CN104874326B - A kind of preparation method of intelligent vermiculate glues - Google Patents
A kind of preparation method of intelligent vermiculate glues Download PDFInfo
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- CN104874326B CN104874326B CN201510171008.9A CN201510171008A CN104874326B CN 104874326 B CN104874326 B CN 104874326B CN 201510171008 A CN201510171008 A CN 201510171008A CN 104874326 B CN104874326 B CN 104874326B
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Abstract
The present invention relates to the preparation method of a kind of intelligent vermiculate glues, belong to the applied technical field of surfactant.Intelligent vermiculate glues of the present invention, is with organic cation salt under the conditions of temperature 15 ~ 40 DEG C, and induction enuatrol (NaOA) is also prepared in the range of 8 ~ 10 by regulation pH value.The proterties of this vermiculate glues can change along with the change of pH value, therefore has pH response.
Description
Technical field
This technology relates to the preparation method of a kind of intelligent vermiculate glues, belongs to the application skill of surfactant
Art field.
Background technology
Surfactant includes little molecule and high molecular surfactant, and both can be transferred through molecular self-assembling shape
Become the multiple orderly body such as micella and vesica.Vermiculate glues, refers to that the surfactant with ad hoc structure exists
Under certain condition, the flexible rod formed along non axial one-dimensional growth by spherical micelle through self assembly in the solution
Shape or cylindrical micellar.Vermiculate glues is mutually wound around, and forms instantaneous three-dimensional net structure, macroscopically shows
It is similar to the viscoelasticity of polymer solution.
Intelligent vermiculate glues refers to external environmental condition (temperature, pH, electrolyte concentration, optical, electrical field etc.)
When there is minor variations, its physicochemical properties (surface tension, aggregated forms etc.) can produce the table of substantially change
Face activating agent.Its in oil field, the numerous areas such as medicine controlled releasing, bioengineering, microfluid, cosmetics has
Important using value.
Enuatrol (NaOA), is a kind of flaxen grease-like solid, has good solubility, water in the hot water
Solution facile hydrolysis becomes alkalescence, and alcohol liquid does not hydrolyzes.Having it is a kind of carboxylate anion's surfactant, molecule
In containing 18 carbon atoms, containing a unsaturated bond in hydrophobic chain, water-soluble very well, its raw materials for production can
With regeneration, cheap, aboundresources.The emulsifying ability that enuatrol is excellent, penetration and detergency, very
Multi-field it is widely used such as cleaning agent, preservative, fabric waterproofing agent.In recent years about vermiform
The existing many document reports of the research of micella, dominant cation surfactant is main.Anionic vermiform
Also someone studies micella, as prune assistant et al. have studied NaCO3、NaPO3Induce Deng containing Na ionic electrolytes
The vermiculate glues that NaOA is formed.Kalur et al. have studied the vermiculate glues that KCl induction enuatrol is formed.
Summary of the invention
The present invention provides a kind of intelligent vermiculate glues, to pH value sensitive, has certain pH and rings
Ying Xing.
The preparation method of a kind of intelligent vermiculate glues, comprises the following steps:
(1) preparation of mother liquor
Preparation enuatrol mother liquor, organic cation salt mother liquor, hydrochloric acid solution and sodium hydroxide solution；
(2) preparation of enuatrol/organic cation salt system
Pipette enuatrol mother liquor respectively, organic cation salt mother liquor mixes and is diluted with water, after mixing through stirring/
Shake and carry out ultrasonic water bath, stand；
(3) preparation of intelligent vermiculate glues
The enuatrol that step (2) obtains/organic cation salt system, control temperature, at 15～40 DEG C, adds step
Suddenly, after the hydrochloric acid solution of (1) gained and sodium hydroxide solution regulation pH value value 8～10, mix homogeneous to system
After i.e. obtain to pH value response intelligent vermiculate glues；
Described organic cation salt is one of following: benzyltrimethylammonium bromide (Benzyltrimethyl
Ammonium bromide, BTAB), triethylamine hydrochloride (Ethanamine, N, N-diethyl-,
hydrochloride,Et3NHCl) or triethanolamine hydrochloride (Triethanolamine hydrochloride,
TEA)。
Further, in described step (1), the molar concentration of enuatrol mother liquor is 0.2～0.3mol/L, You Jiyang
The concentration of ion salt mother liquor is molar concentration 0.8～1.0mol/L, and the mass concentration of hydrochloric acid solution is 30～37%,
Sodium hydroxide solution is its saturated solution.
Further, described step (2) ultrasonic water bath supersonic frequency 30～35kHz ultrasonic time 8～12min,
Time of repose 12～14h.
Further, described step (2) enuatrol molar concentration is all 0.1～0.15mol/L, for enuatrol/
Benzyltrimethylammonium bromide system, benzyltrimethylammonium bromide molar concentration is 0.1～0.5mol/L, for oil
Acid sodium/triethylamine hydrochloride system, triethylamine hydrochloride molar concentration is 0.1～0.5mol/L, for enuatrol/
Triethanolamine hydrochloride system, triethanolamine hydrochloride molar concentration is 0.2～0.4mol/L.
Further, in described step (3), enuatrol/benzyltrimethylammonium bromide system regulation pH value is 8～9,
Enuatrol/triethylamine hydrochloride system regulation pH value is 8.0～9.5, and enuatrol/triethanolamine hydrochloride system is adjusted
Joint pH value is 9～10.
Further, in described step (3), the mode of mixing uses stirring/concussion ultrasonic water bath or mixes
Rear standing 10～60min.
Further, in described step (3), the supersonic frequency of ultrasonic water bath chooses 30～35kHz.
Beneficial effects of the present invention:
The preparation method of the intelligent worm dress micella that the present invention proposes, raw material composition is simple, cheap,
The vermiculate glues viscosity formed is big, and the sensitive to pH, has certain responsive intelligent, at medicine
The fields such as the controlled release of thing have the biggest application potential.
Accompanying drawing explanation
In order to be illustrated more clearly that the embodiment of the present invention or technical scheme of the prior art, below will be to enforcement
In example or description of the prior art, the required accompanying drawing used is briefly described, it should be apparent that, describe below
In accompanying drawing be only some embodiments of the present invention, for those of ordinary skill in the art, do not paying
On the premise of going out creative work, it is also possible to obtain other accompanying drawing according to these accompanying drawings.
Fig. 1 is under different pH, the relation between shear viscosity and the shear rate of NaOA/BTAB system；
Fig. 2 is under different pH, NaOA/Et3Pass between shear viscosity and the shear rate of NHCl system
System；
Fig. 3 is under different pH, between shear viscosity and the shear rate of NaOA/TEA HCl system
Relation；
Fig. 4 is when pH=8.45, NaOA/BTAB system shear viscosity and complex viscosity and shear rate and
The relation of angle of throw frequency
Fig. 5 is under different pH, NaOA/Et3The Cole-Cole figure of NHCl system；
Fig. 6 is under different pH, the Cole-Cole figure of NaOA/TEA HCl system.
Detailed description of the invention
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out clearly
Chu, be fully described by, it is clear that described embodiment be only a part of embodiment of the present invention rather than
Whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art are not making creation
The every other embodiment obtained under property work premise, broadly falls into the scope of protection of the invention.
Embodiment 1
The preparation method of a kind of intelligent vermiculate glues, comprises the following steps:
(1) preparation of mother liquor
Preparation enuatrol mother liquor, benzyltrimethylammonium bromide mother liquor, hydrochloric acid solution and NaOH are molten respectively
Liquid；Wherein the molar concentration of enuatrol mother liquor is 0.2mol/L, benzyltrimethylammonium bromide mother liquor mole dense
Degree is 0.8mol/L, and the mass concentration of hydrochloric acid solution is 30%, and sodium hydroxide solution is its saturated solution；
(2) preparation of enuatrol/organic cation salt system
Pipette enuatrol mother liquor respectively, benzyltrimethylammonium bromide mother liquor mixes and is diluted with water to enuatrol and rubs
Your concentration be 0.1mol/L, BTAB molar concentration be 0.1mol/L, through stirring/shake and choosing after mixing
30～35kHz ultrasonic water bath 8～12min, rear standing 12～14h, obtain enuatrol/benzyltrimethylammonium bromide
(NaOA/BTAB) system；
(3) preparation of pH response type intelligent vermiculate glues
The NaOA/BTAB system that step (2) obtains, adds hydrochloric acid solution and the hydrogen of step (1) gained
Sodium hydroxide solution regulation pH value be 8, stir/shake and choose 30～35kHz ultrasonic water bath to system homogeneous after
I.e. obtain the intelligent vermiculate glues to pH value response.
Embodiment 2
The preparation method of a kind of intelligent vermiculate glues, its operation is same as in Example 1, and distinguishing characteristics exists
In: it is 0.3mol/L that BTAB is diluted in described step (2) molar concentration；In described step (3)
Regulation pH value is 8.5.
Embodiment 3
The preparation method of a kind of intelligent vermiculate glues, its operation is same as in Example 1, and distinguishing characteristics exists
In: it is 0.5mol/L that BTAB is diluted in described step (2) molar concentration；In described step (3)
Regulation pH value is 9.
Embodiment 4
The preparation method of a kind of intelligent vermiculate glues, comprises the following steps:
(1) preparation of mother liquor
Preparation enuatrol mother liquor, triethylamine hydrochloride mother liquor, hydrochloric acid solution and sodium hydroxide solution respectively；
Wherein the molar concentration of enuatrol mother liquor is 0.24mol/L, and the molar concentration of triethylamine hydrochloride mother liquor is 1
Mol/L, the mass concentration of hydrochloric acid solution is 35%, and sodium hydroxide solution is its saturated solution；
(2) preparation of enuatrol/organic cation salt system
Pipette enuatrol mother liquor respectively, triethylamine hydrochloride mother liquor mixes and is diluted with water to concentrations of sodium oleate and is
0.12mol/L, triethylamine hydrochloride concentration are 0.1mol/L, through stirring/shake and choose 30～35kHz after mixing
Ultrasonic water bath 8～12min, rear standing 12～14h, obtain enuatrol/triethylamine hydrochloride (NaOA/Et3NHCl)
System；
(3) preparation of pH response type intelligent vermiculate glues
The NaOA/Et that step (2) obtains3NHCl system, add step (1) gained hydrochloric acid solution and
Sodium hydroxide solution regulation pH value be 8.0, after mixing stand 10～60min to system homogeneous after and get final product
To the intelligent vermiculate glues to pH value response.
Embodiment 5
The preparation method of a kind of intelligent vermiculate glues, its operation is the same as in Example 4, and distinguishing characteristics exists
In: triethylamine hydrochloride concentration is 0.3mol/L by described step (2)；Regulation in described step (3)
PH value is 9.
Embodiment 6
The preparation method of a kind of intelligent vermiculate glues, its operation is the same as in Example 4, and distinguishing characteristics exists
In: triethylamine hydrochloride concentration is 0.5mol/L by described step (2)；；Regulation in described step (3)
PH value is 9.5.
Embodiment 7
The preparation method of a kind of intelligent vermiculate glues, comprises the following steps:
(1) preparation of mother liquor
Preparation enuatrol mother liquor, triethanolamine hydrochloride mother liquor, hydrochloric acid solution and sodium hydroxide solution respectively；
Wherein the molar concentration of enuatrol mother liquor is 0.3mol/L, and the molar concentration of triethanolamine hydrochloride mother liquor is 1
Mol/L, the mass concentration of hydrochloric acid solution is 37%, and sodium hydroxide solution molar concentration is 4.0mol/L；
(2) preparation of enuatrol/organic cation salt system
Pipette enuatrol mother liquor respectively, triethanolamine hydrochloride mother liquor mixes and is diluted with water to enuatrol mole
Concentration is 0.15mol/L, and triethanolamine hydrochloride concentration is 0.2mol/L；Through stirring/shake and selecting after mixing
Take 30～35kHz ultrasonic water bath 8～12min, rear standing 12～14h, obtain enuatrol/triethanolamine hydrochloride
(NaOA/TEA HCl) system；
(3) preparation of pH response type intelligent vermiculate glues
The NaOA/TEA HCl system that step (2) obtains, adds the hydrochloric acid solution of step (1) gained
It is 9 with sodium hydroxide solution regulation pH value；Stir/shake and choose 30～35kHz ultrasonic water bath equal to system
The intelligent vermiculate glues to pH value response is i.e. obtained after one.
Embodiment 8
The preparation method of a kind of intelligent vermiculate glues, its operation is the same as in Example 4, and distinguishing characteristics exists
In: triethanolamine hydrochloride concentration is 0.3mol/L by described step (2)；Described step (3) is adjusted
Joint pH value is 9.5.
Embodiment 9
The preparation method of a kind of intelligent vermiculate glues, its operation is the same as in Example 4, and distinguishing characteristics exists
In: triethanolamine hydrochloride concentration is 0.4mol/L by described step (2)；Described step (3) is adjusted
Joint pH value is 10.
The inspection that vermiculate glues is formed
With the formation of vermiculate glues in rheol method inspection 3 kinds of systems of the present invention, respectively Example 1, Intelligent vermiculate glues obtained by embodiment 4 and embodiment 7, under pH environment, measures them corresponding Shear viscosity (ordinate) and the relation of shear rate (abscissa). as shown in Figure 1, Figure 2 and Figure 3. For NaOA/BTAB system, when pH is less than 8.90, all curves all present shear thinning phenomenon, Illustrate solution has vermiculate glues generate; For NaOA/Et3NHCl system, when pH value is less than 9.02
Time, all curves all present shear thinning phenomenon, illustrate have vermiculate glues to generate in solution；For
NaOA/TEA HCl system, when pH value is less than 12.75, all curves all present shear thinning phenomenon,
Illustrate solution has vermiculate glues generate.
Additionally can also be used with Cox-Merz rule and Cole-Cole figure to prove the formation of vermiculate glues.For
NaOA/BTAB system, when pH=8.58, shear rate is mapped by the shear viscosity recorded by flow graph,
" through the complex viscosity calculating with being obtained storage modulus G' of system by frequency scanning to loss modulus G
Frequency is mapped, as shown in Figure 4.In Fig. 4, ordinate is only numerical value, and abscissa is the shearing of identical numerical value
Speed and hunting angle frequency.As seen from Figure 4, this system is when pH=8.58, and its shear viscosity is with compound
Viscosity, substantially in an order of magnitude, meets Cox-Merz rule, illustrates that this system has defined vermiform glue
Bundle.Fig. 5 is NaOA/Et3NHCl system Cole-Cole is schemed, and Fig. 6 is NaOA/TEA HCl system
Cole-Cole schemes, and has defined vermiculate glues in the two the most provable above-mentioned system.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all at this
Within bright spirit and principle, any modification, equivalent substitution and improvement etc. made, should be included in this
Within bright protection domain.
Claims (7)
1. the preparation method of an intelligent vermiculate glues, it is characterised in that comprise the following steps:
(1) preparation of mother liquor
Preparation enuatrol mother liquor, organic cation salt mother liquor, sodium hydroxide solution and hydrochloric acid solution respectively；
(2) preparation of enuatrol/organic cation salt system
Pipette enuatrol mother liquor respectively, organic cation salt mother liquor mixes and is diluted with water, and through stirring/shake and carry out ultrasonic water bath after mixing, stands；
(3) preparation of pH response type intelligent vermiculate glues
Use the pH value of enuatrol/organic cation salt system of the hydrochloric acid solution of step (1) gained and sodium hydroxide solution regulating step (2) gained to behind 8～10, control temperature is in the range of 15～40 DEG C, and mixing to system i.e. obtains the intelligent vermiculate glues to pH response after homogeneous；
Described organic cation salt is one of following: benzyltrimethylammonium bromide, triethylamine hydrochloride or triethanolamine hydrochloride.
The preparation method of a kind of intelligent vermiculate glues the most according to claim 1, it is characterized in that: in described step (1), the molar concentration of enuatrol mother liquor is 0.2～0.3mol/L, the molar concentration of organic cation salt mother liquor is 0.8～1.0mol/L, the mass concentration of hydrochloric acid solution is 30～37%, and sodium hydroxide solution is its saturated solution.
The preparation method of a kind of intelligent vermiculate glues the most according to claim 1, it is characterised in that: described step (2) ultrasonic water bath supersonic frequency 30～35kHz, ultrasonic time 8～12min, time of repose 12～14h.
The preparation method of a kind of intelligent vermiculate glues the most according to claim 1, it is characterized in that: described step (2) concentrations of sodium oleate is all 0.1～0.15mol/L, for enuatrol/benzyltrimethylammonium bromide system, benzyltrimethylammonium bromide concentration is 0.1～0.5mol/L, for enuatrol/triethylamine hydrochloride system, triethylamine hydrochloride concentration is 0.1～0.5mol/L, for enuatrol/triethanolamine hydrochloride system, triethanolamine hydrochloride concentration is 0.2～0.4mol/L.
The preparation method of a kind of intelligent vermiculate glues the most according to claim 1, it is characterized in that: in described step (3), enuatrol/benzyltrimethylammonium bromide system regulation pH value is 8～9, enuatrol/triethylamine hydrochloride system regulation pH value is 8.0～9.5, and enuatrol/triethanolamine hydrochloride system regulation pH value is 9～10.
The preparation method of a kind of intelligent vermiculate glues the most according to claim 1, it is characterised in that: stand 10～60min after the mode of mixing uses stirring/concussion ultrasonic water bath or mixes in described step (3).
The preparation method of a kind of intelligent vermiculate glues the most according to claim 6, it is characterised in that: in described step (3), the supersonic frequency of ultrasonic water bath chooses 30～35kHz.
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| CN108970535A (en) * | 2018-06-25 | 2018-12-11 | 江南大学 | A kind of dimeric surfactant vermiculate glues and preparation method thereof |
| CN108863817A (en) * | 2018-06-25 | 2018-11-23 | 江南大学 | The vermiculate glues that the four poly- surfactants based on electrostatic are constructed |
| CN108837770A (en) * | 2018-06-25 | 2018-11-20 | 江南大学 | The four poly- surfactant worm-like micelle systems containing azobenzene group |
| CN108837771A (en) * | 2018-06-25 | 2018-11-20 | 江南大学 | A kind of dimeric surfactant vermiculate glues and preparation method thereof |
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