CN105732686B - A kind of tetrasiloxane surface-active ion liquid and preparation method thereof - Google Patents
A kind of tetrasiloxane surface-active ion liquid and preparation method thereof Download PDFInfo
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- CN105732686B CN105732686B CN201610047857.8A CN201610047857A CN105732686B CN 105732686 B CN105732686 B CN 105732686B CN 201610047857 A CN201610047857 A CN 201610047857A CN 105732686 B CN105732686 B CN 105732686B
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- tetrasiloxane
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- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0834—Compounds having one or more O-Si linkage
- C07F7/0838—Compounds with one or more Si-O-Si sequences
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Abstract
The invention discloses a kind of tetrasiloxane surface-active ion liquid and preparation method thereof, and general structure is as follows:Wherein R=CnH2n+1Or CF3;N is 0,1,2,3.The present invention also provides a kind of preparation methods of tetrasiloxane surface-active ion liquid.Tetrasiloxane surface-active ion liquid of the invention has excellent physicochemical property, and the lowest surface tension of aqueous solution is 20-40mN/m;Critical micelle concentration is 20-400mg/L in aqueous solution.
Description
Technical field
The invention belongs to surface-active ion liquid technology fields, and in particular to a kind of tetrasiloxane surface-active ion liquid
Body and preparation method thereof.
Background technique
Ionic liquid refers in room temperature or close to liquid, the salt as composed by zwitterion completely is presented at room temperature,
Referred to as low temperature molten salt.Since ionic liquid has, low volatility, liquid temperature range is wide, thermal stability is good, the characteristics such as less toxic,
It is set to have a wide range of applications in many fields such as chemical science and technology, medical industry.
Surfactant is commonly called as " industrial monosodium glutamate ", refers to that those additions just can significantly reduce solution surface tension, change on a small quantity
The substance of variant system interface state has the characteristics that high surface activity, heat-resist, is widely used in detergents and cosmetic, pesticide, doctor
The fields such as medicine engineering.According to the difference of hydrophobic chain, it is divided into alkanes surfactant, silicon class surfactant, the work of fluorine class surface
The surfactants such as property agent.
Surface-active ion liquid due to the advantages of being integrated with ionic liquid and surfactant, enzymatic, lubricant,
It is had potential application in the various fields such as heat transfer medium.It is ground currently, the research about surface-active ion liquid becomes
Study carefully hot spot.
Common surface-active ion liquid is mainly based on the alkanes ionic liquid of long-chain, Chinese patent
CN103933893A has synthesized a kind of choline-like ionic liquid surfactant, tetradecylmethyl-(2- ethoxy)-dimethyl
Ammonium chloride, tetradecyloxyaniline methyl-(2- ethoxy)-dimethyl tetrafluoro boric acid and tetradecyloxyaniline methyl-(2- ethoxy)-two
Methyl ammonium nitrate, but there are synthesis steps it is cumbersome, surface-active is poor the problems such as.In order to improve its surface-active, existing skill
The surface-active ion liquid of art, is to be synthesized by two-step process, and separating-purifying is more difficult, and synthesis step is cumbersome.
Therefore, the problems such as surface-active ion liquid is of less types and synthetic method is cumbersome is prepared in view of existing, needed out
Hair novel surface active ion liquid simultaneously studies preparation method.
Summary of the invention
Technical problem to be solved by the present invention lies in provide one kind to facilitate abundant surface-active ion class of liquids simultaneously
And the tetrasiloxane surface-active ion liquid and preparation method thereof of structure novel.
The technical issues of to solve above-mentioned first aspect, the present invention provides a kind of tetrasiloxane surface-active ion liquid,
Its general structure is as follows:
Wherein R=CnH2n+1Or CF3;N is 0,1,2,3.
The second aspect of the present invention is to provide a kind of preparation method of tetrasiloxane surface-active ion liquid, this method
Be conducive to significantly shorten reaction process, reduce preparation cost and use and meet industrial amplification production requirement and be beneficial to ensure nothing
Toxicity and use embodiment environmental protection with safety.
The technical issues of to solve the second aspect of the present invention, the present invention provides a kind of tetrasiloxane surface-active ions
The preparation method of liquid, reaction equation are as follows, comprising the following steps:
The preparation of (1) three aminopropyl sealing end tetrasiloxane
With bis- (the 3- aminopropyls) -1 of methyl trialkoxysilane, 1,3-, 1,3,3- tetramethyl disiloxane is raw material, benefit
It with catalyst, reacts at a certain temperature, after reaction, makes catalyst inactivation, vacuum distillation removal excess raw material obtains three
Aminopropyl blocks tetrasiloxane;
(2) preparation of tetrasiloxane surface-active ion liquid
Using three aminopropyls sealing end tetrasiloxane, short chain organic acid as raw material, under low boiling point solvent effect, in certain temperature
Under, certain time is reacted, after reaction, drying after solvent is evaporated off, obtains tetrasiloxane surface-active ion liquid.
In a specific technical solution of the invention, methyl trialkoxysilane is selected from methyl three in the step (1)
Methoxy silane, methyltriethoxysilane.
In another specific technical solution of the invention, methyl trialkoxysilane and 1,3- are bis- in the step (1)
The molar ratio of (3- aminopropyl) -1,1,3,3- tetramethyl disiloxane and catalyst is 1:5-20:0.01-0.08;Control is anti-
Answering temperature is 50-120 DEG C;The control reaction time is 1-30h.
In another specific technical solution of the invention, in the step (1) catalyst be selected from alkali metal hydroxide,
Silicon alkoxide, quaternary ammonium base, quaternary phosphonium hydroxide, silanol quaternary ammonium salt or silanol quaternary alkylphosphonium salt;Wherein, described that catalyst inactivation is made to be: to work as catalysis
When agent is any one in alkali metal hydroxide and silicon alkoxide, acid is added, catalyst is neutralized and makes catalyst inactivation, and
When catalyst is any one in quaternary ammonium base, quaternary phosphonium hydroxide, silanol quaternary ammonium salt and silanol quaternary alkylphosphonium salt, carries out heat resolve and make
Catalyst inactivation.
Of the invention there are one in specific technical solution, alkali metal hydroxide described in the step (1) is
Sodium hydroxide or potassium hydroxide;The silicon alkoxide is sodium silanolate or silanol potassium;The quaternary ammonium base is tetramethylammonium hydroxide;
The quaternary phosphonium hydroxide is Si butyl phosphonium hydroxides;The silanol quaternary ammonium salt is tetramethyl silanol ammonium;The silanol quaternary alkylphosphonium salt
For tetrabutyl silanol Phosphonium.
In an of the invention and then specific technical solution, in the step (2) three aminopropyls sealing end tetrasiloxane with
Short chain organic acid molar ratio is 1:3-9;Controlling reaction temperature is 20-80 DEG C;The control reaction time is 5-50h.
Of the invention more and in a specific technical solution, short chain organic acid is selected from formic acid, second in the step (2)
One or more of acid, propionic acid, butyric acid, trifluoroacetic acid;Low boiling point solvent be selected from methylene chloride, dichloroethanes, acetone,
One or more of ethyl acetate.
Tetrasiloxane surface-active ion liquid provided by the invention is obtained as a kind of new surface-active ion liquid
To enrich the type of modified surface active's ionic liquid, use scope is extended.Due to having abandoned traditional synthesis in preparation method
The two-step method of surface-active ion liquid has preparation process letter without tired using one-step synthesis method, and preparation cost
The advantages that cheap, thus industrial amplification production requirement can be met.Since the tetrasiloxane surface-active ion liquid of synthesis has
Standby excellent surface-active, so as to be applied in the fields such as pesticide, medicine, daily use chemicals, weaving.Tetrasiloxane surface of the invention
Active ion liquid has excellent physicochemical property, and the lowest surface tension of aqueous solution is 20-40mN/m;Face in aqueous solution
Boundary's micellar concentration is 20-400mg/L.
Specific embodiment
The following examples are of the invention to be further described, but the contents of the present invention are without being limited thereto.Present invention explanation
Embodiment in book is only used for that the present invention will be described, does not play restriction effect to protection scope of the present invention.This
The protection scope of invention is only defined by the claims, and those skilled in the art are in embodiment disclosed by the invention on the basis of institute
Any omission, replacement or the modification made fall within protection scope of the present invention.
The tetrasiloxane surface-active ion liquid of preparation structures shown below general formula is said by six embodiments respectively
It is bright.
Wherein R=CnH2n+1Or CF3;N is 0,1,2,3.
Embodiment 1
Methyltrimethoxysilane 13.6Kg (100mol) is added in a kettle, 1,3- bis- (3- aminopropyls) -1,1,
3,3- tetramethyl disiloxane 124.3Kg (500mol), tetramethylammonium hydroxide 0.72Kg (8mol) are dissolved by heating, temperature control
System after reaction 30 hours, is warming up to 140 DEG C, makes catalyst inactivation at 50 DEG C.Rectification under vacuum removal excess raw material obtains three ammonia third
Base blocks tetrasiloxane 43.9Kg (100mol), is added formic acid 13.8Kg (300mol), solvent is made with methylene chloride, at 50 DEG C
Reaction 5 hours, is evaporated off methylene chloride and excess raw material, tetrasiloxane surface-active ion liquid is obtained after vacuum drying
57.7Kg.It is 20mN/m, critical micelle concentration 200mg/ with the lowest surface tension that K12 surface tension instrument measures its aqueous solution
L。
Embodiment 2
Methyltrimethoxysilane 13.6Kg (100mol) is added in a kettle, 1,3- bis- (3- aminopropyls) -1,1,
3,3- tetramethyl disiloxane 248.6Kg (1000mol), Si butyl phosphonium hydroxides 0.27Kg (1mol) are dissolved by heating, temperature control
System after reaction 15 hours, is warming up to 140 DEG C, makes catalyst inactivation at 70 DEG C.Rectification under vacuum removal excess raw material obtains three ammonia third
Base blocks tetrasiloxane 43.9Kg (100mol), is added acetic acid 36.0Kg (600mol), solvent is made with dichloroethanes, at 80 DEG C
Reaction 20 hours, is evaporated off solvent dichloroethanes and excess raw material, tetrasiloxane surface-active ion liquid is obtained after vacuum drying
61.9Kg.It is 25mN/m, critical micelle concentration 100mg/ with the lowest surface tension that K12 surface tension instrument measures its aqueous solution
L。
Embodiment 3
Methyltrimethoxysilane 13.6Kg (100mol) is added in a kettle, 1,3- bis- (3- aminopropyls) -1,1,
3,3- tetramethyl disiloxane 497.2Kg (2000mol), tetramethyl silanol ammonium 1.06Kg (3.0mol) are dissolved by heating, temperature control
System after reaction 1 hour, is warming up to 140 DEG C, makes catalyst inactivation at 120 DEG C.Rectification under vacuum removal excess raw material obtains three ammonia third
Base blocks tetrasiloxane 43.9Kg (100mol), is added propionic acid 66.6Kg (900mol), makees solvent with acetone, react at 20 DEG C
50 hours, solvent acetone and excess raw material is evaporated off, tetrasiloxane surface-active ion liquid 66.1Kg is obtained after vacuum drying.With
The lowest surface tension that K12 surface tension instrument measures its aqueous solution is 30mN/m, critical micelle concentration 300mg/L.
Embodiment 4
Methyltriethoxysilane 17.8Kg (100mol) is added in a kettle, 1,3- bis- (3- aminopropyls) -1,1,
3,3- tetramethyl disiloxane 198.8Kg (800mol), trimethyl silicane sodium alkoxide 0.58Kg (8.0mol) are dissolved by heating, temperature control
System after reaction 10 hours, is warming up to 140 DEG C, makes catalyst inactivation at 90 DEG C.Rectification under vacuum removal excess raw material obtains three ammonia third
Base blocks tetrasiloxane 43.9Kg (100mol), is added butyric acid 35.2Kg (400mol), solvent is made with ethyl acetate, at 70 DEG C
Reaction 30 hours, is evaporated off solvent ethyl acetate and excess raw material, tetrasiloxane surface-active ion liquid is obtained after vacuum drying
70.3Kg.It is 40mN/m, critical micelle concentration 400mg/ with the lowest surface tension that K12 surface tension instrument measures its aqueous solution
L。
Embodiment 5
Methyltriethoxysilane 17.8Kg (100mol) is added in a kettle, 1,3- bis- (3- aminopropyls) -1,1,
3,3- tetramethyl disiloxane 298.2Kg (1200mol), sodium hydroxide 0.24Kg (6mol) are dissolved by heating, and temperature is controlled 90
DEG C, after reaction 10 hours, acid adding is neutralized, and makes catalyst inactivation.Rectification under vacuum removal excess raw material obtains three aminopropyls sealing end four
Siloxanes 43.9Kg (100mol) is added trifluoroacetic acid 57.01Kg (500mol), makees solvent with dichloroethanes, anti-at 60 DEG C
It answers 25 hours, solvent dichloroethanes and excess raw material is evaporated off, tetrasiloxane surface-active ion liquid is obtained after vacuum drying
78.1Kg.It is 33mN/m, critical micelle concentration 260mg/ with the lowest surface tension that K12 surface tension instrument measures its aqueous solution
L。
Embodiment 6
Methyltriethoxysilane 17.8Kg (100mol) is added in a kettle, 1,3- bis- (3- aminopropyls) -1,1,
3,3- tetramethyl disiloxane 372.7Kg (1500mol), potassium hydroxide 0.05Kg (1.0mol) are dissolved by heating, and temperature control exists
After 100 DEG C, reaction 9 hours, acid adding is neutralized, and makes catalyst inactivation.Rectification under vacuum removal excess raw material obtains three aminopropyls sealing end
Tetrasiloxane 43.9Kg (100mol) is added formic acid 36.8Kg (800mol), makees solvent with dichloroethanes, react 17 at 60 DEG C
Hour, solvent dichloroethanes and excess raw material is evaporated off, tetrasiloxane surface-active ion liquid 57.7Kg is obtained after vacuum drying.
It is 27mN/m, critical micelle concentration 320mg/L with the lowest surface tension that K12 surface tension instrument measures its aqueous solution.
The foregoing examples are merely illustrative of the technical concept and features of the invention, its object is to allow the person skilled in the art to be
It cans understand the content of the present invention and implement it accordingly, it is not intended to limit the scope of the present invention.It is all smart according to the present invention
The equivalent transformation or modification that refreshing essence is done, should be covered by the protection scope of the present invention.
Claims (8)
1. a kind of tetrasiloxane surface-active ion liquid, general structure are as follows:
Wherein R=CF3。
2. a kind of preparation method of tetrasiloxane surface-active ion liquid as described in claim 1, which is characterized in that it is anti-
Answer formula as follows, comprising the following steps:
The preparation of (1) three aminopropyl sealing end tetrasiloxane
With bis- (the 3- aminopropyls) -1 of methyl trialkoxysilane, 1,3-, 1,3,3- tetramethyl disiloxane is raw material, using urging
Agent is reacted at a certain temperature, after reaction, makes catalyst inactivation, vacuum distillation removal excess raw material obtains three ammonia third
Base blocks tetrasiloxane;
(2) preparation of tetrasiloxane surface-active ion liquid
Using three aminopropyls sealing end tetrasiloxane, trifluoroacetic acid as raw material, under low boiling point solvent effect, at a certain temperature, instead
Certain time is answered, after reaction, drying after solvent is evaporated off, obtains tetrasiloxane surface-active ion liquid;Wherein, low boiling point
Solvent is selected from methylene chloride, dichloroethanes, acetone, one or more of ethyl acetate.
3. the preparation method of tetrasiloxane surface-active ion liquid according to claim 2, which is characterized in that the step
Suddenly methyl trialkoxysilane is selected from methyltrimethoxysilane, methyltriethoxysilane in (1).
4. the preparation method of tetrasiloxane surface-active ion liquid according to claim 2, which is characterized in that the step
Suddenly methyl trialkoxysilane and bis- (3- the aminopropyl) -1,1,3,3- tetramethyl disiloxanes of 1,3- and catalyst in (1)
Molar ratio is 1:5-20:0.01-0.08;Controlling reaction temperature is 50-120 DEG C;The control reaction time is 1-30h.
5. the preparation method of tetrasiloxane surface-active ion liquid according to claim 2, which is characterized in that the step
Suddenly catalyst is selected from alkali metal hydroxide, silicon alkoxide, quaternary ammonium base, quaternary phosphonium hydroxide, silanol quaternary ammonium salt or silanol quaternary alkylphosphonium salt in (1);
Wherein, described that catalyst inactivation is made to be: when any one in catalyst alkali metal hydroxide and silicon alkoxide, to be added
Acid neutralizes catalyst and makes catalyst inactivation, and when catalyst is quaternary ammonium base, quaternary phosphonium hydroxide, silanol quaternary ammonium salt and silanol quaternary alkylphosphonium salt
In any one when, carry out heat resolve and make catalyst inactivation.
6. the preparation method of tetrasiloxane surface-active ion liquid according to claim 5, which is characterized in that the step
Suddenly the alkali metal hydroxide in (1) is sodium hydroxide or potassium hydroxide;The silicon alkoxide is sodium silanolate or silanol potassium;It is described
Quaternary ammonium base be tetramethylammonium hydroxide.
7. the preparation method of tetrasiloxane surface-active ion liquid according to claim 5, which is characterized in that the step
Suddenly quaternary phosphonium hydroxide is Si butyl phosphonium hydroxides in (1);The silanol quaternary ammonium salt is tetramethyl silanol ammonium;The silanol quaternary phosphine
Salt is tetrabutyl silanol Phosphonium.
8. the preparation method of tetrasiloxane surface-active ion liquid according to claim 2, which is characterized in that the step
Suddenly three aminopropyls sealing end tetrasiloxane and trifluoroacetic acid molar ratio are 1:3-9 in (2);Controlling reaction temperature is 20-80 DEG C;Control
Reaction time is 5-50h.
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CN112044353B (en) * | 2019-06-05 | 2022-06-28 | 新特能源股份有限公司 | Novel Gemini surfactant and preparation method thereof, novel comb-type surfactant and preparation method thereof |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104231274A (en) * | 2014-08-21 | 2014-12-24 | 中国日用化学工业研究院 | Surface activity organosilicon room-temperature ionic liquid and synthetic method thereof |
CN104610338A (en) * | 2015-01-13 | 2015-05-13 | 常熟理工学院 | Glycosyl amide modified tetrasiloxane and preparation method thereof |
CN104645877A (en) * | 2015-02-02 | 2015-05-27 | 常熟理工学院 | Bola type polyether modified organic silicon surfactant and preparation method thereof |
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Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
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CN104231274A (en) * | 2014-08-21 | 2014-12-24 | 中国日用化学工业研究院 | Surface activity organosilicon room-temperature ionic liquid and synthetic method thereof |
CN104610338A (en) * | 2015-01-13 | 2015-05-13 | 常熟理工学院 | Glycosyl amide modified tetrasiloxane and preparation method thereof |
CN104645877A (en) * | 2015-02-02 | 2015-05-27 | 常熟理工学院 | Bola type polyether modified organic silicon surfactant and preparation method thereof |
Non-Patent Citations (1)
Title |
---|
"端氨丙基聚二甲基硅氧烷的合成研究";罗啸秋 等;《日用化学工业》;20140228;第44卷(第2期);第75-78页 |
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