CN115532183A - Preparation and application of efficient temperature-sensitive system - Google Patents

Preparation and application of efficient temperature-sensitive system Download PDF

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CN115532183A
CN115532183A CN202211183150.1A CN202211183150A CN115532183A CN 115532183 A CN115532183 A CN 115532183A CN 202211183150 A CN202211183150 A CN 202211183150A CN 115532183 A CN115532183 A CN 115532183A
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temperature
sensitive system
quaternary ammonium
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宋冰蕾
李宏业
陈钊
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract

The invention discloses preparation and application of an efficient temperature-sensitive system, and belongs to the field of surfactant application and the field of intelligent materials. The invention utilizes a novel quaternary ammonium salt surfactant synthesized by straight-chain saturated fatty acid, methanol, 3-dimethylamino propylamine and (3-bromopropyl) trimethyl ammonium bromide; based on the novel quaternary ammonium salt surfactant, a high-efficiency temperature-sensitive system is obtained. The temperature-sensitive system obtained by the invention has extremely high speed of temperature response and can still keep extremely high viscoelasticity at higher temperature. After a certain amount of additives such as inorganic salt/organic salt and the like are added into the temperature-sensitive system, the compound system still keeps higher temperature response capability, and has important application value in the fields of manufacturing children toys, induction elements, medicament targeted release, thermal recognition systems and the like.

Description

Preparation and application of efficient temperature-sensitive system
Technical Field
The invention relates to preparation and application of a high-efficiency temperature-sensitive system, and belongs to the field of surfactant application and the field of intelligent materials.
Background
Hydrogels have a three-dimensional network structure and are generally obtained by cross-linking water by an aggregated structure of high or small molecules. Some hydrogels contain stimuli-responsive groups that, under certain conditions, can respond to a particular stimulus and cause a significant change in the physicochemical properties of the system, and are referred to as stimuli-responsive hydrogels. The stimulus-responsive hydrogel not only has the advantages of excellent mechanical property, good tissue affinity and the like of the original hydrogel, but also can respond to the change of external conditions, thereby bringing great convenience to the use of people. In recent decades, hydrogels have been increasingly used in cell engineering, in vivo drug delivery, sensing devices, oil exploration, food processing, and intelligent controlled release fields.
Common stimuli-responsive hydrogels can respond to changes in light, temperature, pH, and magnetic field, respectively. In the actual regulation process, special equipment is needed for stimulation such as light, magnetic field and the like. During the pH response, the structure of the groups in the system and the pH of the system change, which can have undesirable consequences in some biological systems. In contrast, a special generating device is not required for temperature response, the regulation and control process is more convenient, and the temperature change hardly affects the structure of the molecules of the crosslinked hydrogel. The temperature-responsive hydrogels formed by crosslinking polymers developed at present have excellent mechanical properties, but have a large molecular structure, and thus the degree of change in viscosity is not large before and after a temperature change, and the efficiency of temperature response is low. Therefore, the development of a hydrogel system with obvious viscosity change before and after temperature change is beneficial to promoting the development of temperature-sensitive hydrogels, and is a problem to be solved urgently at present. In addition, the viscosity of most hydrogel systems is reduced along with the increase of temperature, and if a system with the viscosity increased along with the increase of temperature can be developed, the hydrogel system is expected to have important application prospects in the fields of energy conversion, fluorescence detection and the like.
Disclosure of Invention
Technical problem
The currently developed system responding to ultraviolet/visible light and pH value not only needs a specific generating device or an additive in the regulation and control process, but also may bring troubles in some practical application processes. In contrast, temperature regulation is more convenient and response efficiency is high. The main reports at present are temperature response type polymer hydrogel. Due to the large molecular structure, the viscosity of the system is not changed greatly before and after the temperature is changed, and the response efficiency is low. The invention intends to adopt a novel structure of small molecule surfactant, and utilizes a unique molecular assembly mechanism to solve the problems.
Technical scheme
The invention provides a temperature-sensitive system with high response efficiency, and a preparation method thereof comprises the following steps:
dissolving a quaternary ammonium salt surfactant shown in a formula (1) in water, adding an additive, and uniformly mixing to obtain a temperature-sensitive system; the temperature sensitivity refers to: when the system temperature is not lower than the transition temperature, a hydrogel structure is formed; when the temperature of the system is lower than the transformation temperature, the system is a fluid solution;
Figure BDA0003866094070000021
wherein n is 10-24, m is 1-6, I is 1-6, X-is halogen ion (F, cl, br, I), NO 3 - 、SO 3 - ；
The additive is inorganic salt and/or alkane-free small molecule carboxylate; the concentration of the additive relative to water is 0-100 g.L -1 。
In one embodiment of the invention, the transition temperature is from 30 to 60 ℃.
In one embodiment of the present invention, the concentration of the quaternary ammonium salt surfactant relative to water is 10 mmol.L -1 -1500mmol·L -1 . Specifically, 600-800 mmol.L can be firstly added -1 ；700-800mmol·L -1 。
In one embodiment of the invention, the system is converted from a fluid solution to a hydrogel at a concentration of 0 additive to water above 30 ℃.
Specifically, the concentration of the quaternary ammonium salt surfactant relative to water is 800 mmol.L -1 When the temperature is higher than 30 ℃, the system is converted into hydrogel from a flowing solution; the concentration of the quaternary ammonium salt surfactant relative to water is 700 mmol.L -1 At temperatures above 40 ℃ the system changes from a fluid solution to a hydrogel.
In one embodiment of the invention, the system is converted from a fluid solution to a hydrogel at temperatures above 30 ℃ when the concentration of the additive relative to water is other than 0.
Specifically, the concentration of the quaternary ammonium salt surfactant relative to water is 800 mmol.L -1 Then the system is converted into hydrogel from a flowing solution at the temperature of more than 30 ℃; the concentration of the quaternary ammonium salt surfactant relative to water is 700 mmol.L -1 Then the system is converted into hydrogel from a flowing solution at the temperature of more than 35 ℃; the concentration of the quaternary ammonium salt surfactant relative to water is 600 mmol.L -1 At temperatures above 55 deg.C the system changes from a fluid solution to a hydrogel.
In one embodiment of the present invention, the concentration of the additive to water is further 0.05 to 0.5 g.L -1 (ii) a Specifically, 0.05 g.L can be selected -1 ，0.25g·L -1 Or 0.5 g.L -1 。
In one embodiment of the invention, the inorganic salt comprises NaCl and/or CaCl 2 。
In one embodiment of the invention, the alkane-free small molecule carboxylate is specifically sodium salicylate, naSal.
In one embodiment of the present invention, the quaternary ammonium salt surfactant is synthesized from a linear saturated fatty acid represented by formula 2, methanol, 3-dimethylaminoalkylamine represented by formula 3, and (3-bromoalkyl) trimethylammonium bromide represented by formula 4;
Figure BDA0003866094070000031
in one embodiment of the present invention, the synthetic route for the quaternary ammonium surfactant is as follows:
Figure BDA0003866094070000032
in one embodiment of the present invention, the quaternary ammonium surfactant, denoted as C, is synthesized from a linear saturated fatty acid represented by formula 2, methanol, 3-dimethylaminopropylamine, (3-bromopropyl) trimethylammonium bromide n+3 -3-2N。
In one embodiment of the invention, the viscosity of the system increases with increasing temperature, and higher viscosities can increase to more than 100 ten thousand times the initial system.
The invention also provides application of the temperature-sensitive system in preparation of an induction device.
The invention also provides application of the temperature-sensitive system in construction of a thermal identification system.
The invention also provides application of the temperature-sensitive system in oil exploitation.
The invention also provides application of the temperature-sensitive system in food processing equipment and preparation of children toys.
The invention also provides application of the temperature-sensitive system in preparation of an intelligent controlled release system.
Has the beneficial effects that:
the novel temperature-sensitive composite system provided by the invention has extremely high temperature response speed, and can cause obvious change of system viscosity when the temperature change interval reaches 3 ℃. After the temperature is raised, the viscosity of the system can be changed by 100 ten thousand times compared with the viscosity of the solution at low temperature. The complex system can be converted into hydrogel at a temperature as low as 30 ℃ and still has excellent viscoelasticity at a temperature of 85 ℃ and also has good tolerance to inorganic and organic salts. The sensitive and efficient temperature response performance can be applied to the fields of manufacturing children toys, induction elements, drug targeted release, thermal recognition systems and the like, and the performance that the solution viscosity is increased along with the temperature rise enables the solution to have obvious application potential in the oil reservoir exploitation process.
Drawings
FIG. 1 is C 18 -nuclear magnetic hydrogen spectrum (DMSO) of 3-2N.
FIG. 2 shows 800 mmol.L at different temperatures -1 C 18 Steady state shear rheology profile for 3-2N system.
FIG. 3 shows 800 mmol. L -1 C 18 Plot of zero shear viscosity versus temperature for the 3-2N system.
FIG. 4 shows 700 mmol. L -1 C 18 The 3-2N systems are respectively in different (a) C NaSal 、(b)C NaCl 、(c)C CaCl2 Steady state rheology profile (closed symbols indicate 25 ℃ C., open symbols indicate 65 ℃ C.).
FIG. 5 shows 800 mmol. L -1 C 18 Appearance of the-3-2N system (left image taken at 25 ℃ C., right image taken after heating to 40 ℃ C.).
FIG. 6 shows 800 mmol. L -1 C 18 Appearance of the-3-2N system (left image taken at 40 ℃ C., right image taken after cooling to 25 ℃ C.).
FIG. 7 shows 700 mmol. L -1 C 18 The (E) -3-2N system is respectively 0.25 g.L -1 NaSal(a、d)、NaCl(b、e)、CaCl 2 (c, f) appearance pictures at salt concentration (left picture taken at 25 ℃ C., right picture taken after heating to 50 ℃ C.).
FIG. 8 shows 700 mmol. L -1 C 18 The (E) -3-2N system is respectively 0.25 g.L -1 Appearance pictures at NaSal concentration (left picture taken at 50 ℃ C., right picture taken after cooling to 25 ℃ C.).
Detailed Description
Example 1: preparation of quaternary ammonium salt surfactant
The synthetic route is as follows:
Figure BDA0003866094070000041
250.0g of octadecanoic acid (0.88 mol) and 168.7g of methanol (5.27 mol) were poured into a 2000mL three-necked flask, 3mL of concentrated sulfuric acid was added as a catalyst, and the mixture was refluxed in an oil bath at 70 ℃ for 5 to 6 hours. After the reaction was completed, 100mL of dichloromethane was added, and the mixture was washed with 50mL of deionized water and separated. 100g of anhydrous magnesium sulfate was added to the oil phase, and the mixture was left to stand for 30min, dried and filtered under suction, and the resulting organic phase was freed from methylene chloride and other residual solvents under reduced pressure. And purifying the residual liquid by adopting a reduced pressure distillation method to obtain an intermediate A.
189.3g of intermediate A (0.63 mol) and 194.3g of 3-dimethylaminopropylamine (1.90 mol) were placed in a 1000mL three-necked flask, and reacted at 100 ℃ for 48 hours with 1g of KOH as a catalyst. After the reaction was completed, the mixture was placed in a 1000mL beaker and recrystallized three times with acetone and ethanol to obtain intermediate B.
20.2g of intermediate B (0.05 mol) and 13.3g of (3-bromopropyl) trimethylammonium bromide (0.05 mol) are placed in a 500mL single-necked flask, 80mL of ethanol are added and the reaction is carried out at 85 ℃ for 48h. Removing ethanol under reduced pressure after the reaction is finished, crystallizing the residue for three times by using a mixed solution of acetone and ethanol, and drying in a vacuum drying oven to obtain a final product, namely quaternary ammonium salt surfactant C 18 -3-2N。
C 18 -structure and purity determination of 3-2N:
taking a proper amount of C 18 -3-2N in a nuclear magnetic tube, dissolved in deuterated DMSO and subjected to nuclear magnetic resonance at 25 ℃ using a Bruker Advance III NMR spectrometer 1 And (3) carrying out H NMR (nuclear magnetic resonance) testing, 1 the resonance frequency of H is 400MHz. C 18 The NMR spectrum of 3-2N is shown in FIG. 1. As can be seen from FIG. 1, the chemical shifts of the individual hydrogens are correlated with the target product C 18 A match of 3-2N indicates that the target product is obtained; and no miscellaneous peak exists on the spectrogram, which indicates that the product achieves higher purity.
Example 2: a single component C 18 Preparation of temperature-sensitive system from (E) -3-2N
Preparation of 3mL 800mmol.L -1 C 18 3-2N aqueous solution, namely a temperature-sensitive system.
And (4) heating and raising the temperature to observe the change of the state of the temperature-sensitive system. The appearance of the temperature-sensitive system is shown in FIG. 5. The fluidity of the solution is obviously reduced gradually in the temperature rise process, and when the temperature is raised to 30 ℃, the solution can overcome the self gravity in an inverted glass bottle and does not flow, so that hydrogel with excellent performance is formed; when the aqueous solution is left at room temperature for a while, and the temperature of the solution is reduced to 25 ℃, the solution is returned to a fluid state, and the appearance diagram is shown in fig. 6. The transition temperature was found to be 30 ℃.
Further, each 3mL 700mmol. L was prepared -1 、600mmol·L -1 C 18 And (3) putting the 3-2N aqueous solution into a sample bottle with a cover to obtain a corresponding temperature-sensitive system. As a result, it was found that: 700 mmol. L -1 The transition temperature of the temperature-sensitive system is 40 ℃;600 mmol. L -1 C 18 the-3-2N temperature-sensitive system cannot form hydrogel when the temperature is raised to 60 ℃ and 65 ℃, and has no obvious temperature sensitivity.
Example 3: c 18 -3-2N/salt compound preparation temperature-sensitive system
Preparation of 700 mmol. L -1 C 18 Putting the-3-2N aqueous solution into a sample bottle with a cover, and adding NaSal, naCl and CaCl into the sample bottle 2 Correspondingly, the salt with different concentrations (0.05 g.L) of nine different salts is prepared -1 ，0.25g·L -1 ，0.5g·L -1 ) The total volume of the surfactant mixed solution is 3mL; and (3) placing the prepared solution in a thermostat with the temperature of 25 +/-0.1 ℃ for standing for 24 hours, and naturally dissolving the solution to obtain a corresponding temperature-sensitive system.
And (5) heating and temperature rising to observe the change of the state of the temperature-sensitive system. The photograph of the appearance of the formulated system is shown in FIG. 7. The gradual reduction of the fluidity of the solution can be obviously seen in the temperature rising process, and when the temperature rises to 35 ℃, the solution can overcome the self gravity in an inverted glass bottle without flowing, so that hydrogel with excellent performance is formed. Heating to 50 deg.C to contain 0.05 g.L -1 700 mmol. L of NaSal -1 C 18 The 3-2N aqueous solution is left at room temperature for a period of time, and when the temperature of the solution is reduced to 25 ℃, the solution returns to a fluid state, and the appearance of the solution is shown in FIG. 8.
In addition, the content of the polymer is 0.05 g.L -1 C of NaSal 18 3-2N in water, adding C 18 Concentration of-3-2N is from 700 mmol.L -1 The solution is increased to 800 mmol.L -1 When the temperature is raised to 30 ℃, the product can be formedForming hydrogel, and when the temperature is reduced to 25 ℃, the solution returns to the fluid state. At a content of 0.05 g.L -1 C of NaSal 18 3-2N in aqueous solution, adding C 18 Concentration of-3-2N is from 700 mmol.L -1 Reduced to 600 mmol.L -1 It was found that the solution could also be inverted in a glass bottle against its own weight without flowing when heated to 55 ℃. This shows that after the addition of the additive, the temperature-sensitive system can still form hydrogel after being heated to a certain temperature under the condition of reducing the dosage of the surfactant.
Example 4: steady state rheology test
C in example 2 18 3-2N systems with C in example 3 18 The steady-state rheological test is carried out on the-3-2N/salt compound system, a DHR-3 rotational rheometer is used for the test, a clamp is used and is a concentric cylinder, and the shearing rate is set to be 0.1rad s -1 To 600.0rad · s -1 . Carry out C 18 When a 3-2N system is subjected to rheological test, performing steady-state rheological test every 5 ℃; carry out C 18 During the rheology test of the 3-2N/salt compound system, the steady-state rheology test is only carried out at 25 ℃ and 65 ℃.
The steady-state rheology test results are shown in fig. 2, fig. 3, and fig. 4, respectively.
As can be seen from FIGS. 2 and 3, C is between 35 ℃ and 45 ℃ 18 The viscosity of the 3-2N system (example 2) changed significantly, with a value that increased 3500 times; as the temperature continued to rise to 85 ℃, the viscosity value continued to rise to 2,700,000 times the room temperature viscosity and reached a maximum value.
As can be seen from FIG. 4, at certain concentrations of NaSal, naCl and CaCl 2 In the presence of (example 3), C 18 the-3-2N system still has high-efficiency temperature response capability, and the viscosity change can still reach more than about 6 orders of magnitude. Wherein when the NaCl concentration is 0.5 g.L -1 When, C 18 The 3-2N/NaCl mixed system showed the greatest viscosity change.

Claims (10)

1. A method of preparing a temperature sensitive system, comprising:
dissolving a quaternary ammonium salt surfactant shown in a formula (1) in water, adding an additive, and uniformly mixing to obtain a temperature-sensitive system; the temperature sensitivity refers to: when the system temperature is not lower than the transition temperature, a hydrogel structure is formed; when the temperature of the system is lower than the transition temperature, the system is a fluid solution;
Figure FDA0003866094060000011
wherein n is 10 to 24, m is 1 to 6, i is 1 to 6 - Is halogen ion, NO 3 - 、SO 3 - ；
The additive is inorganic salt and/or alkane-free small molecule carboxylate; the concentration of the additive relative to water is 0-100 g.L -1 。
2. The method of claim 1, wherein the quaternary ammonium surfactant has a concentration of 10 mmol-L relative to water -1 -1500mmol·L -1 。
3. The method of claim 1, wherein the transition temperature is 30-60 ℃.
4. The method of claim 1, wherein the concentration of the additive to water is 0.05 to 0.5 g-L -1 。
5. The method according to claim 1, wherein the quaternary ammonium salt surfactant is synthesized from a linear saturated fatty acid represented by formula 2, methanol, 3-dimethylaminoalkylamine represented by formula 3, and (3-bromoalkyl) trimethylammonium bromide represented by formula 4;
Figure FDA0003866094060000012
6. a temperature-sensitive system prepared by the method of any one of claims 1 to 5.
7. Use of the temperature sensitive system of claim 6 in oil recovery.
8. Use of the temperature sensitive system of claim 6 in the preparation of an induction device.
9. The use of the temperature sensitive system of claim 6 in the construction of a thermal identification system.
10. Use of a temperature-sensitive system according to claim 6 in the manufacture of a toy for children.
CN202211183150.1A 2022-09-27 2022-09-27 Preparation and application of efficient temperature-sensitive system Pending CN115532183A (en)

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