CN114075236A - Foamless silicon branched fatty acid ionic liquid surfactant and preparation method thereof - Google Patents
Foamless silicon branched fatty acid ionic liquid surfactant and preparation method thereof Download PDFInfo
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- CN114075236A CN114075236A CN202111372220.3A CN202111372220A CN114075236A CN 114075236 A CN114075236 A CN 114075236A CN 202111372220 A CN202111372220 A CN 202111372220A CN 114075236 A CN114075236 A CN 114075236A
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- ionic liquid
- fatty acid
- acid ionic
- silicon
- quaternary ammonium
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- 239000002608 ionic liquid Substances 0.000 title claims abstract description 87
- 239000004094 surface-active agent Substances 0.000 title claims abstract description 71
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 63
- 239000010703 silicon Substances 0.000 title claims abstract description 63
- 235000014113 dietary fatty acids Nutrition 0.000 title claims abstract description 58
- 239000000194 fatty acid Substances 0.000 title claims abstract description 58
- 229930195729 fatty acid Natural products 0.000 title claims abstract description 58
- 150000004665 fatty acids Chemical class 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title abstract description 20
- 235000021122 unsaturated fatty acids Nutrition 0.000 claims abstract description 15
- 150000004670 unsaturated fatty acids Chemical class 0.000 claims abstract description 15
- 239000006260 foam Substances 0.000 claims abstract description 10
- 238000005187 foaming Methods 0.000 claims description 31
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 24
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 16
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 12
- 239000005046 Chlorosilane Substances 0.000 claims description 8
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 8
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 150000001768 cations Chemical class 0.000 claims description 7
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 6
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 5
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 5
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 5
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000005642 Oleic acid Substances 0.000 claims description 5
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- VKOBVWXKNCXXDE-UHFFFAOYSA-N icosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCC(O)=O VKOBVWXKNCXXDE-UHFFFAOYSA-N 0.000 claims description 4
- DPUOLQHDNGRHBS-UHFFFAOYSA-N Brassidinsaeure Natural products CCCCCCCCC=CCCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-UHFFFAOYSA-N 0.000 claims description 3
- URXZXNYJPAJJOQ-UHFFFAOYSA-N Erucic acid Natural products CCCCCCC=CCCCCCCCCCCCC(O)=O URXZXNYJPAJJOQ-UHFFFAOYSA-N 0.000 claims description 3
- ABHNFDUSOVXXOA-UHFFFAOYSA-N benzyl-chloro-dimethylsilane Chemical compound C[Si](C)(Cl)CC1=CC=CC=C1 ABHNFDUSOVXXOA-UHFFFAOYSA-N 0.000 claims description 3
- NDKBVBUGCNGSJJ-UHFFFAOYSA-M benzyltrimethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)CC1=CC=CC=C1 NDKBVBUGCNGSJJ-UHFFFAOYSA-M 0.000 claims description 3
- KWYZNESIGBQHJK-UHFFFAOYSA-N chloro-dimethyl-phenylsilane Chemical compound C[Si](C)(Cl)C1=CC=CC=C1 KWYZNESIGBQHJK-UHFFFAOYSA-N 0.000 claims description 3
- DPUOLQHDNGRHBS-KTKRTIGZSA-N erucic acid Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-KTKRTIGZSA-N 0.000 claims description 3
- NKAWWXQVDJITSK-UHFFFAOYSA-M ethyl-(hydroxymethyl)-dimethylazanium;hydroxide Chemical compound [OH-].CC[N+](C)(C)CO NKAWWXQVDJITSK-UHFFFAOYSA-M 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- RWXVMOBDVOAUHW-UHFFFAOYSA-N tert-butyl-chloro-diethylsilane Chemical compound CC[Si](Cl)(CC)C(C)(C)C RWXVMOBDVOAUHW-UHFFFAOYSA-N 0.000 claims description 3
- BCNZYOJHNLTNEZ-UHFFFAOYSA-N tert-butyldimethylsilyl chloride Chemical compound CC(C)(C)[Si](C)(C)Cl BCNZYOJHNLTNEZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 2
- 239000002585 base Substances 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 2
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 239000007864 aqueous solution Substances 0.000 abstract description 12
- 238000001338 self-assembly Methods 0.000 abstract description 3
- 239000003960 organic solvent Substances 0.000 abstract description 2
- 230000010355 oscillation Effects 0.000 abstract 1
- 230000001590 oxidative effect Effects 0.000 abstract 1
- -1 coatings Substances 0.000 description 20
- 239000007788 liquid Substances 0.000 description 12
- 238000001035 drying Methods 0.000 description 11
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 description 7
- 230000002209 hydrophobic effect Effects 0.000 description 7
- 239000000693 micelle Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000005457 ice water Substances 0.000 description 4
- 229940049964 oleate Drugs 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- JCHOSILAAQNQIQ-KVVVOXFISA-M 2-hydroxyethyl(trimethyl)azanium (Z)-octadec-9-enoate Chemical compound C[N+](C)(C)CCO.CCCCCCCC\C=C/CCCCCCCC([O-])=O JCHOSILAAQNQIQ-KVVVOXFISA-M 0.000 description 3
- 238000006065 biodegradation reaction Methods 0.000 description 3
- HVLRVVIFRGPWTJ-XVSDJDOKSA-M (5z,8z,11z,14z)-icosa-5,8,11,14-tetraenoate;tetramethylazanium Chemical compound C[N+](C)(C)C.CCCCC\C=C/C\C=C/C\C=C/C\C=C/CCCC([O-])=O HVLRVVIFRGPWTJ-XVSDJDOKSA-M 0.000 description 2
- YZXBAPSDXZZRGB-DOFZRALJSA-N arachidonic acid Chemical compound CCCCC\C=C/C\C=C/C\C=C/C\C=C/CCCC(O)=O YZXBAPSDXZZRGB-DOFZRALJSA-N 0.000 description 2
- DCMWFYOOJWPWCO-KVVVOXFISA-M benzyl(trimethyl)azanium (Z)-docos-13-enoate Chemical compound CCCCCCCC/C=C\CCCCCCCCCCCC(=O)[O-].C[N+](C)(C)CC1=CC=CC=C1 DCMWFYOOJWPWCO-KVVVOXFISA-M 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- VACHUYIREGFMSP-UHFFFAOYSA-N 9,10-dihydroxyoctadecanoic acid Chemical compound CCCCCCCCC(O)C(O)CCCCCCCC(O)=O VACHUYIREGFMSP-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229940114079 arachidonic acid Drugs 0.000 description 1
- 235000021342 arachidonic acid Nutrition 0.000 description 1
- 229940116226 behenic acid Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- YOUGRGFIHBUKRS-UHFFFAOYSA-N benzyl(trimethyl)azanium Chemical class C[N+](C)(C)CC1=CC=CC=C1 YOUGRGFIHBUKRS-UHFFFAOYSA-N 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- CAKISNDBWAIJMG-UHFFFAOYSA-N n,n-dimethylaniline;hydrate Chemical compound [OH-].C[NH+](C)C1=CC=CC=C1 CAKISNDBWAIJMG-UHFFFAOYSA-N 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/188—Preparation; Treatments not provided for in C07F7/20 by reactions involving the formation of Si-O linkages
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
Abstract
The invention discloses a foamless silicon branched fatty acid ionic liquid surfactant and a preparation method thereof, wherein the silicon branched fatty acid ionic liquid surfactant is prepared by oxidizing and silanizing unsaturated fatty acid ionic liquid, no organic solvent is required to be added, and the yield is over 90 percent. The silicon-branched fatty acid ionic liquid surfactant has strong self-assembly capability, and the aqueous solution of the silicon-branched fatty acid ionic liquid surfactant cannot generate any foam after violent oscillation.
Description
Technical Field
The invention belongs to the field of surfactants, and particularly relates to a foamless silicon branched fatty acid ionic liquid surfactant and a preparation method thereof.
Background
The surfactant is an amphiphilic molecule consisting of a hydrophilic head group and a hydrophobic tail chain, can be self-assembled in an aqueous solution to form various aggregate structures, shows unique physical and chemical properties, and is widely applied to various fields of washing, food, medicines, coatings, textiles, buildings, oil extraction and the like.
Because of the flexibility of silicon-oxygen bonds or silicon-carbon bonds, the silicon surfactant has higher surface activity and lower foaming property of aqueous solution compared with the traditional hydrocarbon chain surfactant, and is widely applied to dyeing and finishing of textiles, pesticide emulsification and the like.
Most of the current silicon surfactants are traditional cations (such as CN109261069A), anions (such as CN 110903312A, CN 108905883A), zwitterions (such as CN 110903312A, CN 111548501A) or nonionic types (such as CN 110437272A), and the ionic liquid type silicon surfactants are less. Most silicon surfactants consist of a silicon-containing hydrophobic backbone with hydrophilic head groups, the molecules mainly exhibiting a T-type structure. Although most silicon surfactants have low foamability in aqueous solution, foam can still be generated and stably exist.
Therefore, there is a need in the art for an ionic liquid type silicon surfactant that is both easily degradable, low in irritation, and free of bubbles.
Disclosure of Invention
This section is for the purpose of summarizing some aspects of embodiments of the invention and to briefly introduce some preferred embodiments. In this section, as well as in the abstract and the title of the invention of this application, simplifications or omissions may be made to avoid obscuring the purpose of the section, the abstract and the title, and such simplifications or omissions are not intended to limit the scope of the invention.
The present invention has been made keeping in mind the above and/or other problems occurring in the prior art.
Therefore, the invention aims to overcome the defects in the prior art and provide a non-foaming silicon branched fatty acid ionic liquid surfactant.
In order to solve the technical problems, the invention provides the following technical scheme: a non-foaming silicon branched fatty acid ionic liquid surfactant has a structural formula shown as a formula (1):
R1、R2and R3Each is any one of methyl, ethyl, propyl, isopropyl, tert-butyl, phenyl and benzyl;
m is a cation, and comprises any one of hydroxyethyl trimethyl quaternary ammonium cation, benzyl trimethyl quaternary ammonium cation, tetramethyl quaternary ammonium cation and tetraethyl quaternary ammonium cation;
r4 is a linear alkyl group having 7 to 15 carbon atoms.
As a preferable embodiment of the non-foaming silicon branched fatty acid ionic liquid surfactant of the present invention, wherein: the silicon branched ionic liquid surfactant does not have foaming capacity after being dissolved in water, and cannot form stable foam.
It is still another object of the present invention to overcome the disadvantages of the prior art and to provide a method for preparing a non-foaming silicone branched fatty acid ionic liquid surfactant.
In order to solve the technical problems, the invention provides the following technical scheme: a preparation method of a silicon branched fatty acid ionic liquid surfactant is characterized by comprising the following steps: comprises the steps of (a) preparing a mixture of a plurality of raw materials,
preparing unsaturated fatty acid ionic liquid: mixing unsaturated fatty acid and organic quaternary ammonium base, stirring at room temperature for 2-6 h, and removing the solvent to obtain unsaturated fatty acid ionic liquid, wherein the unsaturated fatty acid ionic liquid has a structural formula shown in formula (2):
wherein R4 is any one of linear alkyl groups with carbon number of 7-15; m is a cation, and comprises any one of hydroxyethyl trimethyl quaternary ammonium cation, benzyl trimethyl quaternary ammonium cation, tetramethyl quaternary ammonium cation and tetraethyl quaternary ammonium cation;
preparing a dihydroxyl fatty acid ionic liquid: slowly dropwise adding 1-4 times of equivalent hydrogen peroxide into the unsaturated fatty acid ionic liquid at 30 ℃, then continuously stirring for 4-8 h at 60-90 ℃, and removing the solvent by reduced pressure distillation to obtain the dihydroxyl fatty acid ionic liquid, wherein the structural formula of the dihydroxyl fatty acid ionic liquid is shown as a formula (3):
wherein R4 is any one of linear alkyl groups with carbon number of 7-15; m is a cation and comprises any one of hydroxyethyl trimethyl quaternary ammonium cation, benzyl trimethyl quaternary ammonium cation, tetramethyl quaternary ammonium cation and tetraethyl quaternary ammonium cation.
Preparing a silicon branched fatty acid ionic liquid: and adding triethylamine and chlorosilane into the dihydroxy fatty acid ionic liquid, stirring and reacting for 5-10 h, washing with water at low temperature to remove impurities, and thus obtaining the silicon branched fatty acid ionic liquid surfactant.
As a preferable scheme of the preparation method of the non-foaming silicon branched fatty acid ionic liquid surfactant, the preparation method comprises the following steps: the unsaturated fatty acid comprises one of oleic acid, arachidic acid and erucic acid.
As a preferable scheme of the preparation method of the non-foaming silicon branched fatty acid ionic liquid surfactant, the preparation method comprises the following steps: the alkali comprises one of hydroxyethyl trimethyl ammonium hydroxide, benzyl trimethyl ammonium hydroxide, tetramethyl ammonium hydroxide and tetraethyl ammonium hydroxide.
As a preferable scheme of the preparation method of the non-foaming silicon branched fatty acid ionic liquid surfactant, the preparation method comprises the following steps: the amount of unsaturated fatty acids is equal to the amount of fatty acids in the material.
As a preferable scheme of the preparation method of the non-foaming silicon branched fatty acid ionic liquid surfactant, the preparation method comprises the following steps: the chlorosilane comprises one of tert-butyldimethylchlorosilane, tert-butyldiethylchlorosilane, phenyldimethylchlorosilane and benzyldimethylchlorosilane.
As a preferable scheme of the preparation method of the non-foaming silicon branched fatty acid ionic liquid surfactant, the preparation method comprises the following steps: the molar ratio of the chlorosilane to the dihydroxyl fatty acid ionic liquid is 3-2: 1.
As a preferable scheme of the preparation method of the non-foaming silicon branched fatty acid ionic liquid surfactant, the preparation method comprises the following steps: adding triethylamine and chlorosilane into the dihydroxy fatty acid ionic liquid, wherein the temperature of the addition is 50-70 ℃.
As a preferable scheme of the preparation method of the non-foaming silicon branched fatty acid ionic liquid surfactant, the preparation method comprises the following steps: the yield of the non-foam silicon branched fatty acid ionic liquid surfactant is more than 90 percent.
The invention has the beneficial effects that:
(1) the preparation of the non-foaming silicon branched fatty acid ionic liquid surfactant does not need an organic solvent; the fatty acid ionic liquid prepared in each step is a product, is a reactant of the next reaction, and has the function of a solvent;
(2) the aqueous solution formed by dissolving the silicon branched fatty acid ionic liquid surfactant prepared by the invention in water has no foaming capacity, but the surface tension is lower; the silicon branched fatty acid ionic liquid surfactant prepared by the invention is extremely easy to degrade.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without inventive exercise. Wherein:
FIG. 1 shows the NMR spectrum of an ionic liquid of 9, 10-bis (t-butyldimethylsilyloxy) hydroxyethyltrimethylammonium stearate prepared in example 1 of the present invention.
FIG. 2 is a comparative foam plot of aqueous solutions of a silicon branched fatty acid ionic liquid surfactant (9, 10-bis (t-butyldimethylsilyloxy) hydroxyethyltrimethylammonium stearate SiOCho) and two intermediates (hydroxyethyltrimethylammonium oleate OCho, 9, 10-bis-hydroxystearic acid hydroxyethyltrimethylammonium DOCho) in accordance with an embodiment of the present invention.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention more comprehensible, specific embodiments thereof are described in detail below with reference to examples of the specification.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways than those specifically described and will be readily apparent to those of ordinary skill in the art without departing from the spirit of the present invention, and therefore the present invention is not limited to the specific embodiments disclosed below.
Furthermore, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
Example 1
(1) Mixing 10 millimole of oleic acid with 10 millimole of hydroxyethyl trimethyl ammonium hydroxide, stirring for 3 hours at room temperature, and drying to obtain light yellow and viscous liquid, namely the oleic acid hydroxyethyl trimethyl ammonium salt.
(2) Slowly dropwise adding 25 millimole times equivalent hydrogen peroxide into 10 millimole oleic acid hydroxyethyl trimethyl ammonium salt at 30 ℃, then continuously stirring for 6h at 75 ℃, and drying to obtain colorless viscous liquid, namely 9, 10-dihydroxystearic acid hydroxyethyl trimethyl ammonium salt.
(3) Adding 25 millimole triethylamine and 25 millimole tert-butyldimethylsilyl chloride into 10 millimole 9, 10-dihydroxyl stearic acid hydroxyethyl trimethyl ammonium salt ionic liquid at 50 ℃, stirring for reaction for 9 hours, washing the product with ice water at 0 ℃ for 3 times to remove impurities, and drying to obtain transparent viscous liquid, namely 9, 10-bis (tert-butyldimethylsilyloxy) stearic acid hydroxyethyl trimethyl ammonium salt ionic liquid with the yield of 93%.
Example 2
(1) Mixing 6 millimoles of arachidonic acid and 6 millimoles of tetramethylammonium hydroxide, stirring for 2 hours at room temperature, and drying to obtain light yellow viscous liquid, namely the arachidonic acid tetramethylammonium salt ionic liquid.
(2) Slowly dropwise adding 10 millimolar times of equivalent hydrogen peroxide into 5 millimolar arachidonic acid tetramethyl ammonium salt ionic liquid at 30 ℃, then continuously stirring for 8 hours at 60 ℃, and drying to obtain colorless viscous liquid, namely 9, 10-arachidic acid tetramethyl ammonium salt ionic liquid.
(3) Adding 15 mmol of triethylamine and 10 mmol of tert-butyldiethylchlorosilane into 5 mmol of 9, 10-arachidic acid tetramethylammonium salt ionic liquid at 60 ℃, stirring for reaction for 10h, washing the product with ice water at 0 ℃ for 3 times to remove impurities, and drying to obtain transparent viscous liquid, namely 9, 10-bis (tert-butyldiethylsiloxy) arachidic acid tetramethylammonium salt ionic liquid with the yield of 90%.
Example 3
(1) 5 millimole of erucic acid and 5 millimole of benzyl trimethyl ammonium hydroxide are mixed, stirred for 6 hours at room temperature and dried to obtain viscous liquid, namely the erucic acid benzyl trimethyl ammonium salt ionic liquid.
(2) Slowly dropwise adding 20 millimolar times equivalent hydrogen peroxide into 5 millimolar erucic acid benzyl trimethyl ammonium salt ionic liquid at 30 ℃, then continuously stirring for 4 hours at 90 ℃, and drying to obtain colorless viscous liquid, namely 9, 10-docosaccarbonate benzyl trimethyl ammonium salt ionic liquid.
(3) At 70 ℃,10 mmol of triethylamine and 10 mmol of phenyldimethylchlorosilane are added into 5 mmol of 9, 10-docosanoic acid benzyltrimethyl ammonium salt ionic liquid, the mixture is stirred and reacted for 5 hours, the product is washed by ice water at 0 ℃ for 3 times to remove impurities, and transparent viscous liquid, namely 9, 10-bis (phenyldimethylsiloxy) docosanoic acid benzyltrimethyl ammonium salt ionic liquid is obtained after drying, wherein the yield is 92%.
Example 4
(1) Mixing 10 mmol of oleic acid and 10 mmol of phenyl dimethyl ammonium hydroxide, stirring for 4 hours at room temperature, and drying to obtain light yellow and viscous liquid, namely the oleic acid phenyl dimethyl ammonium salt ionic liquid.
(2) Slowly dropwise adding 25 millimole times equivalent hydrogen peroxide into 10 millimole of oleic acid phenyl dimethyl ammonium salt ionic liquid at 30 ℃, then continuously stirring for 5 hours at 75 ℃, and drying to obtain colorless viscous liquid, namely 9, 10-dihydroxystearic acid phenyl dimethyl ammonium salt ionic liquid.
(3) At 50 ℃, adding 30 mmol of triethylamine and 25 mmol of benzyldimethylchlorosilane into 10 mmol of 9, 10-bis (hydroxy) stearic acid phenyl dimethyl ammonium salt ionic liquid, stirring for reaction for 7 hours, washing the product with ice water at 0 ℃ for 3 times to remove impurities, and drying to obtain transparent viscous liquid, namely 9, 10-bis (benzyl dimethyl siloxy) stearic acid phenyl dimethyl ammonium salt ionic liquid, wherein the yield is 94%.
Example 5
(1) Surface performance of the silicon branched fatty acid ionic liquid surfactant:
the critical micelle concentration of the surfactant aqueous solution prepared in examples 1 to 4 at 25 ℃ was measured by a hanging piece method, and hydroxyethyl trimethylammonium oleate and hydroxyethyl trimethylammonium 9, 10-bishydroxy stearate were used as control samples. The results are shown in Table 1.
(2) Foam performance:
the silicon branched surfactant prepared in the examples 1 to 4 was prepared into an aqueous solution of a certain concentration, 3 ml of the aqueous solution was taken out of a small test tube, vigorously shaken for 30 seconds, and the foam volume was recorded. The hydroxyethyl trimethyl ammonium oleate and the hydroxyethyl trimethyl ammonium 9, 10-dihydroxystearate are used as comparison samples. The results are shown in Table 1.
(3) Biodegradability:
the biodegradation degree of the silicon branched surfactant prepared in the embodiment 1-4 is calculated according to a biodegradation experiment carried out by GB/T15818-2018. The hydroxyethyl trimethyl ammonium oleate and the hydroxyethyl trimethyl ammonium 9, 10-dihydroxystearate are used as comparison samples. The results are shown in Table 2.
TABLE 1
TABLE 2
As can be seen from Table 1, after two silicon branched chains are introduced on a hydrophobic chain, the critical micelle concentration and the lowest surface tension of the surfactant are both greatly reduced, which shows that the surfactant has stronger self-assembly capability. Compared with the oleic acid hydroxyethyl trimethyl ammonium salt and the 9, 10-dihydroxystearic acid hydroxyethyl trimethyl ammonium salt which have the same main chain, the critical micelle concentration of the silicon branched surfactant prepared by the invention is 1 to 3 orders of magnitude lower. It is shown that the incorporation of the silicon branched structure is more favorable for the self-assembly of the surfactants prepared in examples 1-4.
As can be seen from Table 1, the aqueous solutions of the silicon branched surfactants prepared in examples 1 to 4 of the present invention have no foaming ability at concentrations higher than the critical micelle concentration, while the comparative examples have better foaming performance, which indicates that the foaming performance of the surfactants is completely destroyed by the introduction of the silicon branched chain structure.
As can be seen from Table 2, the silicon branched surfactants prepared in examples 1-4 of the present invention have a biodegradability of more than 92% in 3 days, and a biodegradability of more than 99.5% in 7 days, which is significantly better than hydroxyethyl trimethylammonium salt of 9, 10-dihydroxystearate and slightly better than hydroxyethyl trimethylammonium salt of oleic acid. This indicates that the introduction of the silicon branched structure favors the biodegradation of the surfactant.
The silicon atoms are positioned on the branched chains of the hydrophobic carbon chains of the surfactant, but not the main chains, and the prepared silicon-containing surfactant has no foaming performance in an aqueous solution, meanwhile, the silicon-containing surfactant is derived from natural fatty acid, and the silicon branched ionic liquid surfactant has no foaming capacity after being dissolved in water, cannot form stable foam, and is related to the introduction of the silicon-containing branched chains in the middle positions of the hydrophobic carbon chains.
Generally, on the premise of the same molecular weight, the critical micelle concentration of a branched structure is larger than that of an unbranched structure, but after two silicon branched chains are introduced on a hydrophobic chain, the critical micelle concentration and the lowest surface tension of a surfactant are both greatly reduced,
at present, the traditional silicon-containing surfactant is a surfactant taking a silicon-oxygen bond or a silicon-carbon bond as a hydrophobic main chain, the number of silicon atoms is more than 4, and the silicon-containing surfactant only contains two silicon atoms and is positioned on a branched chain. The aqueous solution formed by dissolving the silicon branched fatty acid ionic liquid surfactant prepared by the invention in water has no foaming capacity, but the surface tension is lower; the silicon branched fatty acid ionic liquid surfactant prepared by the invention is extremely easy to degrade.
It should be noted that the above-mentioned embodiments are only for illustrating the technical solutions of the present invention and not for limiting, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, which should be covered by the claims of the present invention.
Claims (10)
1. A non-foaming silicon branched fatty acid ionic liquid surfactant is characterized in that: the structural formula of the surfactant is shown as a formula (1):
R1、R2and R3Each is any one of methyl, ethyl, propyl, isopropyl, tert-butyl, phenyl and benzyl;
m is a cation, and comprises any one of hydroxyethyl trimethyl quaternary ammonium cation, benzyl trimethyl quaternary ammonium cation, tetramethyl quaternary ammonium cation and tetraethyl quaternary ammonium cation;
r4 is a linear alkyl group having 7 to 15 carbon atoms.
2. The non-foaming silicon branched fatty acid ionic liquid surfactant of claim 1, wherein: the silicon branched ionic liquid surfactant does not have foaming capacity after being dissolved in water, and cannot form stable foam.
3. A method for preparing the silicon-branched fatty acid ionic liquid surfactant as claimed in any one of claims 1 to 2, wherein: comprises the steps of (a) preparing a mixture of a plurality of raw materials,
preparing unsaturated fatty acid ionic liquid: mixing unsaturated fatty acid and organic quaternary ammonium base, stirring at room temperature for 2-6 h, and removing the solvent to obtain unsaturated fatty acid ionic liquid, wherein the unsaturated fatty acid ionic liquid has a structural formula shown in formula (2):
wherein R4 is any one of linear alkyl groups with carbon number of 7-15; m is a cation, and comprises any one of hydroxyethyl trimethyl quaternary ammonium cation, benzyl trimethyl quaternary ammonium cation, tetramethyl quaternary ammonium cation and tetraethyl quaternary ammonium cation;
preparing a dihydroxyl fatty acid ionic liquid: slowly dropwise adding 1-4 times of equivalent hydrogen peroxide into the unsaturated fatty acid ionic liquid at 30 ℃, then continuously stirring for 4-8 h at 60-90 ℃, and removing the solvent by reduced pressure distillation to obtain the dihydroxyl fatty acid ionic liquid, wherein the structural formula of the dihydroxyl fatty acid ionic liquid is shown as a formula (3):
wherein R4 is any one of linear alkyl groups with carbon number of 7-15; m is a cation and comprises any one of hydroxyethyl trimethyl quaternary ammonium cation, benzyl trimethyl quaternary ammonium cation, tetramethyl quaternary ammonium cation and tetraethyl quaternary ammonium cation.
Preparing a silicon branched fatty acid ionic liquid: and adding triethylamine and chlorosilane into the dihydroxy fatty acid ionic liquid, stirring and reacting for 5-10 h, washing with water at low temperature to remove impurities, and thus obtaining the silicon branched fatty acid ionic liquid surfactant.
4. The method for preparing the non-foaming silicon branched fatty acid ionic liquid surfactant as claimed in claim 3, wherein: the unsaturated fatty acid comprises one of oleic acid, arachidic acid and erucic acid.
5. The method for producing the non-foaming silicon branched fatty acid ionic liquid surfactant according to claim 3, wherein: the alkali comprises one of hydroxyethyl trimethyl ammonium hydroxide, benzyl trimethyl ammonium hydroxide, tetramethyl ammonium hydroxide and tetraethyl ammonium hydroxide.
6. The method for producing the non-foaming silicon branched fatty acid ionic liquid surfactant according to claim 4 or 5, wherein: the amount of unsaturated fatty acids is equal to the amount of fatty acids in the material.
7. The method for preparing the non-foaming silicon branched fatty acid ionic liquid surfactant as claimed in claim 3, wherein: the chlorosilane comprises one of tert-butyldimethylchlorosilane, tert-butyldiethylchlorosilane, phenyldimethylchlorosilane and benzyldimethylchlorosilane.
8. The method of preparing the non-foaming silicon branched fatty acid ionic liquid surfactant of claim 7, wherein: the molar ratio of the chlorosilane to the dihydroxyl fatty acid ionic liquid is 3-2: 1.
9. The method for preparing the non-foaming silicon branched fatty acid ionic liquid surfactant as claimed in claim 3, wherein: adding triethylamine and chlorosilane into the dihydroxy fatty acid ionic liquid, wherein the temperature of the addition is 50-70 ℃.
10. The method for preparing the non-foaming silicon branched fatty acid ionic liquid surfactant as claimed in claim 3, wherein: the yield of the non-foam silicon branched fatty acid ionic liquid surfactant is more than 90 percent.
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| CA2233451A1 (en) * | 1995-09-29 | 1997-04-03 | Dimitris Lappas | Liquid laundry detergents containing selected quaternary ammonium compounds |
| CN106188124A (en) * | 2016-07-12 | 2016-12-07 | 皖西学院 | The preparation method of novel ester organosilicon quaternary ammonium salt |
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