to the metal (tinplate) was enhanced by 50-100% by the addition of the furan-modified silane coupling agent, increasing from 1.5-2MPa to around 3 MPa. The affinity of organic functional groups in the furan-modified silane coupling agent with resin is high, and the affinity of siloxy functional groups with inorganic materials such as carbon black, minerals, metals and the like is good, so that the furan-modified silane coupling agent can form bridging between the resin and the metal, and the adhesion of the resin to the metal is remarkably enhanced. From a comparison of example 1 and comparative example 1, it can be seen that the enhancement of the adhesion of the resin to the metal in the same system is mainly due to the addition of the furan-modified silane coupling agent, and this conclusion can be drawn from example 4 and comparative example 2 as well. When a casing pipe repairing material with stronger metal adhesion capacity is needed, the addition amount of the furan-modified silane coupling agent can be increased by a small amount so as to improve the adhesion effect.
In summary, the present application provides a casing pipe repair material with high adhesion to metal, which comprises the following raw materials in parts by weight: 60-95 parts of furan resin; 5-15 parts of a curing agent; 0.5-5 parts of a crosslinking agent; 0.5-5 parts of furan modified silane coupling agent. The method has the advantages that the furan-modified silane coupling agent replaces the traditional coupling agent, the compatibility between the coupling agent and furan resin can be improved, the adhesion capability of the repairing material and the metal surface is enhanced, the repairing effect is improved, the crosslinking density and the activity of a system are changed by changing the proportion of the curing agent and the crosslinking agent, the controllability of the curing time within a certain time range is realized, and the problem that the prepared casing repairing material cannot meet the requirement of practical use on the adhesion of a metal petroleum casing due to the poor compatibility of the common coupling agent and the furan resin in the prior art is solved. The application also provides a preparation method of the casing pipe repairing material with high adhesion to metal, the method is simple, convenient and easy to implement, good in effect, and high in application value due to the fact that the casing pipe is repaired by the in-situ curing method.
It is to be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that an article or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other identical elements in a process, method, article, or apparatus that comprises the element.
The above description is merely exemplary of the present application and is presented to enable those skilled in the art to understand and practice 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 (9)
1. The casing pipe repairing material with high adhesion to metal is characterized by comprising the following raw materials in parts by weight:
60-95 parts of furan resin; 5-15 parts of a curing agent; 0.5-5 parts of a crosslinking agent; 0.5-5 parts of furan-modified silane coupling agent;
the furan-modified silane coupling agent is prepared by the reaction of furan ring dicarboxylic acid and an amino-containing silane coupling agent, and has the following chemical structure:
wherein R is1Is alkyl containing 1-3 carbon atoms, and the value range of n is 1-5.
2. The metal-highly adhesive sleeve repair material according to claim 1, wherein the furan resin is a resin produced from furfuryl alcohol and furfural having a furan ring as a raw material, and includes one or more of furfuryl alcohol resin, furfural resin, furfuryl ketone-formaldehyde resin, and urea-formaldehyde furan resin.
3. The metal highly adherent casing repair material of claim 1, wherein the curing agent is one or more of benzenesulfonyl chloride, p-toluenesulfonyl chloride, ethyl sulfate, phosphoric acid, and p-toluenesulfonic acid.
4. The metal highly adherent casing repair material according to claim 1, wherein the crosslinking agent is one or more of trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate).
5. The metal highly adhesive sleeve repair material according to claim 1, wherein the repair material comprises the following raw materials in parts by weight:
84 parts of furfuryl alcohol furan resin; 10 parts of ethyl sulfate; 4 parts of tetra (3-mercaptopropionic acid) pentaerythritol ester; 2 parts of furan modified silane coupling agent.
6. The metal highly adhesive sleeve repair material according to claim 1, wherein the repair material comprises the following raw materials in parts by weight:
85 parts of furfuryl alcohol furan resin; 10 parts of benzenesulfonyl chloride; 4 parts of trimethylolpropane tris (3-mercaptopropionate); 1 part of furan modified silane coupling agent.
7. The metal highly adhesive sleeve repair material according to claim 1, wherein the repair material comprises the following raw materials in parts by weight:
85 parts of furfuryl alcohol furan resin; 10 parts of p-toluenesulfonic acid; 4 parts of trimethylolpropane tris (3-mercaptopropionate); 1 part of furan modified silane coupling agent.
8. The metal highly adhesive sleeve repair material according to claim 1, wherein the repair material comprises the following raw materials in parts by weight:
85 parts of urea-formaldehyde furan resin; 10 parts of p-toluenesulfonic acid; 4 parts of tetra (3-mercaptopropionic acid) pentaerythritol ester; 1 part of furan modified silane coupling agent.
9. A method for producing a casing repairing material for use in producing a casing repairing material having high adhesion to a metal according to any one of claims 1 to 8, comprising the steps of:
mixing furan resin and a furan-modified silane coupling agent, and uniformly stirring to obtain a mixture;
adding a curing agent into the uniformly stirred mixture, and uniformly stirring;
adding a cross-linking agent into the mixture after the curing agent is added, and uniformly stirring to obtain a crude material;
and sealing the coarse material, placing the sealed coarse material in an oven, setting the temperature of the oven to be 50-100 ℃, and reacting for 2-20h to obtain the casing repairing material with high adhesion to metal.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102665960A (en) * | 2009-12-25 | 2012-09-12 | 花王株式会社 | Binder composition for the formation of self-curing molds |
| CN105689636A (en) * | 2014-12-10 | 2016-06-22 | 花王株式会社 | Mold-making set |
| CN110814273A (en) * | 2019-11-14 | 2020-02-21 | 安徽索立德铸业有限公司 | Modified molding sand with furan resin loaded with nano ceramic |
| CN111196889A (en) * | 2019-09-20 | 2020-05-26 | 九江智达环能科技有限公司 | Multi-arm cross-linking agent and starch nanocrystal modification-based furan resin material and preparation method and application thereof |
-
2020
- 2020-06-04 CN CN202010500662.0A patent/CN111500231B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102665960A (en) * | 2009-12-25 | 2012-09-12 | 花王株式会社 | Binder composition for the formation of self-curing molds |
| CN105689636A (en) * | 2014-12-10 | 2016-06-22 | 花王株式会社 | Mold-making set |
| CN111196889A (en) * | 2019-09-20 | 2020-05-26 | 九江智达环能科技有限公司 | Multi-arm cross-linking agent and starch nanocrystal modification-based furan resin material and preparation method and application thereof |
| CN110814273A (en) * | 2019-11-14 | 2020-02-21 | 安徽索立德铸业有限公司 | Modified molding sand with furan resin loaded with nano ceramic |
Non-Patent Citations (1)
| Title |
|---|
| "硅烷在冷硬呋喃树脂砂中的应用研究";张祖烈等;《热加工工艺》;19811028(第Z1期);说明书全文 * |
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