CN103848956A - Hydrophilic resin composite and preparation method and application thereof - Google Patents
Hydrophilic resin composite and preparation method and application thereof Download PDFInfo
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- CN103848956A CN103848956A CN201210504426.1A CN201210504426A CN103848956A CN 103848956 A CN103848956 A CN 103848956A CN 201210504426 A CN201210504426 A CN 201210504426A CN 103848956 A CN103848956 A CN 103848956A
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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: performing first contact of epoxy resin and at least one modifier; and under the conditions being enough to enable an acid to from a salt, performing second contact of a mixture obtained by the first contact and at least one alkaline substance. The modifier has at least one amino and at least one hydrophilic groups, and under the first contact condition, part of epoxy groups in the epoxy resin react with the amino in the modifier, and the hydrophilic groups are selected from carboxylic and sulfonic acid groups. The present invention also provides the application of the hydrophilic resin composition in the preparation of a fracturing propping agent. The fracturing propping agent obtained by coating roughing sand with the hydrophilic resin composition has high crushing resistant strength, 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.
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 the coated quartz sand of hydrophobic resin 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:
Epoxy resin and at least one properties-correcting agent are carried out to first to be contacted, described properties-correcting agent has at least one can carry protogenic group and at least one hydrophilic radical, the condition of described the first contact makes can carry protogenic radical reaction in part epoxy group(ing) in described epoxy resin and described properties-correcting agent, described can to carry protogenic group be amido, and described hydrophilic radical is selected from carboxyl and sulfonic group; And
Be enough to that acid is formed under the condition of salt, the mixture that the first contact is obtained carries out second with at least one alkaline matter and contacts.
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 preparation method who the invention provides a kind of hydrophilic resin oil/fat composition, the method comprises:
Epoxy resin and at least one properties-correcting agent are carried out to first to be contacted, described properties-correcting agent has at least one can carry protogenic group and at least one hydrophilic radical, the condition of described the first contact makes can carry protogenic radical reaction in part epoxy group(ing) in described epoxy resin and described properties-correcting agent, described can to carry protogenic group be amido, and described hydrophilic radical is selected from carboxyl and sulfonic group; And
Be enough to that acid is formed under the condition of salt, the mixture that the first contact is obtained carries out second with at least one alkaline matter and contacts.
The method according to this invention, in the molecular structure of described properties-correcting agent, contain and can carry protogenic group---amido, when with epoxy resin contact reacts, part epoxy group(ing) in amido in described properties-correcting agent and epoxy resin molecular structure reacts, thereby properties-correcting agent and epoxy resin are connected together by chemical bond-linking.In described modifier molecules structure, also contain at least one hydrophilic radical, after this hydrophilic radical salify, can improve the wetting ability of epoxy resin.Described hydrophilic radical is selected from carboxyl and sulfonic group.The quantity of the amido in described properties-correcting agent and the quantity of hydrophilic radical are respectively done for oneself at least one, for example, can respectively do for oneself 1 or 2, preferably respectively do for oneself 1.
Described properties-correcting agent can be carried for have at least one in common various molecular structures simultaneously the compound of protogenic group and at least one hydrophilic radical.Particularly, described properties-correcting agent can be selected from amine with hydrophilic radical (as the primary amine with hydrophilic radical, with the secondary amine of hydrophilic radical), is preferably selected from the C with hydrophilic radical
2-C
10amine (as the C with hydrophilic radical
2-C
10primary amine, with the C of hydrophilic radical
2-C
10secondary amine), be more preferably selected from the C with hydrophilic radical
2-C
10primary amine.Particularly, described properties-correcting agent can be selected from benzaminic acid (as para-amino benzoic acid, anthranilic acid) and aniline sulfonic acid (as Sulphanilic Acid, ORTHO AMINO PHENOL SULPHONIC).
Epoxy group(ing) in described epoxy resin is used for reacting with properties-correcting agent on the one hand, thereby introduces hydrophilic radical in epoxy resin molecular structure, on the other hand for reacting with solidifying agent, to form the product with some strength.The amount of hydrophilic radical and the intensity of cured product that the amount of the epoxy group(ing) in epoxy resin can be introduced on the estimation in epoxy resin molecular structure are carried out appropriate selection.Preferably, the oxirane value of described epoxy resin is 0.2-0.6mol/100g, not only can make like this composition being obtained by method of the present invention there is good wetting ability, and the composition that method of the present invention is obtained solidify after still there is gratifying intensity.
The method according to this invention, the consumption of described properties-correcting agent can carry out appropriate selection according to the amount of the quantity that can carry protogenic group in described properties-correcting agent and the hydrophilic radical introduced in epoxy resin molecular structure of expection.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 that can carry protogenic group in epoxy group(ing) in described epoxy resin and described properties-correcting agent can be 1:0.1-0.6, is preferably 1:0.15-0.3.
The method according to this invention, epoxy resin is not particularly limited with described properties-correcting agent first condition contacting of carrying out, as long as the condition of described the first contact is enough to make part epoxy group(ing) in epoxy resin and can carry that protogenic group reacts and substantially not reacting with the hydrophilic radical in properties-correcting agent in described properties-correcting agent.Usually, described the first contact can be carried out at the temperature of 40-60 DEG C.The time of described the first contact can, according to carrying out the temperature of the first contact and the concrete kind of properties-correcting agent is carried out appropriate selection, be not particularly limited.Preferably, the time of described the first contact is 1-5 hour; More preferably, the time of described the first contact is 1-3 hour.
The method according to this invention, at least one alkaline matter is contacted to the mixture obtaining under the condition that is enough to make acid formation salt carry out the second contact with first, described alkaline matter can contact and the hydrophilic radical reaction introduced in epoxy resin molecular structure with by first, forms salt.
Described alkaline matter can be various can reacting with hydrophilic radical, and the hydrogen in described hydrophilic radical 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 M (OH)
n, 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 amount of hydrophilic radical and the hydrophilicity of expection introduced in epoxy resin by the first contact.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 hydrophilic radical in described alkaline matter and described properties-correcting agent can be 0.3-1:1, is preferably 0.5-1:1, more preferably 0.7-1:1.
The method according to this invention, described the second contact is carried out under the condition that is enough to make hydrophilic radical formation salt.The condition of described the second contact can be conventional selection, as long as can make described alkaline matter and described hydrophilic radical form salt.Particularly, described the second contact can be carried out at the temperature of 25-50 DEG C.The time of described the second contact can be carried out appropriate selection according to the temperature of the second contact, is not particularly limited, and no longer describes in detail herein.
The method according to this 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 for the various epoxy resin that can either dissolve as matrix resin, liquid that again can soluble modified dose.Particularly, described solvent can be selected from toluene, butanols (comprising the various isomer of butanols, as 1-propyl carbinol, the trimethyl carbinol) 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 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.
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 product 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 fracturing liquid 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 specifying 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) be dissolved in 50g toluene, follow to stir temperature is increased to 50 DEG C, then add 6.9g para-amino benzoic acid, stirring reaction 2 hours at this temperature; Then add 3.7g triethylamine, continue reaction after 1 hour, at the temperature of 60 DEG C, use Rotary Evaporators desolvation, 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 DEG C, then temperature is reduced to room temperature (being 25 DEG C), 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-54, and oxirane value is 0.54mol/100g) be dissolved in 50g toluene, follow to stir temperature is increased to 50 DEG C, then add 10.3g para-amino benzoic acid, stirring reaction 2 hours at this temperature; Then add 10.7g tri-n-propyl amine, continue reaction after 1 hour, at the temperature of 60 DEG C, use Rotary Evaporators desolvation, 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) mix and blend 2 minutes, then add 25g 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 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.
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) be dissolved in 50g toluene, follow to stir temperature is increased to 50 DEG C, then add 8.7g Sulphanilic Acid, stirring reaction 2 hours at this temperature; Then add 9.3g tri-n-butyl amine, continue reaction after 1 hour, 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 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.
(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, and effectively support fracturing crack, prevents its closure.
Claims (10)
1. a preparation method for hydrophilic resin oil/fat composition, the method comprises:
Epoxy resin and at least one properties-correcting agent are carried out to first to be contacted, described properties-correcting agent has at least one can carry protogenic group and at least one hydrophilic radical, the condition of described the first contact makes can carry protogenic radical reaction in part epoxy group(ing) in described epoxy resin and described properties-correcting agent, described can to carry protogenic group be amido, and described hydrophilic radical is selected from carboxyl and sulfonic group; And
Be enough to that acid is formed under the condition of salt, the mixture that the first contact is obtained carries out second with at least one alkaline matter and contacts.
2. method according to claim 1, wherein, the mol ratio that can carry protogenic group in the epoxy group(ing) in described epoxy resin and described properties-correcting agent is 1:0.1-0.6, is preferably 1:0.15-0.3.
3. method according to claim 1 and 2, wherein, the oxirane value of described epoxy resin is 0.2-0.6mol/100g.
4. method according to claim 1, wherein, the mol ratio of the hydrophilic radical in described alkaline matter and described properties-correcting agent is 0.3-1:1.
5. according to the method described in any one in claim 1,2 and 4, wherein, described properties-correcting agent is selected from the amine with hydrophilic radical, is preferably selected from the C with hydrophilic radical
2-C
10primary amine, more preferably, described properties-correcting agent is selected from benzaminic acid and aniline sulfonic acid.
6. according to the method described in claim 1 or 4, wherein, described alkaline matter is selected from tertiary amine and 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, more preferably Na, n is 1.
7. method according to claim 1, wherein, described the first contact is carried out at the temperature of 40-60 DEG C, and described the second contact is carried out at the temperature of 25-50 DEG C.
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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Application publication date: 20140611 |