CN103848945A - Hydrophilic resin composition and preparation method and application thereof - Google Patents
Hydrophilic resin composition and preparation method and application thereof Download PDFInfo
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- CN103848945A CN103848945A CN201210504779.1A CN201210504779A CN103848945A CN 103848945 A CN103848945 A CN 103848945A CN 201210504779 A CN201210504779 A CN 201210504779A CN 103848945 A CN103848945 A CN 103848945A
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Abstract
The invention provides a hydrophilic resin composition and a preparation method and application thereof. The preparation method is as follows: under esterification reaction conditions, performing first contact of epoxy resin and a first modifier selected from an unsaturated carboxylic acid and an unsaturated acid anhydride; in the presence of a free radical polymerization initiator, and under carbon-carbon double bond addition reaction conditions, performing second contact of a mixture obtained by the first contact and a second modifier selected from an unsaturated carboxylic acid; and under the conditions being enough to enable an acid to from a salt, performing third contact of a mixture obtained by the second contact and an alkaline substance. A fracturing propping agent obtained by coating roughing sand with the hydrophilic resin composition prepared by the preparation method has good dispersion in a water base fracturing fluid, and basically does not agglutinate; and the water base fracturing fluid carrying the fracturing propping agent is low in bubble content. The fracturing propping agent formed by the hydrophilic resin composition prepared by the preparation method also has high crushing resistant strength, can effectively prop fractures, and prevents the fractures from closed.
Description
Technical field
The present invention relates to a kind of hydrophilic resin composition and method of making the same, the invention still further relates to this hydrophilic resin oil/fat composition in the application of preparing in 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 fracturing liquid, 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.
At present, the more fracturing propping agents of field use are mainly haydite and quartz sand.But the percentage of damage of haydite and quartz sand is high, the haydite crushing in reservoir easily moves, and flow conductivity is poor.The propping agent that adopts the coated quartz sand of hydrophobic resin and obtain is widely used in recent years, for example, in the time gathering oil, adopts hydrophobicity resin-coated quartz sand and the propping agent that obtains can improve the recovery ratio of oil.
But, in actual application, find, compare as the fracturing liquid of propping agent with quartz sand with carrying using haydite, the fracturing liquid that carries the propping agent obtaining with the coated quartz sand of hydrophobic resin need to just can be admitted to underground under higher pumping pressure.
Summary of the invention
Just need to can be admitted to underground problem in order to solve the fracturing liquid that carries the propping agent obtaining with the coated quartz sand of hydrophobic resin under higher pumping pressure; the present inventor conducts in-depth research; find: with adopt haydite or quartz sand as compared with the fracturing liquid of propping agent; adopt in the fracturing liquid of the coated quartz sand of hydrophobic resin as propping agent; propping agent agglomeration is obvious, also contains a large amount of bubbles in concurrent fracturing liquid.The existence of the reunion of propping agent and a large amount of bubbles has increased the difficulty that fracturing liquid is carried, thereby needs higher pumping pressure could the fracturing liquid that carry the propping agent obtaining with the coated quartz sand of hydrophobic resin be sent into underground.
Through great many of experiments; the present inventor finds; the quartz sand that has been coated hydrophilic resin can effectively be solved to propping agent as fracturing propping agents the problem of reuniting occurs in fracturing liquid; simultaneously can also significantly reduce the bubbles volume in fracturing liquid, this fracturing liquid is admitted under can the pumping pressure even lower at the pumping pressure suitable as the fracturing liquid of propping agent with adopting haydite or quartz sand underground.Complete on this basis the present invention.
The preparation method who the invention provides a kind of hydrophilic resin oil/fat composition, the method comprises:
Under esterification condition, epoxy resin is carried out to first with at least one first properties-correcting agent and contact;
Under the existence of at least one radical polymerization initiator, under carbon-carbon double bond addition reaction condition, the mixture that the first contact is obtained carries out second with at least one second properties-correcting agent and contacts; And
Be enough to that acid is formed under the condition of salt, the mixture that the second contact is obtained carries out the 3rd with at least one alkaline matter and contacts;
Described the first properties-correcting agent is selected from unsaturated carboxylic acid and unsaturated acid anhydride, and described the second properties-correcting agent is selected from unsaturated carboxylic acid.
The present invention also provides a kind of hydrophilic resin oil/fat composition of being prepared by method of the present invention.
The present invention further provides hydrophilic resin oil/fat composition according to the present invention in the application of preparing in fracturing propping agents.
The fracturing propping agents that the hydrophilic resin oil/fat composition of being prepared by method of the present invention are coated on to the surface of roughing sand and obtain have good dispersiveness in aqueous fracturing fluid, substantially can not reunite; And it is low to carry air bubble content in the aqueous fracturing fluid of these fracturing propping agents.Thereby, adopt fracturing propping agents prepared by hydrophilic resin oil/fat composition of the present invention can under the pumping pressure quite even lower as the fracturing liquid of propping agent with adopting haydite or quartz sand, be admitted to underground.
And the fracturing propping agents that the hydrophilic resin oil/fat composition of being prepared by method of the present invention forms also have higher crushing strength, supporting crack effectively prevents its closure.
Embodiment
The invention provides a kind of preparation method of hydrophilic resin oil/fat composition, the method is included under esterification condition, epoxy resin is carried out to first with at least one first properties-correcting agent and contact;
Under the existence of at least one radical polymerization initiator, under carbon-carbon double bond addition reaction condition, the mixture that the first contact is obtained carries out second with at least one second properties-correcting agent and contacts; And
Be enough to that acid is formed under the condition of salt, the mixture that the second contact is obtained carries out the 3rd with at least one alkaline matter and contacts;
Described the first properties-correcting agent is selected from unsaturated carboxylic acid and unsaturated acid anhydride, and described the second properties-correcting agent is selected from unsaturated carboxylic acid.
In the molecular structure of epoxy resin, conventionally contain hydroxyl, method of the present invention is carried out first by epoxy resin and at least one first properties-correcting agent and is contacted under esterification condition, carboxyl in described the first properties-correcting agent or anhydride group can react with the hydroxyl in epoxy resin, thereby introduce unsaturated group in epoxy resin molecular structure.The hydroxyl value of epoxy resin can be that the routine of this area is selected.Usually, the hydroxyl value of described epoxy resin can be 0.02-0.4mol/100g, more preferably 0.04-0.4mol/100g.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.
Epoxy group(ing) in described epoxy resin is mainly used in reacting with solidifying agent, to form the product with some strength.The amount of the epoxy group(ing) in epoxy resin is not particularly limited, and can be conventional selection.Usually, the oxirane value of described epoxy resin can be 0.2-0.6mol/100g.
The method according to this invention, described the first properties-correcting agent is selected from unsaturated carboxylic acid and unsaturated acid anhydride.
Described unsaturated carboxylic acid refers to the organic compound that simultaneously contains unsaturated carbon-carbon double bond (,-C=C-) and carboxyl (,-COOH) in molecular structure.In molecular structure as the unsaturated carboxylic acid of the first properties-correcting agent, the quantity of unsaturated carbon-carbon double bond can be more than 1, is preferably 1; The quantity of hydroxy-acid group is generally 1.Be preferably unsaturated aliphatic carboxylic acid as the unsaturated carboxylic acid of the first properties-correcting agent, for example, can be selected from C
3-C
12unsaturated aliphatic carboxylic acid, be more preferably selected from C
3-C
12monobasic unsaturated aliphatic carboxylic acid.Particularly, can be selected from maleic acid, FUMARIC ACID TECH GRADE and methylene-succinic acid as the unsaturated carboxylic acid of the first properties-correcting agent.
Described unsaturated aliphatic acid anhydrides refers to and in molecular structure, contains unsaturated carbon-carbon double bond (,-C=C-) and anhydride group (, simultaneously
) organic compound.In molecular structure as the described unsaturated fatty acids acid anhydrides of the first properties-correcting agent, the quantity of unsaturated carbon-carbon double bond can be more than 1, is preferably 1; The quantity of anhydride group is generally 1.Described unsaturated aliphatic acid anhydrides is preferably unsaturated aliphatic acid anhydrides, for example, can be selected from C
3-C
12unsaturated aliphatic acid anhydrides.Particularly, described unsaturated acid anhydride can be MALEIC ANHYDRIDE.
The method according to this invention, described the first contact is preferably carried out under the existence of at least one radical polymerization inhibitor, can prevent like this unsaturated group polymerization in the first properties-correcting agent.Described radical polymerization inhibitor can be for the conventional various materials that can block free radical, for example, as various phenolic compounds (Resorcinol).The consumption of described radical polymerization inhibitor can carry out appropriate selection according to the amount of unsaturated acid anhydride, is not particularly limited.
Described the first properties-correcting agent is for introducing unsaturated group at epoxy resin molecular structure, and then priority and unsaturated fatty acids and alkali substance reaction, to introduce hydrophilic radical in epoxy resin molecular structure.The consumption of described the first properties-correcting agent is as the criterion can make the wetting ability of the final hydrophilic resin oil/fat composition of preparing meet concrete service requirements.At prepared according to the methods of the invention hydrophilic resin oil/fat composition, during for the preparation of fracturing propping agents, the mol ratio of the hydroxyl in described epoxy resin and described the first properties-correcting agent can be 1:0.1-0.8, is preferably 1:0.3-0.7.
Between described epoxy resin and the first properties-correcting agent first contacts under esterification condition and carries out.Usually, described the first contact can be carried out at the temperature of 90-120 ℃, preferably at the temperature of 95-115 ℃, carries out.The time of described the first contact can be carried out appropriate selection according to the temperature of carrying out the first contact, can make the first properties-correcting agent all or substantially all to react and be as the criterion with epoxy resin.Usually, the time of described the first contact can be 1-5 hour.Described the first contact can for example, be carried out under acidic conditions (: pH value is 2-4).
The method according to this invention, described the second properties-correcting agent, for introduce the functional group that can form hydrophilic radical at epoxy resin molecular structure, is selected from unsaturated carboxylic acid.
The method according to this invention, can be more than 1 as the quantity of the carbon-carbon double bond in the unsaturated carboxylic acid molecular structure of the second properties-correcting agent, is preferably 1; The quantity of carboxyl can be more than 1, for example 1 or 2.Described unsaturated carboxylic acid for example can be selected from C
3-C
10unsaturated fatty acids, its specific examples can include but not limited to: vinylformic acid, methacrylic acid, hexenoic acid, maleic acid and FUMARIC ACID TECH GRADE.
Described the second properties-correcting agent is for carrying out addition reaction with the carbon-carbon double bond of the first modifier molecules structure, thereby in epoxy resin molecular structure, introduce the carboxyl that can further form hydrophilic radical, its consumption can carry out appropriate selection according to the concrete application scenario of the hydrophilic resin oil/fat composition of final preparation.Particularly, at prepared according to the methods of the invention hydrophilic resin oil/fat composition, during for the preparation of fracturing propping agents, the mol ratio of described the first properties-correcting agent and described the second properties-correcting agent can be 1:0.5-10, is preferably 1:1-5, more preferably 1:1-2.
The method according to this invention, described first contacts second between the mixture that obtains and the second properties-correcting agent contacts under the existence of at least one radical polymerization initiator and carries out.Described radical polymerization initiator can be the conventional various materials that can make carbon-carbon double bond carry out addition reaction, for example: described radical polymerization initiator can be selected from azo-type radical polymerization initiator and peroxide type radical polymerization initiator.Particularly, described radical polymerization initiator can be selected from Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), dibenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide and dilauroyl peroxide.
The consumption of described radical polymerization initiator can carry out appropriate selection according to the consumption of the first properties-correcting agent or the second properties-correcting agent.Usually, the consumption of described radical polymerization initiator can be the 0.01-1 % by weight of the amount of described the second properties-correcting agent.
Described the second contact is carried out under carbon-carbon double bond addition reaction condition.Particularly, described the second contact can be carried out at the temperature of 50-90 ℃, preferably at the temperature of 60-90 ℃, carries out.The time of described the second contact can be carried out appropriate selection according to the temperature of the second contact, so that the second properties-correcting agent can complete reaction be as the criterion, for example, can be 1-8 hour.
Described alkaline matter can be various can reacting with carboxyl, and the hydrogen ion contacting with second by the first contact in the carboxyl of introducing in epoxy resin molecular structure is replaced by other positively charged ion, thereby forms the material of salt.For example, described alkaline matter can be selected from tertiary amine and/or M (OH)
2, wherein, M is selected from alkali and alkaline earth metal ions, and n is 1 or 2.
Described tertiary amine is preferably suc as formula shown in I,
In formula I, R
1, R
2and R
3c respectively does for oneself
1-C
5straight or branched alkyl.
Described C
1-C
5the specific examples of straight or branched 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.
M (OH)
nin M be preferably basic metal (as Na or K), more preferably Na, n is 1.
Particularly, described alkaline matter can be selected from Trimethylamine 99, triethylamine, tripropyl amine, Tributylamine, sodium hydroxide and potassium hydroxide.
The method according to this invention, the amount of described alkaline matter can be carried out appropriate selection according to the hydrophilicity of the amount of the carboxyl in the second properties-correcting agent and expection.At prepared according to the methods of the invention hydrophilic resin oil/fat composition, during for the preparation of fracturing propping agents, described the second properties-correcting agent is in carboxyl, and the mol ratio of described alkaline matter and described the second properties-correcting agent can be 0.4-1:1, is preferably 0.5-1:1.In the time that described the first properties-correcting agent is unsaturated acid anhydride, can in epoxy resin molecular structure, introduce unsaturated group on the one hand by the first contact, also in epoxy resin molecular structure, introduce carboxyl, therefore the amount of the carboxyl in epoxy resin is for contacting the total amount of the carboxyl of introducing in epoxy resin molecular structure with second by the first contact simultaneously.Contain unsaturated acid anhydride at described the first properties-correcting agent, described the first properties-correcting agent is in acid anhydrides, and described the second properties-correcting agent is in carboxyl, in mole, the ratio of the total amount of the amount of described alkaline matter and described the first properties-correcting agent and the second properties-correcting agent is 0.4-1:1.
The method according to this invention, described the 3rd contact is carried out under the condition that is enough to make acid formation salt, can be conventional selection.Particularly, described the 3rd contact can be carried out at the temperature of 25-80 ℃.The time of described the 3rd contact can be carried out appropriate selection according to the temperature of the 3rd contact, is not particularly limited, and no longer describes in detail herein.
The method according to this invention, described the first contact, the second contact contact with the 3rd preferably and carry 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 the various epoxy resin that can either dissolve as matrix resin, can dissolve again the liquid of the first properties-correcting agent and the second properties-correcting agent.Particularly, described solvent can be selected from toluene, butanols (comprising the various isomer of butanols, as 1-propyl carbinol and the trimethyl carbinol), butyl glycol ether (comprising ethylene glycol monobutyl ether and ethylene glycol bis butyl ether) and butanone.
The consumption of described solvent can be conventional selection.Usually, with respect to 100 weight part epoxy resin, the consumption of described solvent can be 50-200 weight part.
The method according to this invention, described the first contact, described the second contact contacts with the described the 3rd 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 3rd contact obtains.Can adopt the conventional the whole bag of tricks in this area to remove described solvent, for example: underpressure distillation.
The present invention also provides the hydrophilic resin of being prepared by method of the present invention oil/fat composition.
Adopt the coated roughing sand of hydrophilic resin oil/fat composition prepared by method of the present invention and be cured after the material that obtains there is high intensity and in water, there is good dispersiveness, contain air bubble content in the water of this cured article low simultaneously, be particularly suitable for as fracturing propping agents.
Thus, the present invention further provides hydrophilic resin oil/fat composition according to the present invention in the application of preparing in fracturing propping agents.Described fracturing propping agents are the product through being solidified to form by the mixture that contains roughing sand and overlay film binding agent, and wherein, described overlay film binding agent is hydrophilic resin oil/fat composition provided by the invention.The surface of the fracturing propping agents of being prepared by hydrophilic resin oil/fat composition of the present invention has the coating layer being formed by hydrophilic resin oil/fat composition of the present invention, not only there is higher crushing strength, and in aqueous fracturing fluid, demonstrate good dispersiveness, contain air bubble content in the aqueous fracturing fluid of these fracturing propping agents low simultaneously.
According to the present invention, 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.The average particulate diameter of described roughing sand can be determined according to concrete service requirements.Usually, the average particulate diameter of described roughing sand can be 0.04-5 millimeter, is preferably 0.05-2 millimeter, more preferably 0.1-0.85 millimeter.The median size of roughing sand is to adopt method of sieving to measure., make roughing sand measure the median size of silica sand by the sieve aperture of different size.
The degree of sphericity of roughing sand is better, still can keep certain flow conductivity after fragmentation; Relative density is low, constructability pumping, and therefore, under preferable case, circularity and the sphericity of described roughing sand be preferably >=and 0.6.Wherein, " sphericity " refers to the degree of particle subglobular; " circularity " refers to the relative acutance of grain corner or measuring of curvature, and 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.Circularity and the sphericity of the roughing sand using in the embodiment of the present invention are more than 0.6.
The consumption of described overlay film binding agent is as the criterion forming coating layer on the surface of roughing sand.Usually, with respect to roughing sand 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.
Can adopt ordinary method to prepare described fracturing propping agents.Particularly, at least one epoxy curing agent can be mixed with roughing sand and hydrophilic resin oil/fat composition of the present invention, and the mixture obtaining is cured.
Described epoxy curing agent can be conventional selection.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 hydrophilic resin oil/fat 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.
Described curing temperature can be carried out appropriate selection according to the kind of the solidifying agent of selecting, and no longer describes in detail herein.
From avoiding between roughing sand 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 stipulating in SY/T5108-2006, the percentage of damage of fracturing propping agents is measured.
Embodiment 1-3 is for illustrating according to hydrophilic 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-21, and oxirane value is 0.21mol/100g, and hydroxyl value is 0.226mol/100g) be dissolved in 50g toluene, add 0.003g Resorcinol, the pH value of reaction solution is adjusted to 3.Follow to stir temperature is increased to 100 ℃, then add 9.8g MALEIC ANHYDRIDE, stirring reaction 2 hours at this temperature; Then temperature is adjusted to 80 ℃, in reaction mixture, adds 7.2g vinylformic acid and 0.022g Diisopropyl azodicarboxylate, continue reaction after 2 hours, temperature is adjusted to 40 ℃, in the mixture obtaining, add 20.2g triethylamine, continue stirring reaction 0.5 hour; The mixture obtaining is carried out at the temperature of 60 ℃ in rotatory evaporator to reduction vaporization, to remove toluene, thereby obtain hydrophilic resin oil/fat composition of the present invention.
(2) hydrophilic resin oil/fat 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 25g tetrahydrophthalic anhydride and 3g diethylenetriamine, stir 3 minutes at 180 ℃, then temperature is reduced to room temperature (being 25 ℃), thereby obtains fracturing propping agents.The crush resistance of these fracturing propping agents can be listed in table 1.
(3) fracturing propping agents of being prepared by 5g step (2) drop into and are equipped with in the graduated cylinder of 1L water, observe: fracturing propping agents are not substantially reunited in sinking process, and in sinking process and be deposited on that the bubble on fracturing propping agents surface of graduated cylinder bottom is few and diameter is less (for being less than 3mm).This phenomenon is with that haydite is dropped into the phenomenon producing in water is basic identical, show to carry these fracturing propping agents fracturing liquid can with the basic identical even less pumping pressure of the fracturing liquid that carries haydite under be admitted to underground.
Comparative example 1
Adopt the method identical with embodiment 1 to prepare fracturing propping agents, different, the epoxy resin using by embodiment 1 step (1) replaces the hydrophilic resin oil/fat composition in embodiment 1 step (2).The crush resistance of the fracturing propping agents that obtain can be listed in table 1.
Fracturing propping agents prepared by 5g comparative example 1 drop into and are equipped with in the graduated cylinder of 1L water, observe: fracturing propping agents are reunited in sinking process, and in sinking process and be deposited on many and large (for being greater than 3mm) of diameter of the bubble on fracturing propping agents surface of graduated cylinder bottom.Showing to carry the fracturing liquid of these fracturing propping agents just can be admitted under need to the pumping pressure larger at the fracturing liquid than carrying haydite underground.
Embodiment 2
(1) 100g epoxy resin (is purchased from Langfang Nore letter Chemical Co., Ltd., the trade mark is E-51, and oxirane value is 0.51mol/100g, and hydroxyl value is 0.046mol/100g) be dissolved in 50g toluene, add 0.001g Resorcinol, the pH value of reaction solution is adjusted to 2.Follow to stir temperature is increased to 100 ℃, then add 3.0g MALEIC ANHYDRIDE, stirring reaction 2 hours at this temperature; Then temperature is adjusted to 80 ℃, in reaction mixture, add 5.2g methacrylic acid and 0.016g Diisopropyl azodicarboxylate, continue reaction after 2 hours, temperature is adjusted to 40 ℃, in the mixture obtaining, add 12.9g tri-n-propyl amine, continue stirring reaction 0.5 hour; The mixture obtaining is carried out at the temperature of 60 ℃ to reduction vaporization in rotatory evaporator, to remove toluene, thereby obtain hydrophilic resin oil/fat composition of the present invention.
(2) hydrophilic resin oil/fat 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 30g bis-amido ditanes, stir 3 minutes at 180 ℃, then temperature is reduced to room temperature (being 25 ℃), thereby obtains fracturing propping agents.The crushing strength of these fracturing propping agents is listed in table 1.
(3) fracturing propping agents of being prepared by 5g step (2) drop into and are equipped with in the graduated cylinder of 1L water, observe: fracturing propping agents are not substantially reunited in sinking process, and in sinking process and be deposited on that the bubble on fracturing propping agents surface of graduated cylinder bottom is few and diameter is less (for being less than 3mm).This phenomenon is with that haydite is dropped into the phenomenon producing in water is basic identical, show to carry these fracturing propping agents fracturing liquid can with the basic identical even less pumping pressure of the fracturing liquid that carries haydite under be admitted to underground.
Embodiment 3
(1) 100g epoxy resin (is purchased from Langfang Nore letter Chemical Co., Ltd., the trade mark is E-44, and oxirane value is 0.44mol/100g, and hydroxyl value is 0.088mol/100g) be dissolved in 50g toluene, add 0.0015g Resorcinol, the pH value of reaction solution is adjusted to 4.Follow to stir temperature is increased to 100 ℃, then add 4.9g MALEIC ANHYDRIDE, stirring reaction 2 hours at this temperature; Then temperature is adjusted to 80 ℃, in reaction mixture, add 5.8g maleic acid and 0.017g Diisopropyl azodicarboxylate, continue reaction after 2 hours, temperature is adjusted to 40 ℃, in the mixture obtaining, add 27.8g tri-n-butyl amine, continue stirring reaction 0.5 hour; The mixture obtaining is carried out at the temperature of 60 ℃ to reduction vaporization in rotatory evaporator, to remove toluene, thereby obtain hydrophilic resin oil/fat composition of the present invention.
(2) hydrophilic resin oil/fat 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 30g tetrahydrophthalic anhydride and 3g diethylenetriamine, stir 3 minutes at 180 ℃, then temperature is reduced to room temperature (being 25 ℃), thereby obtains fracturing propping agents.The crushing strength of these fracturing propping agents is listed in table 1.
(3) fracturing propping agents of being prepared by 5g step (2) drop into and are equipped with in the graduated cylinder of 1L water, observe: fracturing propping agents are not substantially reunited in sinking process, and in sinking process and be deposited on that the bubble on fracturing propping agents surface of graduated cylinder bottom is few and diameter is less (for being less than 3mm).This phenomenon is with that haydite is dropped into the phenomenon producing in water is basic identical, show to carry these fracturing propping agents fracturing liquid can with the basic identical even less pumping pressure of the fracturing liquid that carries haydite under be admitted to underground.
Table 1
Wherein, " 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.
Can find out from embodiment 1-3 and comparative example 1, the fracturing propping agents of being prepared by hydrophilic resin oil/fat composition of the present invention have good dispersibility in water, and the air bubble content in the water that contains fracturing propping agents of the present invention is low, show that the fracturing liquid that carries the fracturing propping agents of being prepared by hydrophilic resin oil/fat composition of the present invention is easy to pumping, can with carry under the basic identical even less pressure of fracturing liquid of haydite as propping agent, be pumped to underground.Meanwhile, the fracturing propping agents of being prepared by hydrophilic resin oil/fat composition of the present invention also have higher crushing strength, effectively support fracturing crack.
Claims (10)
1. a preparation method for hydrophilic resin oil/fat composition, the method comprises:
Under esterification condition, epoxy resin is carried out to first with at least one first properties-correcting agent and contact;
Under the existence of at least one radical polymerization initiator, under carbon-carbon double bond addition reaction condition, the mixture that the first contact is obtained carries out second with at least one second properties-correcting agent and contacts; And
Be enough to that acid is formed under the condition of salt, the mixture that the second contact is obtained carries out the 3rd with at least one alkaline matter and contacts;
Described the first properties-correcting agent is selected from unsaturated carboxylic acid and unsaturated acid anhydride, and described the second properties-correcting agent is selected from unsaturated carboxylic acid.
2. method according to claim 1, wherein, the mol ratio of the hydroxyl in described epoxy resin and described the first properties-correcting agent is 1:0.1-0.8;
The mol ratio of described the first properties-correcting agent and described the second properties-correcting agent is 1:0.5-10;
Described the first properties-correcting agent is unsaturated carboxylic acid, and described the second properties-correcting agent is in carboxyl, and the mol ratio of described alkaline matter and described the second properties-correcting agent is 0.4-1:1; Or described the first properties-correcting agent contains unsaturated acid anhydride, described the first properties-correcting agent is in acid anhydrides, and described the second properties-correcting agent is in carboxyl, in mole, the ratio of the total amount of the amount of described alkaline matter and described the first properties-correcting agent and the second properties-correcting agent is 0.4-1:1.
3. method according to claim 1 and 2, wherein, described the first properties-correcting agent is selected from C
3-C
12unsaturated fatty acids and C
3-C
12unsaturated fatty acids acid anhydrides, be preferably selected from MALEIC ANHYDRIDE, maleic acid, FUMARIC ACID TECH GRADE and methylene-succinic acid;
Described the second properties-correcting agent is selected from C
3-C
12unsaturated fatty acids, be preferably selected from vinylformic acid, methacrylic acid, hexenoic acid, maleic acid and FUMARIC ACID TECH GRADE.
4. method according to claim 1 and 2, wherein, the hydroxyl value of described epoxy resin is 0.02-0.4mol/100g, oxirane value is preferably 0.2-0.6mol/100g.
5. method according to claim 1 and 2, wherein, described alkaline matter is selected from tertiary amine and/or M (OH)
n, M is selected from alkali and alkaline earth metal ions, and n is 1 or 2;
Described tertiary amine is preferably suc as formula shown in I,
In formula I, R
1, R
2and R
3c respectively does for oneself
1-C
5straight or branched alkyl;
M (OH)
nin M be preferably basic metal, n is 1; More preferably, M is Na.
6. method according to claim 1, described radical polymerization initiator is selected from azo-type radical polymerization initiator and peroxide type radical polymerization initiator.
7. method according to claim 1, wherein, described the first contact is carried out at the temperature of 90-120 ℃, and described the second contact is carried out at the temperature of 50-90 ℃, and described the 3rd contact is carried out at the temperature of 25-50 ℃.
8. the hydrophilic resin oil/fat composition that in claim 1-7 prepared by the method described in any one.
9. hydrophilic resin oil/fat composition claimed in claim 8 is in the application of preparing in fracturing propping agents.
10. application according to claim 9, wherein, described fracturing propping agents are the product through being solidified to form by the mixture that contains roughing sand and overlay film binding agent, described overlay film binding agent is hydrophilic resin oil/fat composition claimed in claim 8, with respect to roughing sand described in 100 weight parts, the amount of described overlay film binding agent is preferably 1-10 weight part, more preferably 2-8 weight part.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109786620A (en) * | 2018-12-13 | 2019-05-21 | 武汉中兴创新材料技术有限公司 | A kind of coated film and its preparation method and application |
| CN114395089A (en) * | 2022-01-14 | 2022-04-26 | 东莞市比翼新材料科技有限公司 | Compression molding type vinyl resin and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1434063A (en) * | 2003-02-13 | 2003-08-06 | 海洋化工研究院 | Aqueous epoxy modified acrylic heat-reflecting thermo-insulating coating |
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2012
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1434063A (en) * | 2003-02-13 | 2003-08-06 | 海洋化工研究院 | Aqueous epoxy modified acrylic heat-reflecting thermo-insulating coating |
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| 高旺来等: "一种树脂覆膜砂支撑剂的研究及现场应用", 《油田化学》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109786620A (en) * | 2018-12-13 | 2019-05-21 | 武汉中兴创新材料技术有限公司 | A kind of coated film and its preparation method and application |
| CN114395089A (en) * | 2022-01-14 | 2022-04-26 | 东莞市比翼新材料科技有限公司 | Compression molding type vinyl resin and preparation method thereof |
| CN114395089B (en) * | 2022-01-14 | 2024-04-16 | 东莞市比翼新材料科技有限公司 | Molded vinyl resin and preparation method thereof |
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