CN111072511B - Quaternary ammonium salt surfactant and preparation method and application thereof - Google Patents
Quaternary ammonium salt surfactant and preparation method and application thereof Download PDFInfo
- Publication number
- CN111072511B CN111072511B CN201811212800.4A CN201811212800A CN111072511B CN 111072511 B CN111072511 B CN 111072511B CN 201811212800 A CN201811212800 A CN 201811212800A CN 111072511 B CN111072511 B CN 111072511B
- Authority
- CN
- China
- Prior art keywords
- formula
- quaternary ammonium
- group
- compound represented
- ammonium salt
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C235/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms
- C07C235/02—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton
- C07C235/04—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton being acyclic and saturated
- C07C235/10—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton being acyclic and saturated having the nitrogen atom of at least one of the carboxamide groups bound to an acyclic carbon atom of a hydrocarbon radical substituted by nitrogen atoms not being part of nitro or nitroso groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C245/00—Compounds containing chains of at least two nitrogen atoms with at least one nitrogen-to-nitrogen multiple bond
- C07C245/02—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides
- C07C245/06—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides with nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings
- C07C245/08—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides with nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings with the two nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings, e.g. azobenzene
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
-
- 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
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a quaternary ammonium salt surfactant, a preparation method and application thereof. The quaternary ammonium salt surfactant of the present invention, and a combination thereofThe structure is shown in formula (I):
wherein the definition of each group is shown in the specification. The quaternary ammonium salt surfactant can be used as a high-efficiency low-consumption wetting agent for the field of tertiary oil recovery. In the tertiary oil recovery process, the quaternary ammonium salt surfactant can effectively convert the surface of a carbonate reservoir wrapped by crude oil into water wettability or neutral wettability to realize wettability reversal, thereby being beneficial to the improvement of oil washing efficiency.
Description
Technical Field
The invention relates to a quaternary ammonium salt surfactant, in particular to a quaternary ammonium salt surfactant with high efficiency and low consumption.
Background
Oligomeric surfactants are amphiphilic molecules containing two, three or more amphiphiles in the molecule, wherein the amphiphiles in the molecule are linked together by means of a linking group in a chemical bond manner at or near the head group. Compared with the traditional single-chain surfactant, the increase of the polymerization degree enables the synergistic effect among a plurality of amphiphilic elements in the oligomeric surfactant molecule to be stronger, thereby showing excellent performances with high efficiency and low consumption, and being expected to become a new-generation surfactant. On the other hand, CN 105561865A suggests that a dendritic surfactant has a higher oil removing ability and a higher ability to lower the oil-water interfacial tension than a linear oligomeric surfactant. Therefore, by adjusting the degree of oligomerization and the structure of the linking group, an oligomeric surfactant having excellent properties can be obtained.
At present, the synthesis of the oligomeric quaternary ammonium salt surfactant generally takes multi-level alcohol or multi-level amine as raw materials, and the linear or branched oligomeric quaternary ammonium salt surfactant is prepared through two-step reactions of amidation and quaternization. For example, the literature (Langmuir, 2010,26, 7922-7927) discloses a method for preparing a dendritic trimeric quaternary ammonium salt surfactant by using tris (2-aminoethyl) amine as a raw material through two steps of reactions of amidation and quaternization. The method has the main problems that chloroacetyl chloride which has high toxicity and is easy to inactivate when meeting water is used in the amidation reaction of polyamine, and the reaction conditions are harsh. In addition, the literature (Colloids surf. A,2014,457, 374-381) discloses a method for preparing star-shaped trimeric quaternary ammonium salt surfactant by taking tris (hydroxyethyl) amine as a raw material and through two steps of reactions of amidation and quaternization. The method needs bromoacetyl bromide during amidation reaction, and also has harsh reaction conditions, thus being not beneficial to industrial production.
In general, the method of synthesizing the oligomeric quaternary ammonium salt surfactant by two-step reaction of amidation and quaternization using polyol or polyamine as a starting material has the following disadvantages: (1) The polyamine serving as the starting material has strong corrosivity and strong irritation; the reaction activity of the polyhydric alcohol is low, and the solubility of the polyhydric alcohol in an organic solvent is poor; (2) In the reaction process, acyl chloride or acyl bromide with high toxicity is used, and the acyl chloride or the acyl bromide is easy to inactivate when meeting water, so that the reaction condition is harsh. Therefore, it is very critical to further select cheap and green starting materials and optimize the preparation method for expanding the theoretical research and industrial application of the oligomeric quaternary ammonium salt surfactant.
Disclosure of Invention
Aiming at the defects of the prior art, the inventor provides a quaternary ammonium salt surfactant and a preparation method and application thereof through diligent research.
The quaternary ammonium salt surfactant disclosed by the invention has a structure shown as a formula (I):
wherein a L groups, which are identical or different from one another, are each independently selectedFrom optionally substituted m-valent C 1～50 Hydrocarbyl and C 3～50 A heterohydrocarbyl group, m is an integer between 1 and 20 (preferably an integer between 1 and 10), a is an integer between 1 and 20 (preferably an integer between 1 and 10, more preferably 1,2 or 3); n is a radical of an alkyl radical 0 Is composed of
Number of charges of group, n 0 Is an integer of 1 to 20 (preferably an integer of 1 to 10); n X Z- The radicals, equal to or different from each other, are each independently selected from F - 、Cl - 、Br - 、I - And OH - N is an integer of 1 to 20 (preferably an integer of 1 to 10), and Z-is X Z- The number of charges of the group, z is selected from 1,2 or 3; n number of X Z- The absolute value of the total number of charges of the radical being equal to n 0 ；
In formula (I), b A groups, which are identical or different from each other, are each independently selected from hydrogen, optionally substituted C 1～20 A linear or branched alkyl group and a group of formula (II), at least one A group being selected from the group of formula (II); b is an integer of between 1 and 20 (preferably an integer of between 2 and 10, more preferably 2, 3, 4, 5 or 6);
in the group of formula (II), the L 'group is selected from optionally substituted n' valent C 1～50 Hydrocarbyl and C 3～50 A heterohydrocarbyl group; n 'repeating units are the same or different from each other, and n' is an integer of 1 to 20 (preferably an integer of 1 to 10); r of n' repeating units 0 Each independently selected from hydrogen, optionally substituted C 1～20 Straight or linear alkyl and optionally substituted C 3～20 Straight or branched heteroalkyl (preferably selected from C) 1～20 Straight or linear alkyl); each of the m ' repeating units a ', b ', c ', d ', which are the same or different from each other, is independently selected from an integer of 0 to 5 (preferably 0, 1 or 2), and at least one a ' is an integer of 1 to 5 and at least one d ' is an integer of 1 to 5; m' pieces are heavyEach R in the complex unit 1 Each independently selected from hydrogen, optionally substituted C 1～20 Straight or linear alkyl, optionally substituted C 3～20 A linear or linear heteroalkyl group and a group of formula (III); each R of m' repeating units 2 Each independently selected from optionally substituted C 1～20 Straight or branched alkylene and optionally substituted C 3～20 Linear or linear heteroalkylene; m' is an integer of 1 to 20 (preferably an integer of 1 to 10); * Represents the bonding end of the group of formula (II) to the L group of formula (I); Δ represents the binding end of the group of formula (II) to which the R group of formula (I) is bonded;
in the formula (III), the groups and symbols are as defined in the formula (II), and R's in the m' repeating units 1 ' each is independently selected from hydrogen, optionally substituted C 1～20 Straight or linear alkyl, optionally substituted C 3～20 A linear or linear heteroalkyl group and a group of formula (III) (preferably each independently selected from hydrogen, optionally substituted C 1～20 Straight or linear alkyl and optionally substituted C 3～20 Linear or linear heteroalkyl);
c R groups are each independently selected from optionally substituted m b C of valence 1～50 Hydrocarbyl or C 3～50 Heterocarbyl (preferably optionally substituted m) b C of valence 1～20 Straight or branched alkyl and C 3～20 Linear or branched heteroalkyl), m b Is an integer of 1 to 20 (preferably an integer of 1 to 10); c is an integer of 1 to 20 (preferably an integer of 1 to 10, more preferably 1,2, 3, 4 or 5);
the number of (hydrocarbyl) bonded ends present in the a L groups is the same as the number of (carbonyl) bonded ends present in the b a groups, the a L groups being bonded to each other via their (hydrocarbyl) bonded ends to the (carbonyl) bonded ends of the b a groups;
the number of tertiary amine nitrogen atoms present in the b A groups is greater than the number of (hydrocarbyl) bound ends present in the c R groups, the number of (tertiary amine) bound ends, as indicated by Δ, present in the b A groups is equal to the number of (hydrocarbyl) bound ends present in the c R groups, and the b A groups are bonded to each other through the (tertiary amine) bound ends, as indicated by Δ, present therein and the (hydrocarbyl) bound ends of the c R groups;
said optionally substituted means optionally substituted with one or more (such as 1 to 5, 1 to 4, 1 to 3, 1 to 2 or 1) groups selected from hydroxy, amino, mercapto, halogen and C 1-5 Linear or branched alkoxy;
the structure shown in formula (I) conforms to the bonding rule.
According to the present invention, preferably, the quaternary ammonium surfactant has a structure represented by formula (I-I):
wherein a L groups, equal to or different from each other, are each independently selected from optionally substituted m-valent C 1～50 Hydrocarbyl and C 3～50 A heterohydrocarbyl group, m is an integer between 1 and 20 (preferably an integer between 1 and 10), a is an integer between 1 and 20 (preferably an integer between 1 and 10, more preferably 1,2 or 3); n is 0 Is composed of
Number of charges of radical, n 0 Is an integer of 1 to 20 (preferably an integer of 1 to 10); n X Z- The radicals, equal to or different from each other, are each independently selected from F - 、Cl - 、Br - 、I - And OH - N is an integer of 1 to 20 (preferably an integer of 1 to 10), and Z-is X Z- The number of charges of the group, z is selected from 1,2 or 3; n X Z- The absolute value of the total number of charges of the radical being equal to n 0 ；
In the formula (I-I), b A groups are the same or different from each other and are independently selected from hydrogen and optionally substituted C 1～20 A linear or branched alkyl group and a group of formula (II-I), at least one A group being selected from the group of formula (II-I); b is an integer of 1 to 20 (preferably 2 to 10)More preferably 2, 3, 4, 5 or 6);
in the group of formula (II-I), the L 'group is selected from optionally substituted n' valent C 1～50 Hydrocarbyl and C 3～50 A heterohydrocarbyl group; n 'repeating units are the same or different from each other, and n' is an integer of 1 to 20 (preferably an integer of 1 to 10); r of n' repeating units 0 Each independently selected from hydrogen, optionally substituted C 1～20 Straight or linear alkyl and optionally substituted C 3～20 Straight or branched heteroalkyl (preferably selected from C) 1～20 Straight or linear alkyl); each of the m ' repeating units a ', b ', c ', d ', which are the same or different from each other, is independently selected from an integer of 0 to 5 (preferably 0, 1 or 2), and at least one a ' is an integer of 1 to 5 and at least one d ' is an integer of 1 to 5; each R of m' repeating units 1 Each independently selected from hydrogen, optionally substituted C 1～20 Straight or linear alkyl, optionally substituted C 3～20 A linear or linear heteroalkyl group and a group of formula (III-I); each R of m' repeating units 2 Each independently selected from optionally substituted C 1～20 Straight or branched alkylene and optionally substituted C 3～20 Linear or linear heteroalkylene; each R of m' repeating units 3 Each independently selected from optionally substituted C 1～20 Straight or branched chain alkyl and optionally substituted C 3～20 A linear or linear heteroalkyl group; m' is an integer of 1 to 20 (preferably an integer of 1 to 10); * Represents the binding end of the group of formula (II-I) to which the group L of formula (I-I) is bonded;
in the formula (III-I), each group and each symbol are as defined in the formula (II-I), and each R in m' repeating units 1 ' each is independently selected from hydrogen,Optionally substituted C 1～20 Straight or branched chain alkyl, optionally substituted C 3～20 A linear or linear heteroalkyl group and a group of formula (III-I) (preferably each independently selected from hydrogen, optionally substituted C 1～20 Straight or linear alkyl and optionally substituted C 3～20 Linear or linear heteroalkyl);
the number of (hydrocarbyl) bound ends present in the a groups is the same as the number of (carbonyl) bound ends present in the b A groups, and the a groups are bonded to each other via their (hydrocarbyl) bound ends to the (carbonyl) bound ends of the b A groups;
said optionally substituted means optionally substituted with one or more (such as 1 to 5, 1 to 4, 1 to 3, 1 to 2 or 1) groups selected from hydroxy, amino, mercapto, halogen and C 1-5 Linear or branched alkoxy;
the structure shown in the formula (I-I) conforms to the bonding rule.
According to the invention, the quaternary ammonium salt surfactant is selected from quaternary ammonium salt surfactants with the following specific structures or a mixture thereof in any proportion:
the invention provides a preparation method of a quaternary ammonium salt surfactant, which comprises the steps of reacting a compound shown in a formula (X), a compound shown in a formula (Y) and a compound shown in a formula (Z);
in formula (X), the L 'group is selected from optionally substituted n' valent C 1～50 Hydrocarbyl and C 3～50 A heterohydrocarbyl group; n 'repeating units are the same as or different from each other, and n' is an integer of 1 to 20 (preferably an integer of 1 to 10); r in n' repeating units 0 Each independently selected from hydrogen, optionally substituted C 1～20 Straight or linear alkyl and optionally substituted C 3～20 Straight or branched heteroalkyl (preferably selected from C) 1～20 Straight or linear alkyl); each a "of the m" repeating units is the same as or different from each other, and is independently selected from an integer of 1 to 5 (preferably 1,2 or 3); each R of m' repeating units 1 Each independently selected from hydrogen, optionally substituted C 1～20 Straight or branched chain alkyl, optionally substituted C 3～20 A linear or linear heteroalkyl group and a group of formula (X-I); each R of m' repeating units 2 Each independently selected from optionally substituted C 1～20 Straight or branched alkylene and optionally substituted C 3～20 Linear or linear heteroalkylene; m "is an integer of 1 to 20 (preferably an integer of 1 to 10);
in the formula (X-I), R 0 、R 2 A ' and m ' are as defined for formula (X), each R in m ' repeating units 1 ' each is independently selected from hydrogen, optionally substituted C 1～20 Straight or linear alkyl, optionally substituted C 3～20 A linear or linear heteroalkyl group and a group of formula (X-I) (preferably each independently selected from hydrogen, optionally substituted C 1～20 Straight or linear alkyl and optionally substituted C 3～20 Straight or branched heteroalkyl) in which at least one R is 1 ' is hydrogen;
in formula (Y), the R' group is optionally substituted m a C of valence 1～50 Hydrocarbyl radicals or C 3～50 Heterocarbyl (preferably optionally substituted m) a Valence of C 1～20 Straight or branched alkyl and C 3～20 Linear or branched heteroalkyl); m is a The Y groups in the repeating units are the same or different from each other and are each independently selected from F, cl, br, I, OH and optionally substituted C 1～5 Straight or branched chain alkyl (preferably methyl); m is a unit of a Is an integer of 1 to 20 (preferably an integer of 1 to 10);
in formula (Z), the R group is optionally substituted m b C of valence 1～50 Hydrocarbyl radicals or C 3～50 Heterohydrocarbyl (preferably optionally substituted m) b Valence of C 1～20 Straight or branched alkyl and C 3～20 Linear or branched heteroalkyl); m is b The X groups in the repeating units are the same or different from each other and are each independently selected from F, cl, br, I and OH; m is b Is an integer of 1 to 20 (preferably an integer of 1 to 10).
According to the preparation method of the present invention, the molar ratio between the compound represented by the formula (X) (in terms of amine group) and the compound represented by the formula (Y) (in terms of carbonyl group) and the compound represented by the formula (Z) (in terms of X group) is preferably 1:0.1 to 10:0.1 to 10 (more preferably 1.25 to 1.
According to the present invention, the production method may comprise a step of reacting the compound represented by the formula (X) with the compound represented by the formula (Y) or the compound represented by the formula (Z), a step A of reacting the compound represented by the formula (X) with the compound represented by the formula (Y) first and a step B of reacting the product of the step A with the compound represented by the formula (Z), or a step B of reacting the compound represented by the formula (X) with the compound represented by the formula (Z) first and a step A of reacting the product of the step B with the compound represented by the formula (Y).
According to the production method of the present invention, a solvent may or may not be added, and preferably a solvent is added, in the reaction of the compound represented by the formula (X), the compound represented by the formula (Y) and the compound represented by the formula (Z). The solvent is preferably selected from sulfone, sulfoxide, furan, C 1～6 Alcohol of (1), C 1～6 The ketone (b) may be, for example, one or more selected from dimethyl sulfoxide, tetrahydrofuran, methanol, ethanol, isopropanol, n-butanol, acetone, methyl ethyl ketone and methyl ethyl ketone. The solvent may be removed by a method known in the art after the completion of the reaction, and is not particularly limited, and examples thereof include distillation and evaporation.
According to the preparation method of the present invention, preferably, an inert gas is introduced into the reaction of the compound represented by the formula (X), the compound represented by the formula (Y), and the compound represented by the formula (Z), and the inert gas is preferably one or more of nitrogen, argon, and helium.
According to the preparation method of the present invention, the reaction temperature of the compound represented by the formula (X), the compound represented by the formula (Y) and the compound represented by the formula (Z) is preferably 0 to 200 ℃, preferably 20 to 150 ℃, and more preferably 30 to 110 ℃; the reaction time may be generally 0.5 to 7 days, preferably 0.5 to 72 hours.
According to the production method of the present invention, preferably, the production method comprises a step a of reacting a compound represented by the formula (X) with a compound represented by the formula (Y), and a step B of reacting the product of the step a with a compound represented by the formula (Z).
According to the preparation process of the present invention, preferably, the compound represented by the formula (X) is preferably selected from C 1～50 And/or C 1～50 Alkyl alcohol amine (more preferably C) 2～20 And/or C 2～20 The alkanolamine of (2) may be selected from, for example, N-dimethylethylenediamine, N-dimethylpropylenediamine, N, 2-tetramethyl-1, 3-propanediamine, 3- (dibutylamino) propylamine, N- (3-aminopropyl) diethanolamine, N, one or more of N-dimethyl-1, 3-cyclohexanediamine, N-diethylethylenediamine, N-dipropylethylenediamine, 2-amino-5-diethylaminopentane and N, N-diisopropylethylenediamine.
According to the preparation method of the present invention, preferably, the compound represented by the formula (Y) is preferably selected from C 1～50 Polycarboxylic acid esters, polycarboxylic acids and polycarboxylic acid halides (more preferably C) 2～30 The polybasic carboxylic acid ester of (b) which may be selected from the group consisting of a dibasic carboxylic acid ester, a tribasic carboxylic acid ester, a tetrabasic carboxylic acid ester, a pentabasic carboxylic acid ester and a hexahydric carboxylic acid ester.
According to the preparation method of the present invention, the dicarboxylic acid ester is preferably selected from one or more of the following structures:
wherein the value of x is preferably selected from integers between 0 and 9, such as 0, 1,2 or 3; the value of y is preferably selected from integers between 1 and 10, such as 1,2, 3, 4, 5 or 6; r a Each independently selected from C 1-12 And cycloalkyl groups such as methyl, ethyl, propyl, isopropyl, and the like.
According to the preparation method of the present invention, the tricarboxylic acid ester is preferably selected from one or more of the following structures:
wherein R is a The definition of (A) is as described above.
According to the preparation method of the present invention, the tetracarboxylic acid ester is preferably selected from one or more of the following structures:
wherein R is a As defined above, the value of s is preferably selected from integers between 0 and 9, such as 0, 1,2 or 3.
According to the production method of the present invention, the five-membered carboxylic acid ester and six-membered carboxylic acid ester are preferably selected from compounds of the following structures:
wherein R is a The definition of (A) is as described above.
According to the preparation process of the present invention, preferably, the compound represented by the formula (Z) is preferably selected from C 1～50 Alkyl halide (preferably selected from C) 5～30 The alkyl halide of (4) such as 1-bromododecane, 1-bromotetradecane, 1-bromohexadecane, 1-chlorododecane, 1-chlorotetradecane, 1-chlorohexadecane, 1-iodododecane, 1-iodotetradecane, 1-iodohexadecane and the like.
The invention also provides the use of the quaternary ammonium surfactant described above. The quaternary ammonium salt surfactant can be used as a high-efficiency low-consumption wetting agent for the field of tertiary oil recovery. In the tertiary oil recovery process, the quaternary ammonium salt surfactant can effectively convert the surface of a carbonate reservoir wrapped by crude oil into water wettability or neutral wettability to realize wettability reversal, thereby being beneficial to the improvement of oil washing efficiency.
Technical effects
The preparation method is simple, the reaction condition is mild, and the yield is high.
The preferable preparation method of the invention can not use acyl halide, can avoid toxic action brought by acyl halide, simultaneously avoids the limitation of anhydrous and anaerobic conditions, and simplifies the reaction conditions.
The preferable preparation method of the invention uses the polycarboxylic acid ester which is widely available, green and cheap, and is suitable for industrial production.
The quaternary ammonium salt surfactant has excellent surface activity and aggregation capacity, and can be used as a high-efficiency and low-consumption wetting agent in the field of tertiary oil recovery. The quaternary ammonium salt surfactant can achieve an excellent wetting effect at a lower concentration.
Drawings
FIG. 1 is an ESI mass spectrum of a quaternary ammonium surfactant intermediate prepared in example 1 of the present invention.
FIG. 2 shows NMR of intermediate of quaternary ammonium salt surfactant prepared in example 1 of the present invention 1 H NMR spectrum.
FIG. 3 is an ESI mass spectrum of a quaternary ammonium surfactant prepared in example 1 of the present invention.
FIG. 4 shows NMR spectra of quaternary ammonium salt surfactant prepared in example 1 of the present invention 1 H NMR spectrum.
FIG. 5 is an ESI mass spectrum of a quaternary ammonium surfactant intermediate prepared in example 2 of the present invention.
FIG. 6 shows NMR of intermediate of quaternary ammonium salt surfactant prepared in example 2 of the present invention 1 H NMR spectrum.
FIG. 7 is a high resolution ESI mass spectrum of the quaternary ammonium surfactant prepared in example 2 of the present invention.
FIG. 8 shows NMR spectra of quaternary ammonium salt surfactant prepared in example 2 of the present invention 1 H NMR spectrum.
Detailed Description
Reference will now be made in detail to the present embodiments of the present invention, but it should be understood that the scope of the invention is not limited by the embodiments, but is defined by the appended claims.
All publications, patent applications, patents, and other references mentioned in this specification are herein incorporated by reference in their entirety. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. In case of conflict, the present specification, including definitions, will control.
When the specification concludes with claims with the heading "known to those skilled in the art", "prior art", or the like, to derive materials, substances, methods, steps, devices, or components, etc., it is intended that the subject matter derived from the heading encompass those conventionally used in the art at the time of filing this application, but also include those that are not currently used, but would become known in the art to be suitable for a similar purpose.
In the context of the present description, anything or things not mentioned apply directly to what is known in the art without any changes, except where explicitly stated. Moreover, any embodiment described herein may be freely combined with one or more other embodiments described herein, and the technical solutions or concepts resulting therefrom are considered part of the original disclosure or original disclosure of the invention, and should not be considered as new matters not disclosed or contemplated herein, unless a person skilled in the art would consider such a combination to be clearly unreasonable.
In the context of the present invention, the expression "halo" refers to fluoro, chloro, bromo or iodo.
In the context of the present invention, the term "hydrocarbon group" has the meaning conventionally known in the art and includes straight-chain or branched alkyl, straight-chain or branched alkenyl, straight-chain or branched alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl or a combination thereof, wherein straight-chain or branched alkyl, straight-chain or branched alkenyl, cycloalkyl, cycloalkenyl, aryl or a combination thereof is preferred. Specific examples of the hydrocarbon group include C 1-50 A hydrocarbon radical comprising C 1 - 50 Straight or branched alkyl, C 2-50 Straight-chain or branched alkenyl, C 2-50 Straight-chain or branched alkynyl, C 3-50 Cycloalkyl radical, C 3-50 Cycloalkenyl radical, C 3-50 Cycloalkynyl group, C 6-50 Aryl or a combination thereof, wherein C is preferred 1-50 Straight or branched alkyl, C 2-50 Straight-chain or branched alkenyl, C 3-50 Cycloalkyl radical, C 3-50 Cycloalkenyl radical, C 6-50 Aryl or a combination thereof. As said combination group, for example, there may be mentioned one or more C 1-50 Straight or branched chain alkyl (preferably one or more C) 1-20 Straight or branched alkyl) with one or more C 6-50 Radicals obtained by direct substitution or bonding of aryl radicals, preferably one or more phenyl or naphthyl radicals, one or more C 1-50 Straight or branched alkenyl (preferably one or more C) 1-20 Straight or branched alkenyl) with one or more C 6-50 Radicals obtained by direct substitution or bonding of aryl radicals, preferably one or more phenyl or naphthyl radicals, one or more C 1-50 Straight or branched chain alkyl (preferably one or more C) 1-20 Straight or branched alkyl) with one or more C 3-50 A group obtained by direct substitution or bonding of cycloalkyl (preferably one or more cyclobutyl, cyclopentyl or cyclohexyl), one or more C 1-50 Straight or branched alkenyl (preferably one or more C) 1-20 Straight or branched alkenyl) with one or more C 3-50 A group obtained by direct substitution or bonding of cycloalkyl (preferably one or more cyclobutyl, cyclopentyl or cyclohexyl), one or more C 1-50 Straight or branched chain alkyl (preferably one or more C) 1-20 Straight or branched alkyl) with one or more C 3-50 A group obtained by direct substitution or bonding of cycloalkenyl (preferably one or more cyclobutenyl, cyclobutadienyl, cyclopentenyl, cyclopentadienyl, cyclohexenyl or cyclohexadienyl), one or more C 1-50 Straight or branched alkenyl (preferably one or more C) 1-20 Straight or branched alkenyl) with one or more C 3-50 Cycloalkenyl (preferably one or more cyclobutenyl, cyclobutadienyl, cyclopentenyl, cyclopentadienyl, cyclohexenyl or cyclohexadienyl) groups obtained by direct substitution or bonding. Said substitution being indicatedIs a group that acts as a substituent to replace a hydrogen atom in another group. The total number of carbon atoms in the combined group is an integer between 3 and 50, preferably between 3 and 20. As the above-mentioned combination group, there may be mentioned, for example, one or more C 1-20 Straight or branched alkylphenyl, phenyl C 1-20 Straight or branched chain alkyl or mono-or poly-C 1-20 Straight-chain or branched alkylphenyl C 1-20 Straight or branched chain alkyl, etc., of which C is more preferable 1-10 Straight or branched alkylphenyl radicals, e.g. tert-butylphenyl, phenyl C 1-10 Straight or branched alkyl (e.g. benzyl) or C 1-10 Straight or branched alkylphenyl C 1-10 Straight or branched chain alkyl (such as t-butylbenzyl).
In the context of the present invention, by "heterohydrocarbyl" is meant one or more (such as 1 to 4, 1 to 3, 1 to 2 or 1) -CH within the hydrocarbyl molecular structure (excluding the end of the backbone or any side chain in the hydrocarbyl molecular structure) 2 The radical-is selected from-O-, -S-, -N = N-and-NR '- (R' is H or C 1 - 4 Straight or branched chain alkyl), or one or more (such as 1 to 4, 1 to 3, 1 to 2 or 1) -CH inside the hydrocarbon-based molecular structure (excluding the end of the main chain or any side chain in the hydrocarbon-based molecular structure)<Radical substituted by radical-N<A group obtained by direct substitution. As said substituent, it is preferably-O-or-S-. It is clear that, from the point of view of structural stability, in the presence of a plurality of-O-) -NR' -, -N = N-or-N<When used, these substituent groups are not directly bonded to each other; where multiple-S-groups are present, these substituent groups may be bonded directly to each other. In addition, the number of carbon atoms of the hydrocarbon group is represented by the group-CH 2 -or a group-CH<Substituted with a corresponding decrease, but for the sake of simplicity, the number of carbon atoms of the hydrocarbon group before the substitution is still used to refer to the number of carbon atoms of the heterohydrocarbon group. By "heterocarbyl" is meant a straight or branched heteroalkyl, straight or branched heteroalkenyl, straight or branched heteroalkynyl, straight or branched heterocyclyl, straight or branched heterocyclenyl, straight or branched heterocyclylalkynyl, straight or branched heteroaryl, or combinations thereof, where straight or branched heteroalkynyl, straight or branched heteroaryl, or combinations thereof are preferredA linear or branched heteroalkyl, a linear or branched heteroalkenyl, a linear or branched heterocyclyl, a linear or branched heterocyclenyl, a linear or branched heteroaryl, or a combination thereof. The total number of carbon atoms in the combination group is an integer between 3 and 50 (preferably 3 to 20).
As the heterohydrocarbyl group, specifically exemplified is C 4 Straight chain alkyl radicals such as
(the group indicated by the arrow in the formula is not located within the molecular structure but at the end of the main chain) direct substitution with a substituent-O-will give-CH 2 -O-CH 2 -CH 3 or-CH 2 -CH 2 -O-CH 3 Is called C 4 A linear heteroalkyl group; c 4 Straight chain alkyl radicals such as
(the group indicated by the arrow in the formula is not located within the molecular structure but at the end of the main chain) direct substitution with a substituent-NH-will give-CH 2 -NH-CH 2 -CH 3 or-CH 2 -CH 2 -NH-CH 3 Also known as C 4 A linear heteroalkyl group. Or, C 4 Branched alkyl radicals such as
(the groups indicated by the arrows are not located within the molecular structure but at the ends of the main and side chains) by a substituent-N<Direct substitution will result in
Is called C 4 A branched heteroalkyl group. According to the invention, as the heterohydrocarbyl group, there may be mentioned, for example, C 3-50 Straight or branched heterohydrocarbyl, of which C is preferred 3-20 Straight or branched heterohydrocarbyl radicals or C 3-6 Straight or branched heterohydrocarbyl.
In the context of the present invention, said optionally substituted hydrocarbyl and heterohydrocarbyl groups are one or more of the hydrocarbyl and heterohydrocarbyl groups optionally described previouslyMultiple (such as 1 to 5, 1 to 4, 1 to 3, 1 to 2, or 1) hydrogens with one or more groups selected from the group consisting of hydroxy, amino, mercapto, halogen, and C 1-5 Straight or branched alkoxy-substituted hydrocarbyl and heterohydrocarbyl.
In the context of the present specification, the expression "number + valence + group" or the like refers to a group obtained by removing the number of hydrogen atoms represented by the number from the basic structure (such as a chain, a ring, a combination thereof, or the like) to which the group corresponds, and preferably refers to a group obtained by removing the number of hydrogen atoms represented by the number from a carbon atom (preferably a saturated carbon atom and/or a non-identical carbon atom) contained in the structure. For example, "3-valent straight or branched alkyl" refers to a group obtained by removing 3 hydrogen atoms from a straight or branched alkane (i.e., the base chain to which the straight or branched alkyl corresponds), and "2-valent straight or branched heteroalkyl" refers to a group obtained by removing 2 hydrogen atoms from a straight or branched heteroalkane (preferably from a carbon atom contained in the heteroalkane, or further, from a non-identical carbon atom).
In the present specification, the term "single bond" is sometimes used in the definition of a group. By "single bond", it is meant that the group is absent. For example, assume the formula-CH 2 -A-CH 3 Wherein the group a is defined as being selected from the group consisting of a single bond and a methyl group. In this respect, if A is a single bond, this means that the group A is absent, in which case the formula is correspondingly simplified to-CH 2 -CH 3 。
Unless otherwise explicitly indicated, all percentages, parts, ratios, etc. referred to in this specification are by weight unless not otherwise generally recognized by those of skill in the art.
According to the invention, preferably, the L group is selected from the following groups: c having a valence of 2 to 6 (preferably 1,2 or 3) 1-50 Straight or branched alkyl, C having a valence of 2 to 6 (preferably 1,2 or 3) 2-50 Straight or branched alkenyl, C substituted with one or more (preferably one, two, three or four) hydroxy groups having a valency of 2 to 6 (preferably 1,2 or 3) 1-50 Straight chainOr branched alkyl, C substituted with one or more (preferably one, two, three or four) hydroxy groups having a valency of 2 to 6 (preferably 1,2 or 3) 2-50 Straight or branched alkenyl, C having a valence of 1 to 6 (preferably 1,2 or 3) 3-50 Cycloalkyl or cycloheteroalkyl, C having a valency of 1 to 6 (preferably 1,2 or 3) 3-50 Cycloalkenyl or cycloheteroalkenyl, 1 to 6 (preferably 1,2 or 3) valent C 6-50 Aryl or heteroaryl.
According to the invention, preferably the L group is selected from the group consisting of cyclobutyl groups having a valency of 1 to 4 (preferably 1,2 or 3), cyclopentyl groups having a valency of 1 to 5 (preferably 1,2 or 3), cyclohexyl groups having a valency of 1 to 6 (preferably 1,2 or 3), cyclobutenyl groups having a valency of 1 to 4 (preferably 1,2 or 3), cyclopentenyl groups having a valency of 1 to 5 (preferably 1,2 or 3), cyclopentadienyl groups having a valency of 1 to 5 (preferably 1,2 or 3), cyclohexenyl groups having a valency of 1 to 6 (preferably 1,2 or 3), cyclohexadienyl groups having a valency of 1 to 6 (preferably 1,2 or 3), furyl groups having a valency of 1 to 4 (preferably 1,2 or 3), thienyl having a valence of 1 to 4 (preferably 1,2 or 3), pyrrolyl having a valence of 1 to 4 (preferably 1,2 or 3), indolyl having a valence of 1 to 6 (preferably 1,2 or 3), pyrazolyl having a valence of 1 to 3 (preferably 1 or 2), imidazolyl having a valence of 1 to 3 (preferably 1 or 2), thiazolyl having a valence of 1 or 2, oxazolyl having a valence of 1 to 3 (preferably 1 or 2), pyridyl having a valence of 1 to 5 (preferably 1,2 or 3), quinolyl having a valence of 1 to 7 (preferably 1,2 or 3), phenyl having a valence of 1 to 6 (preferably 1,2, 3, 4 or 5), naphthyl having a valence of 1 to 8 (preferably 1,2, 3, 4 or 5), a group represented by the formula (L-I), a group represented by the formula (L-II), a group represented by the formula (L-III), a group represented by the formula (L-IV),
in formula (L-I): denotes the binding ends of the phenyl groups, j is the number of binding ends of the phenyl groups, each j is independently selected from an integer between 0 and 5 (preferably 1,2 or 3), at least one j is an integer between 1 and 5;
in the formula (L-II), R j Each is independentSelected from C 1-10 Linear or branched alkylene of (C) 1-10 Linear or branched heteroalkylene of (C) 1-10 And C is a linear or branched alkyleneoxy group 1-10 Is a linear or branched heteroalkyleneoxy group (i.e., C having a valence of 2) 1-10 Straight or branched alkyl of (2), C 1-10 Linear or branched heteroalkyl, 2-valent C 1-10 And C having a valence of 2 1-10 Linear or branched heteroalkyloxy) represents R j At the bound end of the radical, j is R j The number of bound ends of the groups, each j being independently selected from an integer of 0 to 5 (preferably 1,2 or 3), at least one j being an integer of 1 to 5;
in the formula (L-III), each R j Each independently selected from C 1-10 Linear or branched alkylene and C 1-10 Represents R j Bound end of a radical, j being R to which it belongs j The number of bound ends of the groups, each j is independently selected from 0, 1 or 2 (preferably 1 or 2), at least one j is 1 or 2; each R is j ' the groups are each independently selected from C 1-10 Is straight-chain or branched alkyl, j' is R to which it belongs j 'the number of groups, each j' is independently selected from 0, 1 or 2 (preferably 1 or 2); for R bound to the same N atom j Group and R j 'for groups, the sum of j and j' is 2; j "is an integer between 0 and 5 (preferably 1,2, 3 or 4); in formula (L-IV), the Ar ring group is selected from the group consisting of cyclobutyl, cyclopentyl, cyclohexyl, cyclobutenyl, cyclopentenyl, cyclopentadienyl, cyclohexenyl, cyclohexadienyl, phenyl and naphthyl (preferably selected from the group consisting of cyclobutyl, cyclopentyl, cyclohexyl, cyclopentadienyl, phenyl and naphthyl); each R is j Each independently selected from C 1-10 Linear or branched alkylene and C 1-10 Represents R j The bound end of the radical, j being R to which it belongs j The number of termini bonded to the group, each j is independently selected from 0, 1 or 2 (preferably 1 or 2), at least one j is 1 or 2; each R is j ' the groups are each independently selected from C 1-10 Is straight-chain or branched alkyl, j' is R to which it belongs j ' the number of the groups,each j' is independently selected from 0, 1 or 2 (preferably 1 or 2); for R bound to the same N atom j Group and R j 'for the group, the sum of j and j' is 2; j "is an integer between 0 and 5 (preferably 1,2, 3 or 4).
According to the present invention, in the method for preparing the quaternary ammonium salt surfactant, the reaction product may be a single quaternary ammonium salt surfactant or a mixture containing a plurality of quaternary ammonium salt surfactants. These reaction products are all contemplated by the present invention, and the difference in the form of existence thereof does not affect the achievement of the effects of the present invention. Thus, the reaction products are collectively referred to herein, without distinction, as the quaternary ammonium surfactants of the present invention. In view of this, according to the present invention, there is no absolute necessity to further purify these reaction products or to further separate a quaternary ammonium surfactant of a specific structure from these reaction products. Of course, such purification or isolation is sometimes preferable for further improvement of the intended effect of the present invention, but is not essential to the present invention. As the purification or separation method, for example, the reaction product may be purified or separated by a column chromatography method, a preparative chromatography method or the like.
The main raw materials used in the embodiment are as follows:
| name of article | Source | Purity of |
| DL-malic acid dimethyl ester | Alfa Aesar | >97％ |
| Citric acid trimethyl ester | Alfa Aesar | >97％ |
| Azobenzene-3, 3' -dicarboxylic acids | TCI | >95％ |
| 2, 5-Furancarboxylic acid | TCI | >98％ |
| N, N-dimethylethylenediamine | Alfa Aesar | >98％ |
| 1-bromododecane | TCI | >98％ |
| Organic solvent | BEIJING CHEMICAL PLANT | AR |
EXAMPLE 1 preparation of dimeric quaternary ammonium surfactant
The preparation method of the dimeric quaternary ammonium salt surfactant is as follows:
the specific method comprises the following steps:
(1) The synthesis steps of intermediate product diamide: 14.1g (160.0 mmol) of N, N-dimethylethylenediamine was added to 3.2g (20.0 mmol) of DL-malic acid dimethyl ester and refluxed at 106 ℃ for 3 hours. After the reaction was completed, excess N, N-dimethylethylenediamine was removed by a rotary evaporator to obtain an intermediate with a yield of 99%.
ESI-MS characterization of the intermediates: 275.2 (M + H), 297.2 (M + Na).
1 H NMR(CDCl 3 400 MHz): δ =2.24 (singlet, 12H, -N (CH) 3 ) 2 ) 2.44 (multiplet, 4H, -NH-CH) 2 -CH 2 -N(CH 3 ) 2 ) 2.51,2.82 (multiplet, 2H, -NH-CO-CH) 2 -CH (OH) -CO-NH-), 3.25 (multiplet, 4H, -NH-CH) 2 -CH 2 -N(CH 3 ) 2 ) 4.42 (singlet, 1H, -CH-OH), 5.95 (singlet, 1H, -CH-OH), 7.04,7.49 (singlet, 2H, -NH-CO-CH 2 -CH(OH)-CO-NH-)。
(2) Preparation of dimeric quaternary ammonium salt surfactant:
1.6g (6.0 mmol) of the intermediate and 6.0g (24.0 mmol) of 1-bromododecane were dissolved in a mixed solvent of methanol and acetone, and reacted at 40 ℃ for 72 hours. The solvent was removed by rotary evaporation and the crude product was recrystallized from methanol/ethyl acetate to give the product as a powder with a yield of 90%.
Map results for dimeric quaternary ammonium surfactant: 1 H NMR(CD 3 OD,400 MHz): δ =0.87 (triplet, 6H, -CH) 3 ) 1.29-1.80 (multiplet, 40H 3 -(CH 2 ) 10 -CH 2 -N + -, 2.71-2.85 (multiplet, 4H 3 -(CH 2 ) 10 -CH 2 -N + -), 3.13-3.20 (multiplet, 12H, -N + (CH 3 ) 2 ) 3.45-3.52 (multiplet, 7H, -CO-NH-CH) 2 -CH 2 -N + -，-NH-CO-CH 2 -CH (OH) -CO-NH-), 3.55-3.76 (multiplet, 4H, -CO-NH-CH) 2 -CH 2 -N + -, 4.46 (triplet, 1H, -NH-CO-CH) 2 -CH (OH) -CO-NH-). MS-ESI (m/z): theoretical value 772.82; and (3) testing results: 306.6 ([ M-2 Br)] 2+ /2)。 1 The results of H NMR and MS-ESI show that the product is consistent with the target product. Elemental analysis results: theoretical values are as follows: c 36 H 76 N 4 O 3 Br 2 : c,55.95; h,9.91; and N,7.25. And (3) testing results: c,55.90; h,9.88; and N,7.20.
These spectrum results show that the compound prepared in this example is a dimeric quaternary ammonium salt surfactant product.
EXAMPLE 2 preparation of Triquaternary ammonium salt surfactant
The preparation method of the trimeric quaternary ammonium salt surfactant is as follows:
the specific method comprises the following steps:
(1) Synthesis of intermediate tripolyamide: 10.6g (120.0 mmol) of N, N-dimethylethylenediamine was added to 2.3g (10.0 mmol) of trimethyl citrate, and the mixture was refluxed at 106 ℃ for 3 hours. After the reaction is finished, removing redundant N, N-dimethyl ethylenediamine by using a rotary evaporator to obtain an intermediate with the yield of 99%.
ESI-MS characterization of the intermediates: 403.2 (M + H), 425.3 (M + Na).
1 H NMR(CDCl 3 400 MHz): δ =2.24 (singlet, 18H, -N (CH) 3 ) 2 ) 2.41 (multiplet, 6H, -NH-CH) 2 -CH 2 -N(CH 3 ) 2 ) 2.60-2.73 (multiplet, 4H, -NH-CO-CH) 2 -CH (OH) -), 3.32 (multiplet, 6H, -NH-CH 2 -CH 2 -N(CH 3 ) 2 ) 5.20 (singlet, 1H, -CH-OH), 7.10,7.47 (singlet, 3H, -NH-CH) 2 -CH 2 -N(CH 3 ) 2 )。
(2) Preparation of trimeric quaternary ammonium salt surfactant: 4.0g (6.4 mmol) of the intermediate and 16.0g (63.7 mmol) of 1-bromododecane were dissolved in a mixed solvent of methanol and acetone and reacted at 40 ℃ for 72 hours. The solvent was removed by rotary evaporation and the crude product was recrystallized from methanol/ethyl acetate to give the product as a powder in 85% yield.
Map results for the trimeric quaternary surfactant: 1 H NMR(CD 3 OD,400 MHz): δ =0.88 (triplet, 9H, -CH) 3 ) 1.29-1.39 (multiplet, 54H 3 -(CH 2 ) 9 -CH 2 -CH 2 -N + -, 1.80 (singlet, 6H, CH) 3 -(CH 2 ) 9 -CH 2 -CH 2 -N + -, 2.64-2.91 (multiplet, 6H, CH) 3 -(CH 2 ) 9 -CH 2 -CH 2 -N + -), 3.16-3.25 (multiplet, 18H, -N + (CH 3 ) 2 ) 3.45-3.55 (multiplet, 11H, -CO-NH-CH) 2 -CH 2 -N + -，-NH-CO-CH 2 -OH), 3.65-3.72 (multiplet, 6H, -CO-NH-CH) 2 -CH 2 -N + -). MS-ESI (m/z): theoretical value 1146.64; and (3) testing results: 495.40 ([ M-2 Br)] 2+ /2)。 1 The results of H NMR and MS-ESI show that the product is consistent with the target product. Elemental analysis results: theoretical value: c 54 H 113 N 6 O 4 Br 3 : c,56.39; h,9.90; and N,7.31. And (3) testing results: c,56.26; h,9.82; and N,7.29.
The results of the spectrograms show that the compound prepared in the embodiment is the trimeric quaternary ammonium salt surfactant product.
EXAMPLE 3 preparation of dimeric surfactants whose linking group contains an aromatic Ring
The preparation method of the dimeric surfactant with the linking group containing the aromatic ring is as follows:
the specific method comprises the following steps:
(1) And (3) synthesis of intermediate dimethyl ester: 2.7g (10.0 mmol) of azobenzene-3, 3' -dicarboxylic acid was added to 50mL of methanol, and a catalytic amount of concentrated sulfuric acid was added thereto and refluxed for 3 hours. After the reaction is finished, the solvent is removed by a rotary evaporator, and the intermediate dimethyl ester can be obtained with the yield of 99%.
(2) Synthesis of intermediate diamine: 3.5g (40.0 mmol) of N, N-dimethylethylenediamine was added to 3.0g (10.0 mmol) of intermediate dimethyl ester and refluxed at 106 ℃ for 3 hours. After the reaction was completed, excess N, N-dimethylethylenediamine was removed by a rotary evaporator to obtain an intermediate with a yield of 99%.
(3) Preparation of dimeric quaternary ammonium salt surfactant with aromatic ring-containing linking group: 4.1g (10.0 mmol) of the intermediate and 10.0g (40.0 mmol) of 1-bromododecane were dissolved in a mixed solvent of methanol and acetone and reacted at 40 ℃ for 72 hours. The solvent was removed by rotary evaporation and the crude product was recrystallized from methanol/ethyl acetate to give the product as a powder with a yield of 80%.
EXAMPLE 4 preparation of dimeric surfactants whose linking groups contain heterocycles
The preparation method of the dimeric surfactant with the heterocyclic ring in the connecting group is as follows:
the specific method comprises the following steps:
(1) Synthesis of intermediate dimethyl ester: 1.6g (10.0 mmol) of 2, 5-furandicarboxylic acid was added to 50mL of methanol, and a catalytic amount of concentrated sulfuric acid was added thereto and refluxed for 3 hours. After the reaction is finished, the solvent is removed by a rotary evaporator, and the intermediate dimethyl ester can be obtained with the yield of 99%.
(2) Synthesis of intermediate diamine: 3.5g (40.0 mmol) of N, N-dimethylethylenediamine was added to 1.8g (10.0 mmol) of intermediate dimethyl ester and refluxed at 106 ℃ for 3 hours. After the reaction was completed, excess N, N-dimethylethylenediamine was removed by a rotary evaporator to obtain an intermediate with a yield of 99%.
(3) Preparation of dimeric quaternary ammonium salt surfactant with heterocyclic ring in the connecting group: 3.0g (10.0 mmol) of the intermediate and 10.0g (40.0 mmol) of 1-bromododecane were dissolved in a mixed solvent of methanol and acetone, and reacted at 40 ℃ for 72 hours. The solvent was removed by rotary evaporation and the crude product was recrystallized from methanol/ethyl acetate to give a powder with a yield of 86%.
Example 5 measurement of surface tension and measurement of critical aggregation concentration
The surface tension of aqueous surfactant solutions of different concentrations was measured using a K100 surface tension meter, KRUSS, germany, using a slinger. Each surface tension value (. Gamma.)) Repeating for more than five times, and repeating for three times for each surface tension curve. The test temperature was controlled at 25.0. + -. 0.1 ℃. Respectively measuring the surface tension values of dimeric and trimeric quaternary ammonium salt surfactants with different concentrations, defining the turning point of the obtained surface tension-concentration logarithm (gamma-logC) curve as the critical aggregation concentration of the surfactant, and defining the surface tension value of the curve in a platform region as the gamma-concentration of the surfactant CAC 。
EXAMPLE 6 determination of Critical aggregation concentration of surfactant by conductivity method
Conductivity values of the surfactant at different concentrations were measured using a model DDS-11A laboratory conductivity meter from shanghai wisdom light instruments ltd. In the experimental process, a high-concentration surfactant solution is continuously added into 10.00mL of water, and the reading of a conductivity meter is carried out after the system is completely balanced. In the experimental process, the surfactant solution is placed in a constant-temperature water bath, so that the temperature of the solution in the experimental process is constant at (25.0 +/-0.1). Conductivity values of the quaternary ammonium salt surfactants of examples 1 to 4 at different concentrations were measured, respectively, and the turning point of the conductivity-concentration (κ -C) curve was the critical aggregation concentration of the surfactant.
TABLE 1 Critical aggregation concentration of Quaternary ammonium surfactants in aqueous solution (25 ℃ C.)
Table 1 shows the Critical Aggregation Concentration (CAC) and the average value (CAC) of the quaternary ammonium salt surfactant obtained by the surface tension and electric conductivity method a ) And gamma CAC . Meanwhile, the corresponding data of the conventional single-chain Quaternary ammonium salt surfactant Dodecyl Trimethyl Ammonium Bromide (DTAB) reported in the literature (Esumi K., taguma K., koide Y.aqueous Properties of Multi-chain Quaternary ammonium surfactants Langmuir 1996, 4039-4041). Compared with the traditional quaternary ammonium salt surfactant DTAB, the quaternary ammonium salt surfactant has extremely low critical aggregation concentration. At the same time, the surface tension (gamma) of the quaternary ammonium surfactants of the invention is comparable to DTAB CAC ) Lower valueIndicating that it has stronger surface activity.
On the other hand, the surface tension (. Gamma.) of the trimeric surfactant obtained in example 2 of the present invention CAC ) The surfactant is 33.0mN/m, and the value is obviously lower than that of two trimeric cationic quaternary ammonium salt surfactants (45.0 mN/m and 42.0 mN/m) in the literature (Langmuir, 2010,26, 7922-7927) and a star-shaped trimeric cationic quaternary ammonium salt surfactant (41.8 mN/m) in the literature (Colloids surf.A,2014,457, 374-381) under the condition that the alkyl chain length is the same, and the result shows that the quaternary ammonium salt surfactant disclosed by the invention has more excellent surfactant. When the micro-pore structure is applied to crude oil exploitation, the micro-pore structure is favorable for reducing the capillary resistance of the carbonate rock micro-pores to oil drops, so that the oil washing efficiency is improved.
Example 7 wettability test
A mica sheet is used for simulating reservoir rock, thick oil of a Tahe, thick oil of a spring breeze, thick oil of Shengli Chen 25, thick oil of Yongli 8 and thick oil of Shengli offshore are respectively used as oil phases, 0.5mM or 5.0mM quaternary ammonium salt surfactant solutions of examples 1-4 are respectively used as water phases, and a three-phase method is used for measuring a contact angle on a DSA100 contact angle measuring instrument. The contact angle results are shown in table 2.
TABLE 2 results of wettability tests
(continuation table 2)
From the results of Table 2, it can be seen that at fixed concentrations of 0.5mM and 5.0mM, the contact angle of the quaternary ammonium salt surfactant of the present invention is smaller than that of the single-chain quaternary ammonium salt surfactant DTAB, indicating that it has stronger wettability. At the same time, the contact angle of DTAB at 0.5mM was very large (over 110 ℃ C.), indicating that the interface was still an oil-wet interface at this time. When the quaternary ammonium salt surfactant is 0.5mM, the contact angle is respectively reduced to about 80 degrees or 50 degrees, the quaternary ammonium salt surfactant is neutral-wetting and weak-water-wetting, and the oil displacement recovery rate of rock sample water in the wetting state is highest. Therefore, the quaternary ammonium salt surfactant obtained by the invention can realize wetting reversion at a lower concentration, thereby being beneficial to the improvement of the recovery ratio of crude oil.
In conclusion, compared with the traditional surfactant, the quaternary ammonium salt surfactant prepared by the invention has stronger surface activity and aggregation capability, thereby showing the characteristics of high efficiency and low consumption. And the quaternary ammonium salt surfactant is also superior to the traditional surfactant in the aspect of wettability to crude oil, can realize wetting reversal at lower concentration, and is favorable for improving the oil washing efficiency.
Although the embodiments of the present invention have been described in detail with reference to the examples, it should be noted that the scope of the present invention is not limited by the embodiments, but is defined by the appended claims. Those skilled in the art can appropriately modify the embodiments without departing from the technical spirit and scope of the present invention, and the modified embodiments are also clearly included in the scope of the present invention.
Claims (11)
1. A quaternary ammonium surfactant has the structure as follows:
2. the method for producing a quaternary ammonium salt surfactant according to claim 1, comprising a step A of reacting a compound represented by the formula (X) with a compound represented by the formula (Y), and a step B of reacting the product of the step A with a compound represented by the formula (Z);
the compound shown in the formula (X) is N, N-dimethylethylenediamine, the compound shown in the formula (Y) is azobenzene-3, 3' -dicarboxylic acid or 2, 5-furandicarboxylic acid, and the compound shown in the formula (Z) is 1-bromododecane.
3. The process according to claim 2, wherein the compound of formula (X) is represented by an amine group, the compound of formula (Y) is represented by a carbonyl group, the compound of formula (Z) is represented by an X group, and the molar ratio of the compound of formula (X) to the compound of formula (Y) or the compound of formula (Z) is 1:0.1 to 10:0.1 to 10.
4. The process according to claim 2, wherein the molar ratio of the compound of formula (X) to the compound of formula (Y) and the compound of formula (Z) is 1:0.25 to 1:0.5 to 5.
5. The process according to claim 2, wherein a solvent selected from the group consisting of sulfone, sulfoxide, furan and C is added to the reaction of the compound represented by the formula (X), the compound represented by the formula (Y) and the compound represented by the formula (Z) 1～6 Alcohol of (1), C 1～6 The ketone of (1).
6. The process according to claim 2, wherein a solvent selected from one or more of dimethyl sulfoxide, tetrahydrofuran, methanol, ethanol, isopropanol, n-butanol, acetone, methyl ethyl ketone and methyl ethyl ketone is added to the reaction of the compound represented by the formula (X), the compound represented by the formula (Y) and the compound represented by the formula (Z).
7. The process according to claim 2, wherein an inert gas is introduced into the reaction of the compound represented by the formula (X), the compound represented by the formula (Y) or the compound represented by the formula (Z).
8. The process according to claim 2, wherein the compound represented by the formula (X), the compound represented by the formula (Y) and the compound represented by the formula (Z) are reacted at a temperature of 0 to 200 ℃.
9. The process according to claim 2, wherein the compound represented by the formula (X), the compound represented by the formula (Y) and the compound represented by the formula (Z) are reacted at a temperature of 20 to 150 ℃.
10. The quaternary ammonium salt surfactant according to claim 1 or the quaternary ammonium salt surfactant produced by the method according to any one of claims 2 to 9 is used as a wetting agent.
11. The quaternary ammonium salt surfactant according to claim 1 or the quaternary ammonium salt surfactant produced by the method according to any one of claims 2 to 9 is used as a wetting agent in the field of tertiary oil recovery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811212800.4A CN111072511B (en) | 2018-10-18 | 2018-10-18 | Quaternary ammonium salt surfactant and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811212800.4A CN111072511B (en) | 2018-10-18 | 2018-10-18 | Quaternary ammonium salt surfactant and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111072511A CN111072511A (en) | 2020-04-28 |
| CN111072511B true CN111072511B (en) | 2023-01-13 |
Family
ID=70308302
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811212800.4A Active CN111072511B (en) | 2018-10-18 | 2018-10-18 | Quaternary ammonium salt surfactant and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111072511B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114181689B (en) * | 2020-09-14 | 2023-04-07 | 中国石油化工股份有限公司 | High-temperature-resistant composite emulsion viscosity-reducing system and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109111906A (en) * | 2018-09-19 | 2019-01-01 | 中国石油化工股份有限公司 | A kind of emulsifying and viscosity-reducing agent for condensed oil |
-
2018
- 2018-10-18 CN CN201811212800.4A patent/CN111072511B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109111906A (en) * | 2018-09-19 | 2019-01-01 | 中国石油化工股份有限公司 | A kind of emulsifying and viscosity-reducing agent for condensed oil |
Non-Patent Citations (7)
| Title |
|---|
| Design, synthesis, anticorrosion efficiency, and applications of novel Gemini surfactants for preparation of small-sized hollow spheres mesoporous silica nanoparticles;El-Said, W.A. 等;《Materials Chemistry and Physics》;20180219;第211卷;第128页图1和第134页图解2 * |
| Preparation, Characterization and Properties of Novel Cationic Gemini Surfactants with Rigid Amido Spacer Groups;Xu, Dongqing 等;《Journal of Surfactants and Detergents》;20151016;第19卷(第1期);第92页图解1，第92页实施例 * |
| Xu, Dongqing 等.Preparation, Characterization and Properties of Novel Cationic Gemini Surfactants with Rigid Amido Spacer Groups.《Journal of Surfactants and Detergents》.2015,第19卷(第1期),第92页图解1，第92页实施例. * |
| 侯研博 等.寡聚度对低聚阳离子季铵盐表面活性剂的聚集行为、油-水界面性能及润湿性的影响.《石油学报（石油加工）》.2018,第34卷(第3期),第531页图1. * |
| 季铵盐类Gemini表面活性剂的合成与表面活性;杨百勤 等;《印染助剂》;20140420;第31卷(第4期);第16页右栏第3段 * |
| 寡聚度对低聚阳离子季铵盐表面活性剂的聚集行为、油-水界面性能及润湿性的影响;侯研博 等;《石油学报（石油加工）》;20180525;第34卷(第3期);第531页图1 * |
| 寡聚表面活性剂的合成及其聚集行为的研究;韩玉淳 等;《中国科学：化学》;20150420;第45卷(第4期);第328页图2、第329页图3、第331页图12-14和第332页图15-16 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111072511A (en) | 2020-04-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR100958876B1 (en) | Ionic liquids miscible with various polar/non-polar solvents and method for preparing the same | |
| JP6626924B2 (en) | Hyperbranched cationic phosphonium salt, forward osmosis extract using the same, and forward osmosis seawater desalination process | |
| EP3303454B1 (en) | Method for producing organosilicon compounds having amino acid groups | |
| CN111072511B (en) | Quaternary ammonium salt surfactant and preparation method and application thereof | |
| Hornung et al. | Bent and twisted: the electronic structure of 2-azapropenylium ions obtained by guanidine oxidation | |
| CN111333582A (en) | Imidazolyl organic molybdenum ionic liquid and preparation method thereof | |
| Haak et al. | Kinetic evidence for a critical hydrophobic interaction concentration | |
| JPH0288586A (en) | Organic functional betaine modified siloxane and its production | |
| Demberelnyamba et al. | Ionic liquids based on N-vinyl-γ-butyrolactam: potential liquid electrolytes and green solvents | |
| DE10036522A1 (en) | Novel linear aminoacid modified polyquaternary polysiloxanes are useful in cosmetic formulations for skin and hair care, in polishes and as softeners | |
| JPS5946252A (en) | Fluorine-containing aminocarboxylate and its preparation | |
| JP2010095473A (en) | Onium salt having trialkylsilyl group | |
| CN108837773A (en) | A kind of viscoelastic solution formed by abietyl dipeptides surfactant | |
| CN110156641B (en) | Synthesis method of substituted guanidine | |
| CN105218540A (en) | The preparation method of a kind of C-3 position thiocarbamoyl imidazole also [1,2-a] pyridine compounds and their | |
| un Nisa et al. | Some newly synthesized ferrocene based esters: Characterization, DNA interaction and DFT studies | |
| KR100867978B1 (en) | Novel bi-functional ionic liquids and the preparation method thereof | |
| JPH04182492A (en) | Ascorbic acid derivative and production thereof | |
| CN108854841B (en) | Pyrrolidine chiral Gemini surfactant with ester group-containing connecting group and preparation method thereof | |
| DE4234105C1 (en) | Quaternary ammonium group-containing siloxane derivatives, process for their preparation and their use | |
| Chen et al. | Synthesis and surface tension study of the spacer chain length effect on the adsorption and micellization properties of a new kind of carboxylate gemini surfactant | |
| CN116396196B (en) | Method for preparing amido isothiocyanate/amido thiourea compound in one pot | |
| JP4741789B2 (en) | Synthesis method of polymer complex with adsorption performance | |
| Holeček et al. | Infrared, 119 Sn, 13 C and 1 H NMR, 119 Sn and 13 C CP/MAS NMR and Mössbauer Spectral Study of Some Tributylstannyl Citrates and Propane-1, 2, 3-tricarboxylates | |
| CN111925291B (en) | Preparation method of 3, 4-disubstituted alpha-tetralone compound |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |