CN103849374A - Fracturing propping agent and preparation method thereof - Google Patents
Fracturing propping agent and preparation method thereof Download PDFInfo
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- CN103849374A CN103849374A CN201210504522.6A CN201210504522A CN103849374A CN 103849374 A CN103849374 A CN 103849374A CN 201210504522 A CN201210504522 A CN 201210504522A CN 103849374 A CN103849374 A CN 103849374A
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- polysiloxane
- epoxy resin
- coupling agent
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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
- 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
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/80—Compositions for reinforcing fractures, e.g. compositions of proppants used to keep the fractures open
- C09K8/805—Coated proppants
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
- C04B26/30—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Other silicon-containing organic compounds; Boron-organic compounds
- C04B26/32—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Other silicon-containing organic compounds; Boron-organic compounds containing silicon
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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
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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Abstract
The invention provides a fracturing propping agent and a preparation method thereof, the fracturing propping agent is prepared by curing a mixture containing aggregate particles and a laminating adhesive, the laminating adhesive is a hydrophobic resin composition containing epoxy resin and polysiloxane, the polysiloxane is connected with at least part of the epoxy resin by a coupling agent, one end of the coupling agent is in covalent linkage with at least part of the epoxy resin by a first coupling part, the other end of the coupling agent is in covalent linkage with the polysiloxane by a second coupling part, and the fracturing propping agent has high water plugging capability and high crushing resistant strength.
Description
Technical field
The present invention relates to the preparation method of a kind of fracturing propping agents and a kind of fracturing propping agents.
Background technology
In the recovery process of oil and gas, high locking pressure deposits of low permeability is after fracture treatment, Oil gas-containing rock layer is split, the passage that oil gas forms from crack, collect, fracturing propping agents enter Filling in rock crack in company with high-pressure solution, play support crack not stress discharge and closed effect, thereby keep high flow conductivity, make oil gas unimpeded, increase the output of oil and gas.
Existing fracturing propping agents are mainly haydite (generally taking bauxitic clay as main raw material, and forming through 800 DEG C of above high temperature sinterings) and quartz sand, and its water blockoff ability needs further to improve.
Summary of the invention
The object of the present invention is to provide the preparation method of a kind of new fracturing propping agents and a kind of fracturing propping agents.Fracturing propping agents provided by the invention have higher water blockoff ability.
The invention provides a kind of fracturing propping agents, described fracturing propping agents are the product through being solidified to form by the mixture that contains particles of aggregates and overlay film binding agent, wherein, described overlay film binding agent is the hydrophobic resin composition that contains epoxy resin and polysiloxane, described polysiloxane links together by coupling agent and at least part of epoxy resin, described coupling agent has at least two isocyanate group, described at least part of epoxy resin has hydroxyl, described polysiloxane has can carry protogenic group, together with one end of described coupling agent is covalently bound with described at least part of epoxy resin by the first coupling part, together with the other end of described coupling agent is covalently bound with polysiloxane by the second coupling part, described the first coupling part is formed by the hydroxyl in the isocyanate group in described coupling agent and described at least part of epoxy resin, described the second coupling part is formed by the protogenic group of can carrying in the isocyanate group in described coupling agent and polysiloxane.
The present invention also provides a kind of preparation method of fracturing propping agents, the method comprises and will contain the mixture solidified of particles of aggregates and overlay film binding agent, wherein, described overlay film binding agent is the hydrophobic resin composition that contains epoxy resin and polysiloxane, described polysiloxane links together by coupling agent and at least part of epoxy resin, described coupling agent has at least two isocyanate group, described at least part of epoxy resin has hydroxyl, described polysiloxane has can carry protogenic group, together with one end of described coupling agent is covalently bound with described at least part of epoxy resin by the first coupling part, together with the other end of described coupling agent is covalently bound with polysiloxane by the second coupling part, described the first coupling part is formed by the hydroxyl in the isocyanate group in described coupling agent and described at least part of epoxy resin, described the second coupling part is formed by the protogenic group of can carrying in the isocyanate group in described coupling agent and polysiloxane.
The mixture of described particles of aggregates and hydrophobic resin composition is not only had to high water blockoff ability through the fracturing propping agents that solidify preparation, but also have higher crush strength, supporting crack effectively, prevents its closure.
Embodiment
Fracturing propping agents provided by the invention are the product through being solidified to form by the mixture that contains particles of aggregates and overlay film binding agent, wherein, described overlay film binding agent is the hydrophobic resin composition that contains epoxy resin and polysiloxane, described polysiloxane links together by coupling agent and at least part of epoxy resin, described coupling agent has at least two isocyanate group, described at least part of epoxy resin has hydroxyl, described polysiloxane has can carry protogenic group, together with one end of described coupling agent is covalently bound with described at least part of epoxy resin by the first coupling part, together with the other end of described coupling agent is covalently bound with polysiloxane by the second coupling part, described the first coupling part is formed by the hydroxyl in the isocyanate group in described coupling agent and described at least part of epoxy resin, described the second coupling part is formed by the protogenic group of can carrying in the isocyanate group in described coupling agent and polysiloxane.
According to the present invention, the hydroxyl in described epoxy resin is used for reacting with coupling agent, and then epoxy resin and polysiloxane are connected together by chemical bond-linking.The content of described hydroxyl can carry out appropriate selection according to the amount of the polysiloxane of expection.The angle of the water plugging property of the fracturing propping agents of being prepared by described hydrophobic resin composition from further raising, the hydroxyl value of described epoxy resin is preferably 0.02-0.4mol/100g, more preferably 0.04-0.2mol/100g.The epoxy resin that hydroxyl value meets above-mentioned requirements can be commercially available, and also can adopt the conventional the whole bag of tricks in this area synthetic, no longer describes in detail herein.Described hydroxyl value can be measured according to the disclosed method in the 3.1-3.3 joint (thermosetting resin, 4:42-45, nineteen ninety-five) of " epoxy resin hydroxyl value measuring method " such as Huang Biwu, in the description of product of the epoxy resin that also can be available commercially, knows.In the embodiment of the present invention, the hydroxyl value of epoxy resin comes from the description of product of the epoxy resin being commercially available.
According to the present invention, the epoxy group(ing) in described epoxy resin is used for and solidifying agent contact reacts, to form crosslinking structure.The content of epoxy group(ing) in described epoxy resin is so that described hydrophobic resin composition can form on the surface of particles of aggregates the coating layer with some strength is as the criterion.The angle of the crushing strength of the fracturing propping agents of being prepared by described hydrophobic resin composition from further raising, the oxirane value of described epoxy resin is preferably 0.05-0.6mol/100g, more preferably 0.12-0.55mol/100g, more preferably 0.25-0.51mol/100g.
According to the present invention, described polysiloxane can be common various using silica chain link as repeating unit, and has at least one and can carry the polymkeric substance of protogenic group.
The described group that can carry protogenic group and namely have reactive hydrogen, its specific examples can include but not limited to hydroxyl and amido.The described end group that can carry protogenic group and can be used as polysiloxane, also can be used as the side group of described polysiloxane, preferably as the end group of polysiloxane.Described, can carry protogenic group as the end group of polysiloxane time, preferably two end groups of the molecular chain of polysiloxane are and can carry protogenic group.The present invention is not particularly limited for the described content of protogenic group in polysiloxane of can carrying, as long as the composition finally obtaining has good consistency.Usually, the amount that can carry protogenic group in polysiloxane is 5-12 % by weight.Having at least one polysiloxane that can carry protogenic group can be commercially available, and also can adopt common the whole bag of tricks synthetic, no longer describes in detail herein.
On the Siliciumatom of described polysiloxane, be connected with at least one organic group, the present invention is not particularly limited and can selects for conventional for the kind that is connected to the organic group on the Siliciumatom of polysiloxane.For example: the organic group being connected on the Siliciumatom of polysiloxane can be selected from C
1-C
5alkyl and C
6-C
12replacement or unsubstituted phenyl.In the present invention, C
1-C
5the specific examples of alkyl can include but not limited to: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, tert-pentyl and neo-pentyl; C
6-C
12replacement or the specific examples of unsubstituted phenyl can include but not limited to: phenyl, naphthyl, 4-aminomethyl phenyl, 2-aminomethyl phenyl, 2-ethylphenyl and 4-ethylphenyl.Usually, the organic group on the Siliciumatom of described polysiloxane is methyl and/or phenyl.In the time that the organic group on the Siliciumatom of described polysiloxane is methyl and phenyl, the mol ratio between methyl and phenyl can be conventional selection, as 1:0.1-1.
According to the present invention, polysiloxane is used for improving the hydrophobicity as the epoxy resin of matrix resin, thereby makes the fracturing propping agents of being prepared by described hydrophobic resin composition have good water plugging property.In described hydrophobic resin composition, the content of polysiloxane has gratifying hydrophobicity with final fracturing propping agents and is as the criterion.Preferably, with respect to 100 weight part epoxy resin, the content of described polysiloxane is 1-50 weight part.The water plugging property of the fracturing propping agents of being prepared by described hydrophobic resin composition from further raising, the angle that simultaneously also makes epoxy resin and polysiloxane have good consistency is set out, with respect to 100 weight part epoxy resin, the content of described polysiloxane is 2-40 weight part more preferably, more preferably 5-35 weight part.In described hydrophobic resin composition, the content of polysiloxane can be calculated by feed ratio when this hydrophobic resin composition by preparation.
According to the present invention, described coupling agent has at least two isocyanate group, thereby polysiloxane can be linked together by chemical bond and at least part of epoxy resin.Described coupling agent can be for having the compound of at least two isocyanate group in common various molecular structures, its specific examples can include but not limited to: one or more in alkylidene group vulcabond, tolylene diisocyanate, isophorone diisocyanate, diphenylmethanediisocyanate and cyclohexyl diisocyanate.The water blockoff ability of the fracturing propping agents of being prepared by described hydrophobic resin composition from further raising and the angle of crushing strength, described coupling agent is preferably one or more in tolylene diisocyanate, isophorone diisocyanate and cyclohexyl diisocyanate.
According to the present invention, described coupling agent is for being connected together polysiloxane and epoxy resin by chemical bond-linking, and the amount of described coupling agent can be carried out appropriate selection according to the amount of polysiloxane in described hydrophobic resin composition.Particularly, the mol ratio that can carry protogenic group in described coupling agent and described polysiloxane can be 1-1.2:1.Under preferable case, the mol ratio of the hydroxyl in described coupling agent and described epoxy resin is 1-1.2:1.
According to the present invention, described particles of aggregates can be the existing various particulate materials of preparing fracturing propping agents that can be used in, and for example, described particles of aggregates can be selected from one or more in roughing sand, slag, haydite and glass microballon.Wherein, described roughing sand can be both natural silica Sand, can be also artificial silica sand.Described natural silica Sand can be river sand, extra large sand and aeolian sand, is preferably the aeolian sand from desert.
According to the present invention, the mean diameter of described particles of aggregates can in very large range change, and can reasonably select according to actual needs, for example, the mean diameter of described particles of aggregates can be 0.04-5 millimeter, is preferably 0.05-2 millimeter, more preferably 0.1-0.85 millimeter.The mean diameter of described particles of aggregates is to adopt method of sieving to measure., make particles of aggregates measure its mean diameter by the sieve aperture of different size.
According to the present invention, the degree of sphericity of described particles of aggregates can be selected and change in wider scope, and as a rule, degree of sphericity is better, and the flow conductivity after fragmentation is stronger, and therefore, under preferable case, the circularity of described particles of aggregates and sphericity are preferably >=0.6.Wherein, " sphericity " refers to the degree of particle subglobular; " circularity " refers to the relative acutance of grain corner or measuring of curvature.The measuring method of sphericity and circularity is conventionally known to one of skill in the art, for example, can adopt chart method to measure.
According to the present invention, the content of described particles of aggregates and overlay film binding agent can be selected and change in wider scope, and for example, with respect to particles of aggregates described in 100 weight parts, the amount of described overlay film binding agent can be 1-10 weight part, is preferably 2-8 weight part.
In addition, the present invention also provides a kind of preparation method of fracturing propping agents, the method comprises and will contain the mixture solidified of particles of aggregates and overlay film binding agent, wherein, described overlay film binding agent is the hydrophobic resin composition that contains epoxy resin and polysiloxane, described polysiloxane links together by coupling agent and at least part of epoxy resin, described coupling agent has at least two isocyanate group, described at least part of epoxy resin has hydroxyl, described polysiloxane has can carry protogenic group, together with one end of described coupling agent is covalently bound with described at least part of epoxy resin by the first coupling part, together with the other end of described coupling agent is covalently bound with polysiloxane by the second coupling part, described the first coupling part is formed by the hydroxyl in the isocyanate group in described coupling agent and described at least part of epoxy resin, described the second coupling part is formed by the protogenic group of can carrying in the isocyanate group in described coupling agent and polysiloxane.
According to the present invention, described hydrophobic resin composition can adopt existing the whole bag of tricks to prepare, under preferable case, the preparation method of described hydrophobic resin composition comprises that epoxy resin and coupling agent are carried out to first to be contacted, and the mixture obtaining and polysiloxane are carried out to second contact, described at least part of epoxy resin has hydroxyl, described polysiloxane has can carry protogenic group, described coupling agent has at least two isocyanate group, the condition of described the first contact makes the part isocyanate group in hydroxyl and the described coupling agent in epoxy resin form covalently bound, the condition of described the second contact makes the remaining isocyanate group in protogenic group and described coupling agent of can carrying in described polysiloxane form covalently bound.
According to the present invention, the kind of described epoxy resin, polysiloxane, coupling agent and particles of aggregates is described in detail above, repeats no more herein.
The present invention is not particularly limited with the second condition contacting described the first contact, under optimum condition, described first contact with the second condition contacting make epoxy group(ing) in epoxy resin substantially not with described coupling agent in isocyanate group react.Can the hydroxyl in isocyanate group and the epoxy resin in described coupling agent be reacted by controlling the temperature of the first contact, and substantially not with epoxy resin in epoxy group(ing) react, for example: can make described the first contact contact with second at the temperature of each comfortable 50-90 DEG C and carry out, preferably make described first to contact and second contact at the temperature of 50-70 DEG C and carry out.Described the first contact can be carried out appropriate selection according to the concrete kind of the reactant that carries out the temperature of this contact and react with the second time contacting, preferably, the time of described the first contact is 1-3 hour, and the time of described the second contact is 1-8 hour.
According to the present invention, described the first contact contacts with second preferably to be carried out under the existence of at least one solvent, can regulate the severe degree of reaction more easily so on the one hand, can also make on the other hand the contact of each reactant more abundant.Described solvent can be various can either dissolved epoxy, can dissolve again the liquid of coupling agent and polysiloxane.Particularly, described solvent can be selected from toluene, butanols (comprising its isomer, for example 1-propyl carbinol and the trimethyl carbinol) and butanone.
The consumption of described solvent can be conventional selection.Usually, with respect to 100 weight part matrix resins, the consumption of described solvent can be 50-200 weight part.
According to the present invention, described the first contact contacts with described second while carrying out under the existence of at least one solvent, and method of the present invention also comprises the solvent removing in the mixture that the second contact obtains.Can adopt the conventional the whole bag of tricks in this area to remove described solvent, for example: underpressure distillation.
According to the present invention, the consumption of described overlay film binding agent is as the criterion forming coating layer on the surface of particles of aggregates.Usually, with respect to particles of aggregates described in 100 weight parts, the amount of described overlay film binding agent can be 1-10 weight part, is preferably 2-8 weight part.
According to the present invention, in the process of preparing fracturing propping agents, can also optionally add epoxy curing agent according to practical situation.Particularly, described epoxy curing agent can be selected from conventional various amine curing agent and/or the acid anhydride type curing agents that can make epoxy resin generation crosslinking reaction.Its specific examples can include but not limited to: Tetra hydro Phthalic anhydride, trimellitic anhydride, pyromellitic acid anhydride, Benzophenone carboxylic acid dianhydride, MALEIC ANHYDRIDE, tung oil acid anhydride, alkylene Succinic anhydried, tetrahydrophthalic anhydride, HHPA, methyl tetrahydro phthalic anhydride, methyl hexahydrophthalic anhydride, norbornene dicarboxylic anhydride, Pyroglutaric acid, terpenes acid anhydrides, tetrahydrotoluene tetracarboxylic dianhydride, dodecenylsuccinic acid acid anhydride, poly-nonane diacid acid anhydride, poly sebacic polyanhydride, PHT4, tetrachlorophthalic anhydride, trimellitic anhydride glycol ester, trimellitic anhydride glyceryl ester, sulfobenzide tetracarboxylic dianhydride, quadrol, diethylenetriamine, two amido sulfobenzides, two amido ditanes, mphenylenediamine, Dyhard RU 100, polyetheramine, diethylenetriamine, hexanediamine, trimethylhexamethylenediamine and tetraethylene pentamine.Preferably, described epoxy curing agent is selected from tetrahydrophthalic anhydride, HHPA, two amido ditanes, diethylenetriamine and Dyhard RU 100.
The consumption of described epoxy curing agent can carry out appropriate selection according to its kind, so that the epoxy resin in described hydrophobic resin composition can solidify, and the fracturing propping agents that make finally to obtain have certain intensity and are as the criterion.Usually, the consumption of described epoxy curing agent can be this solidifying agent theoretical consumption 0.9-1.2 doubly.Can adopt known the whole bag of tricks to determine the theoretical consumption of solidifying agent.For example, in the time that described epoxy curing agent is amine curing agent, can calculate its theoretical consumption by following formula:
W=(M/H
n)×E，
Wherein, W is the quality of the needed solidifying agent of every 100g epoxy resin, g;
M is the molecular weight of solidifying agent;
H
nfor the number of reactive hydrogen on amido in each solidifying agent molecule;
E is the oxirane value of epoxy resin, mol/100g.
Again for example, in the time that described epoxy curing agent is acid anhydride type curing agent, can calculate by following formula the theoretical consumption of solidifying agent:
W=A
E×E×K，
Wherein, W is the quality of the needed solidifying agent of every 100g epoxy resin, g;
A
efor the molecular weight of acid anhydrides;
E is the oxirane value of epoxy resin, mol/100g;
K is an empirical value within 0.5-1.1, is generally 0.85.
According to the present invention, described curing condition can be that the routine of this area is selected, and as a rule, described curing condition can comprise solidification value and set time.Described solidification value can suitably be selected according to the kind of the solidifying agent of selecting, and as a rule, in the time that described curing temperature is 100-250 DEG C, just can make described solidifying carry out smoothly.As a rule, the prolongation of described set time is conducive to solidify more completely, but set time, the long amplitude that state of cure is improved was also not obvious, therefore, considered effect and efficiency, was preferably 0.05-0.5 hour described set time.
From avoiding between particles of aggregates the angle of bonding mutually, be solidificated under the condition of following stirring described in preferably and carry out.
Describe the present invention in detail below in conjunction with embodiment.
In following examples and comparative example, according to the method specifying in SY/T5108-2006, the performance of fracturing propping agents is detected.
In following examples and comparative example, adopt following methods to measure the water plugging property of the fracturing propping agents of preparation: the fracturing propping agents of preparation to be filled in to sidewall and to have in scale and the punctulate cylindrical, hollow container of bottom tool, on the upper surface of fracturing propping agents, continue to add water until the bottom of hollow container starts to have water to ooze out, record the height of the water layer on the upper surface of hollow container bottom fracturing propping agents while having water to ooze out, wherein, the height of described hollow container is 1m, and internal diameter is 5cm; The packing height of fracturing propping agents in hollow container is 5cm.The height value of water layer when hollow container bottom has water to ooze out on the upper surface of fracturing propping agents is larger, illustrates that the water plugging property of these fracturing propping agents is better.
Embodiment 1-3 is used for illustrating hydrophobic resin composition and method of making the same of the present invention and application.
Embodiment 1
(1) 100g epoxy resin (is purchased from Langfang Nore letter Chemical Co., Ltd., the trade mark is E-44, oxirane value is 0.44mol/100g, hydroxyl value is 0.088mol/100g) be dissolved in 50g toluene, follow to stir temperature is increased to 50 DEG C, then add 15.3g tolylene diisocyanate, stirring reaction 2 hours at this temperature; Then add 18.7g polysiloxane (be purchased from the special organosilicon material of Dongguan City Aurion company limited, hydroxyl value is 8 % by weight), continue reaction after 2 hours, temperature is increased to 70 DEG C and reacts again 1 hour.The mixture obtaining is carried out at the temperature of 60 DEG C in rotatory evaporator to reduction vaporization, to remove toluene, thereby obtain hydrophobic resin composition of the present invention.
(2) hydrophobic resin composition 100g step (1) being obtained and 2000g roughing sand (are purchased from propping agent company limited of Qingtongxia City Jin Sheng unit, particle diameter is 30-50 order) mix and blend 2 minutes, then add 40g tetrahydrophthalic anhydride and 3g diethylenetriamine, stir 3 minutes at 180 DEG C, then temperature is reduced to room temperature (being 25 DEG C), thereby obtains fracturing propping agents.The performance of these fracturing propping agents is listed in table 1; And the surperficial non-greasy of these fracturing propping agents, illustrates that fracturing propping agents surface does not exist free polysiloxane.
Comparative example 1
Adopt the method identical with embodiment 1 step (2) to prepare fracturing propping agents, different, use the epoxy resin that embodiment 1 step (1) is used to replace hydrophobic resin composition, thereby obtain fracturing propping agents.The performance of these fracturing propping agents is listed in table 1.
Embodiment 2
(1) 100g epoxy resin (is purchased from Langfang Nore letter Chemical Co., Ltd., the trade mark is E-31, oxirane value is 0.31mol/100g, hydroxyl value is 0.166mol/100g) be dissolved in 50g toluene, follow to stir temperature is increased to 50 DEG C, then add 27.6g cyclohexyl diisocyanate, stirring reaction 2 hours at this temperature; Then add 35.3g polysiloxane (to be purchased from the special organosilicon material of Dongguan City Aurion company limited, hydroxyl value is 8 % by weight), continue reaction after 2 hours, the mixture obtaining is carried out at the temperature of 60 DEG C in rotatory evaporator to reduction vaporization, to remove toluene, thereby obtain hydrophobic resin composition of the present invention.
(2) hydrophobic resin composition 160g step (1) being obtained and 2000g roughing sand (are purchased from propping agent company limited of Qingtongxia City Jin Sheng unit, particle diameter is 30-50 order) mix and blend 2 minutes, then add 20g bis-amido ditanes, stir 3 minutes at 180 DEG C, then temperature is reduced to room temperature (being 25 DEG C), thereby obtains fracturing propping agents.The performance of these fracturing propping agents is listed in table 1; And the surperficial non-greasy of these fracturing propping agents, illustrates that fracturing propping agents surface does not exist free polysiloxane.
Embodiment 3
(1) 100g epoxy resin (is purchased from Langfang Nore letter Chemical Co., Ltd., the trade mark is E-51, oxirane value is 0.51mol/100g, hydroxyl value is 0.046mol/100g) be dissolved in 50g toluene, follow to stir temperature is increased to 50 DEG C, then add 10.2g isophorone diisocyanate, stirring reaction 2 hours at this temperature; Then add 9.8g polysiloxane (be purchased from the special organosilicon material of Dongguan City Aurion company limited, hydroxyl value is 8 % by weight), continue reaction after 2 hours, temperature is increased to 70 DEG C and reacts again 1 hour.The mixture obtaining is carried out at the temperature of 60 DEG C in rotatory evaporator to reduction vaporization, to remove toluene, thereby obtain hydrophobic resin composition of the present invention.
(2) hydrophobic resin composition 100g step (1) being obtained and 2000g roughing sand (are purchased from propping agent company limited of Qingtongxia City Jin Sheng unit, particle diameter is 30-50 order) mix and blend 2 minutes, then add 40g tetrahydrophthalic anhydride and 3g Dyhard RU 100, stir 3 minutes at 180 DEG C, then temperature is reduced to room temperature (being 25 DEG C), thereby obtains fracturing propping agents.The performance of these fracturing propping agents is listed in table 1; And the surperficial non-greasy of these fracturing propping agents, illustrates that fracturing propping agents surface does not exist free polysiloxane.
Table 1
Wherein, " sphericity " refers to the degree of proppant particles subglobular; " circularity " refers to the relative acutance of its corner angle or measuring of curvature, adopts chart method to measure; " volume density " refers to the propping agent of unit mass and the ratio of its stacking volume; " volume density " refers to the propping agent of unit mass and the ratio of its particle volume; " turbidity " refers to add the propping agent of certain volume in the distilled water of unit volume, then stirs, and the muddy degree of liquid is called the turbidity of propping agent; " acid solubility " refers at the acid solution of regulation and in the acid-soluble time, determines that certain mass propping agent is by the per-cent of the quality of acid-soluble solution and total propping agent quality; " percentage of damage " refers to the propping agent to certain volume, carries out pressure-bearing test under rated pressure, and definite percentage of damage has characterized the ability of the anti-fragmentation of propping agent.
As can be seen from Table 1, the fracturing propping agents of being prepared by described hydrophobic resin composition not only have good water plugging property, but also have higher crushing strength, and effectively support fracturing crack, prevents its closure.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition each the concrete technical characterictic described in above-mentioned embodiment, in reconcilable situation, can combine by any suitable mode.For fear of unnecessary repetition, the present invention is to the explanation no longer separately of various possible array modes.
In addition, also can carry out arbitrary combination between various embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (10)
1. fracturing propping agents, described fracturing propping agents are the product through being solidified to form by the mixture that contains particles of aggregates and overlay film binding agent, it is characterized in that, described overlay film binding agent is the hydrophobic resin composition that contains epoxy resin and polysiloxane, described polysiloxane links together by coupling agent and at least part of epoxy resin, described coupling agent has at least two isocyanate group, described at least part of epoxy resin has hydroxyl, described polysiloxane has can carry protogenic group, together with one end of described coupling agent is covalently bound with described at least part of epoxy resin by the first coupling part, together with the other end of described coupling agent is covalently bound with polysiloxane by the second coupling part, described the first coupling part is formed by the hydroxyl in the isocyanate group in described coupling agent and described at least part of epoxy resin, described the second coupling part is formed by the protogenic group of can carrying in the isocyanate group in described coupling agent and polysiloxane.
2. fracturing propping agents according to claim 1, wherein, with respect to epoxy resin described in 100 weight parts, the content of described polysiloxane is 1-50 weight part, is preferably 2-40 weight part, more preferably 5-35 weight part.
3. fracturing propping agents according to claim 1, wherein, the content that can carry protogenic group in described polysiloxane is 5-12 % by weight; It is preferably, described that can to carry protogenic group be hydroxyl and/or amido.
4. fracturing propping agents according to claim 1, wherein, described coupling agent is one or more in alkylidene group vulcabond, tolylene diisocyanate, isophorone diisocyanate, diphenylmethanediisocyanate and cyclohexyl diisocyanate, is preferably one or more in tolylene diisocyanate, isophorone diisocyanate and cyclohexyl diisocyanate.
5. fracturing propping agents according to claim 1 and 2, wherein, the hydroxyl value of described epoxy resin is 0.02-0.4mol/100g, oxirane value is preferably 0.05-0.6mol/100g.
6. fracturing propping agents according to claim 1 and 2, wherein, taking the particles of aggregates of 100 weight parts as benchmark, the content of described overlay film binding agent is 1-10 weight part, is preferably 2-8 weight part.
7. the preparation method of fracturing propping agents, the method comprises and will contain the mixture solidified of particles of aggregates and overlay film binding agent, it is characterized in that, described overlay film binding agent is the hydrophobic resin composition that contains epoxy resin and polysiloxane, described polysiloxane links together by coupling agent and at least part of epoxy resin, described coupling agent has at least two isocyanate group, described at least part of epoxy resin has hydroxyl, described polysiloxane has can carry protogenic group, together with one end of described coupling agent is covalently bound with described at least part of epoxy resin by the first coupling part, together with the other end of described coupling agent is covalently bound with polysiloxane by the second coupling part, described the first coupling part is formed by the hydroxyl in the isocyanate group in described coupling agent and described at least part of epoxy resin, described the second coupling part is formed by the protogenic group of can carrying in the isocyanate group in described coupling agent and polysiloxane.
8. preparation method according to claim 7, wherein, the preparation method of described hydrophobic resin composition comprises that epoxy resin and coupling agent are carried out to first to be contacted, and the mixture obtaining and polysiloxane are carried out to second contact, epoxy resin has hydroxyl at least partly, described polysiloxane has can carry protogenic group, described coupling agent has at least two isocyanate group, the condition of described the first contact makes the part isocyanate group in hydroxyl and the described coupling agent in described at least part of epoxy resin form covalently bound, the condition of described the second contact makes the remaining isocyanate group in protogenic group and described coupling agent of can carrying in described polysiloxane form covalently bound.
9. preparation method according to claim 8, wherein, described the first contact contacts with described second at the temperature of each comfortable 50-90 DEG C to be carried out, and at the temperature of preferred each comfortable 50-70 DEG C, carries out.
10. according to the preparation method described in any one in claim 7-9, wherein, described curing condition comprises that solidification value is 100-250 DEG C, and be 0.05-0.5 hour set time.
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