CN115926140A - N, N-dibutyl polyetheramine nonionic surfactant, preparation thereof, tetrabutyl ammonium hydroxide developer based on N, N-dibutyl polyetheramine nonionic surfactant and preparation - Google Patents
N, N-dibutyl polyetheramine nonionic surfactant, preparation thereof, tetrabutyl ammonium hydroxide developer based on N, N-dibutyl polyetheramine nonionic surfactant and preparation Download PDFInfo
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Abstract
N, N-dibutyl polyetheramine nonionic surfactant, preparation thereof, tetrabutyl ammonium hydroxide developer based on the surfactant and preparation. The invention belongs to the field of surfactants and the field of chip integrated circuit development processes. The invention aims to provide a tetrabutylammonium hydroxide developing solution with potential commercial value and solve the technical problem of large surface tension of tetrabutylammonium hydroxide. The process for preparing the N, N-dibutyl polyether amine nonionic surfactant does not involve a metal catalyst, and the reaction yield is high. The developing solution is compounded with tetrabutylammonium hydroxide aqueous solution to obtain the developing solution, and the developing solution has the characteristics of low surface tension, stable storage performance, capability of effectively reducing the problem of image collapse, excellent developing effect and huge future commercial prospect.
Description
Technical Field
The invention belongs to the field of surfactants and the field of chip integrated circuit development processes, and particularly relates to an N, N-dibutyl polyether amine nonionic surfactant, a preparation method thereof, a tetrabutyl ammonium hydroxide developing solution based on the N, N-dibutyl polyether amine nonionic surfactant, and a preparation method of the tetrabutyl ammonium hydroxide developing solution.
Background
The developing refers to a process of using a developing solution to react with the photoresist at the middle and later stages of the photoetching process so that the graph of the mask can be accurately projected onto the photoresist of the wafer. The developing solution is a chemical solvent that dissolves the photoresist-soluble region resulting from exposure, and can be generally classified into two types, positive and negative. Wherein the positive developing solution is usually a strong alkaline solution diluted with water. The conventional developing solution generally uses inorganic alkali KOH, but with the technological progress, the design and manufacture of integrated circuits need to meet various complex process conditions, and the requirements for chemical impurities are more and more strict. The developing solution produced by using inorganic alkali such as KOH and the like needs a large amount of water to wash the substrate after development, and K cannot be guaranteed + Can be thoroughly washed. Excessive metal ion residues cannot meet some harsh process conditions, for example, the number of electronic components in a single manufacturing unit is increasing, and the line width is becoming narrower, which all become an important bottleneck restricting the development of the electronic industry. Thus, organic bases such as tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and the like are used.
The organic base just overcomes the defects of KOH, no metal ion residue is left after the use, and the organic base is easy to decompose at high temperature. The mainstream product on the market today is a developer prepared from TMAH, whereas developers prepared from tetraethyl/tetrabutylammonium hydroxide are very rare for process and market reasons. However, as the requirements of the photolithography process for line width and uniformity become higher and higher, the TMAH developing solution also gradually exposes some problems. For example, when a common 2.38wt.% TMAH developer is used to manufacture a fine pattern with a line width of 45nm or less, the problem of pattern collapse due to swelling is present, which is one of the limitations of the TMAH developer in advanced semiconductor processes. If the semiconductor industry wants to develop to the fine level of nanometer level in the future, the developing solution composition must be continuously updated. Tetrabutylammonium hydroxide developer has been shown to reduce swelling of the photoresist during development and make the patterned surface of the photoresist less hydrophilic, effectively reducing image collapse. Also, tetrabutylammonium hydroxide has higher development sensitivity. Therefore, the development of a tetrabutylammonium hydroxide developer is certainly a trend choice in the future.
However, the tetrabutylammonium hydroxide developer has a large surface tension, and cannot sufficiently wet the photoresist in an advanced process when used alone, so that poor developing effect or unobvious developing effect is caused, and the yield of products is finally reduced. Therefore, it is usually necessary to add a surfactant to lower the surface tension and expand the range of applications.
The polyetheramine nonionic surfactant has been widely used in recent years because of its excellent surface properties, and currently, methods for producing the same mainly include reductive amination, hydrolysis, leaving group, and nitro-capping, but most of them are reported to be reductive amination because of its short reaction time, high conversion rate, and good selectivity.
Chinese patent CN114669302A discloses a method for preparing polyether amine, which adopts gamma-Al 2 O 3 As a carrier, basic copper carbonate, basic nickel carbonate and basic cobalt carbonate are used as precursors of load metals to prepare a load type metal catalyst, and the load type metal catalyst is successfully applied to hydroamination reaction of polyether polyol.
Chinese patent CN12759758A discloses a method for preparing polyether amine by intermittent catalytic amination, which comprises the following specific operations: polyether is used as a raw material to perform reductive amination reaction with hydrogen and liquid ammonia in the presence of a supported nickel catalyst and a modification auxiliary agent by using an intermittent method to prepare polyether amine.
Chinese patent CN114874431A discloses a method for preparing polyether amine, which takes M2070 and paraformaldehyde as raw materials, hydrogen as a reducing agent, ni-Cu-W/gamma-Al 2 O 3 The catalyst is subjected to reductive amination reaction in a fixed bed to prepare the polyether amine.
However, the above methods all involve the use of metal catalysts, and the produced polyetheramines have a risk of metal residues if used for the preparation of a developer, resulting in poor developing effects.
Disclosure of Invention
In order to solve the technical problems, the invention provides the following technical scheme: an N, N-dibutyl polyether amine nonionic surfactant, a preparation method thereof, a tetrabutyl ammonium hydroxide developer based on the surfactant and a preparation method thereof.
One of the objects of the present invention is to provide a process for preparing N, N-dibutyl polyetheramine nonionic surfactant, comprising,
s1: sequentially adding polyether amine, n-butyl aldehyde, hindered Lewis acid and hindered Lewis base into a high-pressure reaction kettle, adding a dissolving solution, respectively purging with nitrogen and hydrogen, and magnetically stirring for reaction under certain hydrogen pressure and temperature;
s2: and after the reaction is finished, naturally cooling to room temperature, decompressing and rotary-steaming to remove the solvent and impurities, and then repeatedly extracting in petroleum ether for 3-4 times to obtain the N, N-dibutyl polyetheramine nonionic surfactant.
In a preferred embodiment of the present invention, the blocked Lewis acid in S1 is tris (pentafluorophenyl) boron.
As a preferable embodiment of the present invention, the hindered Lewis base in S1 is N, N-dimethylaniline.
In a preferred embodiment of the present invention, the molar ratio of the polyether amine to n-butyraldehyde, hindered lewis acid and hindered lewis base in S1 is 1: (2-4): (3-4): (3-4).
In a preferred embodiment of the present invention, the solution in S1 is dichloroethane, chloroform or dichloromethane.
As a preferable scheme of the invention, the hydrogen pressure in S1 is 1.2-1.8 MPa, the temperature is 120-150 ℃, and the time is 8-12 h.
In a preferable embodiment of the present invention, the polyether amine in S1 is M2070.
The invention also aims to provide the N, N-dibutyl polyether amine nonionic surfactant prepared by the method, wherein the molecular structure of the N, N-dibutyl polyether amine nonionic surfactant is as follows:
the invention also provides a tetrabutylammonium hydroxide developing solution based on the N, N-dibutyl polyether amine nonionic surfactant, and the developing solution is prepared by compounding an aqueous tetrabutylammonium hydroxide solution and an aqueous solution of the N, N-dibutyl polyether amine nonionic surfactant.
In a preferred embodiment of the present invention, the developing solution contains tetrabutylammonium hydroxide in an amount of 3 to 12wt.% and N, N-dibutyl polyetheramine nonionic surfactant in an amount of 5 to 10wt.%.
The fourth purpose of the invention is to provide a preparation method of tetrabutylammonium hydroxide developing solution based on N, N-dibutyl polyether amine nonionic surfactant, which comprises the following steps:
and mixing tetrabutylammonium hydroxide, N-dibutyl polyether amine and water in proportion, and uniformly stirring to obtain the developing solution.
In a preferred embodiment of the present invention, the water is ultrapure water.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a preparation method of an N, N-dibutyl polyetheramine nonionic surfactant and a tetrabutyl ammonium hydroxide developing solution based on the N, N-dibutyl polyetheramine nonionic surfactant, and the preparation method has the following advantages:
1. in the process of preparing the N, N-dibutyl polyether amine nonionic surfactant, tris (pentafluorophenyl) boron is used as hindered Lewis acid, N, N-dimethylaniline is used as hindered Lewis base, and the hindered Lewis acid and the hindered Lewis base form a hindered Lewis acid-base pair activated hydrogen. The main reaction process is as follows: the amino on M2070 and the carbonyl on butyraldehyde firstly undergo addition reaction to generate amino alcohol, the amino alcohol is dehydrated to generate imine, and finally the imine undergoes hydrogenation reaction to obtain a target product. The invention selects the hindered Lewis acid-base pair to replace common metal catalysts, such as VIII family transition metal elements of platinum, palladium, nickel and the like, to activate the hydrogen, thereby not only avoiding the participation of metals, but also improving the conversion rate of the reaction. At present, the reports on the preparation of polyether amine by using hindered Lewis acid-base pair activated hydrogen are rare, and the yield of the N, N-dibutyl polyether amine nonionic surfactant prepared by the method is high.
2. According to the invention, the N, N-dibutyl polyetheramine nonionic surfactant and tetrabutyl ammonium hydroxide are compounded to prepare the developing solution, the problem of image collapse is effectively reduced, and the storage performance is stable. Also, tetrabutylammonium hydroxide has higher developing sensitivity and excellent developing effect. Therefore, the development of tetrabutylammonium hydroxide developing solutions is certainly a future trend of choice.
Drawings
FIG. 1 is a NMR hydrogen spectrum of M2070;
FIG. 2 is the NMR spectrum of the N, N-dibutyl polyetheramine nonionic surfactant obtained in example 1;
FIG. 3 is a mass spectrum of M2070;
FIG. 4 is the flight mass spectrum of the N, N-dibutyl polyether amine nonionic surfactant obtained in example 1.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention more comprehensible, embodiments accompanying the present invention are described in detail below with reference to examples.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, however, the present invention may be practiced otherwise than as specifically described herein, and it will be appreciated by those skilled in the art that the present invention may be practiced without departing from the spirit and scope of the present invention and that the present invention is not limited by 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
The preparation method of the N, N-dibutyl polyetheramine nonionic surfactant of this example was carried out according to the following steps:
s1: sequentially adding 20g (10 mmol) of M2070, 2.64mL (30 mmol) of N-butyraldehyde, 17.9g (35 mmol) of tris (pentafluorophenyl) boron and 4.44mL (35 mmol) of N, N-dimethylaniline into a high-pressure reaction kettle, adding dichloroethane as a dissolving solution, respectively purging 3 times with nitrogen and hydrogen, and then magnetically stirring and reacting for 10 hours at the hydrogen pressure of 1.6MPa and the temperature of 130 ℃;
s2: and when the temperature of the reaction kettle is reduced to room temperature, collecting a product in a flask, carrying out reduced pressure rotary evaporation to remove the solvent and impurities, and then repeatedly extracting in petroleum ether for 3 times to obtain the N, N-dibutyl polyetheramine nonionic surfactant with the yield of 96.9%.
Nuclear magnetic resonance hydrogen spectroscopy of M2070 in fig. 1: 1 h NMR (400mhz, deuterium Oxide) δ 3.84-3.78 (m, 13H), 3.74 (s, 124H), 3.56 (dd, J =16.9,10.1hz, 19h), 3.42 (s, 3H), 1.20 (d, J =6.2hz, 27h), 1.06 (d, J =6.5hz, 3h); the integrated total number of hydrogen in FIG. 1 is 189, wherein the peak at 3.42 is the leftmost end methyl peak of M2070, and can be used for calibration of new substances.
NMR hydrogen spectroscopy analysis of the N, N-dibutyl polyetheramine nonionic surfactant obtained in example 1 in FIG. 2: 1 h NMR (400mhz, deuterium Oxide) δ 3.78 (td, J =8.0,6.8,3.8hz, 13h), 3.73 (s, 124H), 3.56 (qd, J =11.0,9.5,5.0hz, 19h), 3.40 (s, 3H), 2.36 (dd, J =21.3,7.8hz, 4h), 1.40-1.29 (m, 4H), 1.18 (d, J =6.2hz, 29h), 1.09 (d, J =6.7hz, 3h), 0.96-0.90 (m, 6H); in fig. 2, the integrated total number of hydrogen is 205, which is consistent with the hydrogen number of the target product, and the peak at 3.40 is taken as a calibration peak, and it is found that the rightmost characteristic methyl peak of the butyl carbon chain appears in the interval of 0.96-0.90, and the integrated number of hydrogen is 6, which corresponds to the methyl number.
From a comparison of the results of the NMR analyses of the two substances, it can be confirmed that example 1 indeed successfully produced N, N-dibutylpolyetheramine.
FIGS. 3 and 4 are the results of the flight mass spectrometry of M2070 and N, N-dibutyl polyether amine obtained in example 1, respectively, and the molecular weight of M2070 was found to be about 2000 in FIG. 3 and the molecular weight of N, N-dibutyl polyether amine was found to be about 2112 in FIG. 4, which is consistent with the molecular structure of the compound.
Example 2:
the difference from example 1 is that: 1.76mL (20 mmol) of n-butyraldehyde was added to S1, and the remaining parameters and procedures were the same as in example 1.
The final product of N, N-dibutyl polyether amine non-ionic surface active agent is pure, and the yield is 80.1%.
Example 3:
the difference from example 1 is that: 3.52mL (40 mmol) of n-butyraldehyde was added to S1, and the remaining parameters and procedures were the same as in example 1.
The pure product of the N, N-dibutyl polyether amine nonionic surfactant is obtained, and the yield is 97.2%.
Example 4:
the difference from example 1 is that: to S1 were added 15.4g (30 mmol) of tris (pentafluorophenyl) boron and 3.8mL (30 mmol) of N, N-dimethylaniline, and the remaining parameters and steps were the same as in example 1.
Finally, the pure product of the N, N-dibutyl polyether amine nonionic surfactant is obtained, and the yield is 85.2%.
Example 5:
the difference from example 1 is that: 20.5g (40 mmol) of tris (pentafluorophenyl) boron and 5.1mL (40 mmol) of N, N-dimethylaniline were added to S1, and the remaining parameters and steps were the same as in example 1.
Finally, the pure product of the N, N-dibutyl polyether amine nonionic surfactant is obtained, and the yield is 90.3%.
Example 6:
the difference from example 1 is that: the hydrogen pressure in S1 was 1.2MPa, and the remaining parameters and procedures were the same as in example 1.
The final pure product of the N, N-dibutyl polyether amine nonionic surfactant is obtained, and the yield is 77.4%.
Example 7:
the difference from example 1 is that: the hydrogen pressure in S1 was 1.8MPa, and the remaining parameters and procedures were the same as in example 1.
Finally, the pure product of the N, N-dibutyl polyether amine nonionic surfactant is obtained, and the yield is 95.8%.
Example 8:
the difference from example 1 is that: the temperature of the reaction in S1 was 120 ℃ and the remaining parameters and procedure were the same as in example 1.
The final product of N, N-dibutyl polyether amine nonionic surfactant is pure, and the yield is 82.9%.
Example 9:
the difference from example 1 is that: the temperature of the reaction in S1 was 150 ℃ and the remaining parameters and procedure were the same as in example 1.
The final product of N, N-dibutyl polyether amine nonionic surfactant is pure, and the yield is 96.4%.
Example 10:
the difference from example 1 is that: the reaction time in S1 was 8h, and the remaining parameters and procedure were the same as in example 1.
The final product was pure N, N-dibutyl polyetheramine nonionic surfactant with a yield of 87.3%.
Example 11:
the difference from example 1 is that: the reaction time in S1 was 12h, and the remaining parameters and procedure were the same as in example 1.
The pure product of the N, N-dibutyl polyether amine nonionic surfactant is obtained, and the yield is 97.8%.
Example 12:
the difference from example 1 is that: the solution in S1 was chloroform, and the remaining parameters and steps were the same as in example 1.
The final product of N, N-dibutyl polyether amine nonionic surfactant is pure, and the yield is 93.2%.
Example 13:
the difference from example 1 is that: the solvent in S1 was dichloromethane, and the remaining parameters and procedures were the same as in example 1.
The final product was pure N, N-dibutyl polyetheramine nonionic surfactant with a yield of 86.7%.
Comparative example: an unmodified polyetheramine (M2070) surfactant was used as a control.
And (3) detection test:
the surface tension of comparative M2070 nonionic surfactant and the N, N-dibutyl polyetheramine nonionic surfactant of example 1 was tested as follows:
surface tension test method: measuring the surface tension of surfactants with different concentrations at 25.0 +/-0.1 ℃ by using a BZY-2 type surface tension meter through a platinum plate method, calibrating the meter by using ultrapure water before measurement, placing a vessel containing liquid on a sample platform to enable the vessel to be positioned under a platinum plate, enabling the reading of the meter to return to zero, adjusting the sample platform to enable the solution to slowly rise until the bottom of the platinum plate just contacts with the surface of the solution, and recording the stable reading of the surface tension meter. The platinum gold plate is cleaned, then repeated measurement is carried out, 3 times of continuous measurement are carried out, an average value is taken as a measurement result, and the error of two times of continuous measurement is not more than 0.5mN/m. The experimental data are shown in table 1:
table 1 surface tension test results
As can be seen from Table 1, the surface tension of the unmodified polyetheramine M2070 nonionic surfactant was about 44mN/M at the lowest, whereas the surface tension of the N, N-dibutyl polyetheramine nonionic surfactant of the present invention was about 30mN/M at the lowest. The results prove that the surface performance of the N, N-dibutyl polyether amine nonionic surfactant is greatly improved.
(II) the emulsifying properties of comparative M2070 nonionic surfactant and the N, N-dibutyl polyetheramine nonionic surfactant of example 1 were tested as follows:
the test method comprises the following steps: pouring 40mL of surfactant aqueous solution with the mass fraction of 0.1% and 40mL of liquid paraffin oil into a 100mL stoppered measuring cylinder, covering a plug, keeping the temperature in a water bath at 25 ℃ for 5min, taking out, shaking vigorously for 5 times, placing the mixture into the water bath at 25 ℃ for standing for 1min, taking out, shaking vigorously for 5 times, repeating the same step for 5 times, standing, starting a stopwatch to time, and recording the time required for 10mL of bottom-layer aqueous phase to separate. Repeating the steps for three times, and calculating an average value. The experimental data are shown in table 2.
Table 2 emulsifying property test results of surfactants
| M2070 | Example 1 | |
| Time of water diversion | 239s | 1085s |
Compared with the unmodified polyether amine M2070 surfactant, the water separation time of the N, N-dibutyl polyether amine nonionic surfactant prepared in the example 1 is obviously prolonged, and the emulsifying property of the N, N-dibutyl polyether amine nonionic surfactant prepared in the example 1 is improved by 4.5 times compared with that of the M2070 surfactant, so that the emulsifying property of the N, N-dibutyl polyether amine nonionic surfactant is obviously improved.
Application example 1
The preparation method of the developing solution of the application example comprises the following steps:
step (1)
First, 14wt.% aqueous tetrabutylammonium hydroxide solution was prepared;
then preparing 16wt.% of N, N-dibutyl polyether amine nonionic surfactant aqueous solution;
step (2)
10kg of 1699 wt.% N, N-dibutyl polyetheramine nonionic surfactant aqueous solution and 10kg of 14wt.% tetrabutylammonium hydroxide aqueous solution are mixed, and stirring is continuously carried out until the solution is clear and transparent, so that the tetrabutylammonium hydroxide developing solution with the mass fraction of 7wt.% is obtained.
The surface tension of the developer of this example was measured to be 37.4mN/m by a surface tension meter, and 100g of the developer of application example 1 was placed in air, and pH was measured at intervals, and it was found through experiments that the initial pH of the developer was 13.25, the pH was 12.74 after being left in air for 72 hours, and the pH was 11.34 after being left for 168 hours, indicating that the developer had good storage stability.
And (3) spraying the developing solution on a photoresist test piece at a constant pressure at 25 ℃, wherein the spraying time lasts for 60s, then cleaning the photoresist test piece by using ultrapure water and drying the cleaned photoresist test piece, and observing a developing pattern under a scanning electron microscope.
Application example 2:
the difference from application example 1 is that: the concentration of the aqueous solution of the N, N-dibutyl polyetheramine nonionic surfactant in the step (1) is 10wt.%, and the content of the N, N-dibutyl polyetheramine nonionic surfactant in the developer is 5wt.%. The remaining parameters and procedures were the same as in example 1.
The surface tension of the developer of this example was measured to be 40.38mN/m by a surface tension meter, and 100g of the developer of application example 2 was placed in air, and pH was measured at intervals, and it was found through experiments that the initial pH of the developer was 13.59, the pH was 12.15 after being placed in air for 72 hours, and the pH was 10.98 after being placed for 168 hours, indicating that the developer had good storage stability.
And (3) spraying the developing solution on a photoresist test piece at a constant pressure at 25 ℃, wherein the spraying time lasts for 60s, then cleaning the photoresist test piece with ultrapure water and drying the photoresist test piece, and observing a developing pattern under a scanning electron microscope.
Application example 3:
the difference from application example 1 is that: the concentration of the aqueous solution of the N, N-dibutyl polyetheramine nonionic surfactant in the step (1) is 20wt.%, and the content of the N, N-dibutyl polyetheramine nonionic surfactant in the developer is 10wt.%. The remaining parameters and procedures were the same as in example 1.
The surface tension of the developer solution of this example was measured to be 36mN/m by a surface tension meter, 100g of the developer solution of application example 3 was placed in air, and the pH was measured at regular intervals, and it was found through experiments that the initial pH of the developer solution was 13.14, the pH was 12.46 after being placed in air for 72 hours, and the pH was 11.14 after being placed for 168 hours, indicating that the developer solution had good storage stability.
Spraying the developing solution on a photoresist test piece at a constant pressure at 25 ℃ for 60s, cleaning with ultrapure water, and drying. The development pattern is observed under a scanning electron microscope, and the result shows that the development is good and no image collapse phenomenon exists.
Application example 4:
the difference from application example 1 is that: the concentration of the aqueous tetrabutylammonium hydroxide solution in step (1) was 6wt.%, and the content of tetrabutylammonium hydroxide in the developer was 3wt.%. The remaining parameters and procedures were the same as in example 1.
The surface tension of the developer of this example was measured to be 39.5mN/m by a surface tension meter, and 100g of the developer of application example 4 was placed in air, and pH was measured at intervals, and it was found through experiments that the initial pH of the developer was 13.08, the pH was 12.32 after being placed in air for 72 hours, and the pH was 11.35 after being placed for 168 hours, indicating that the developer had good storage stability.
Spraying the developing solution on a photoresist test piece at a constant pressure at 25 ℃ for 60s, cleaning with ultrapure water, and drying. The development pattern is observed under a scanning electron microscope, and the result shows that the development is good and no image collapse phenomenon exists.
Application example 5:
the difference from application example 1 is that: the concentration of the aqueous tetrabutylammonium hydroxide solution in step (1) was 24wt.%, and the content of tetrabutylammonium hydroxide in the developer was 12wt.%. The remaining parameters and procedures were the same as in example 1.
The surface tension of the developing solution of this example was measured to be 36.4mN/m by a surface tension meter, 100g of the developing solution of application example 5 was placed in the air, and the pH was measured at intervals, and it was found through experiments that the initial pH of the developing solution was 13.79, the pH was 12.25 after being placed in the air for 72 hours, and the pH was 10.79 after being placed for 168 hours, indicating that the developing solution had good storage stability.
Spraying the developing solution on a photoresist test piece at a constant pressure at 25 ℃ for 60s, cleaning with ultrapure water, and drying. The development pattern is observed under a scanning electron microscope, and the result shows that the development is good and no image collapse phenomenon exists.
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 is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made to 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 preparation method of N, N-dibutyl polyether amine nonionic surfactant is characterized by comprising the following steps of,
s1: sequentially adding polyether amine, n-butyl aldehyde, hindered Lewis acid and hindered Lewis base into a high-pressure reaction kettle, adding a dissolving solution, respectively purging with nitrogen and hydrogen, and magnetically stirring for reaction under certain hydrogen pressure and temperature;
s2: and after the reaction is finished, naturally cooling to room temperature, decompressing and rotary-steaming to remove the solvent and impurities, and then repeatedly extracting in petroleum ether for 3-4 times to obtain the N, N-dibutyl polyetheramine nonionic surfactant.
2. The process of claim 1 wherein the hindered lewis acid in S1 is tris (pentafluorophenyl) boron and the hindered lewis base is N, N-dimethylaniline.
3. The process according to claim 1, wherein the molar ratio of polyetheramine to n-butyraldehyde, hindered lewis acid and hindered lewis base in S1 is 1: (2-4): (3-4): (3-4).
4. The method according to claim 1, wherein the solvent in S1 is dichloroethane, chloroform or dichloromethane.
5. The method according to claim 1, wherein the hydrogen pressure in S1 is 1.2-1.8 MPa, the temperature is 120-150 ℃ and the time is 8-12 h.
6. The method of claim 1, wherein the polyetheramine in S1 is M2070.
7. The N, N-dibutyl polyetheramine nonionic surfactant prepared by the process of any one of claims 1 to 6, characterized by the following molecular structure:
8. the tetrabutylammonium hydroxide developer solution based on an N, N-dibutyl polyetheramine nonionic surfactant of claim 7, wherein the developer solution is formulated from an aqueous tetrabutylammonium hydroxide solution and an aqueous solution of an N, N-dibutyl polyetheramine nonionic surfactant.
9. The developer according to claim 8, wherein the developer comprises tetrabutylammonium hydroxide in an amount of 3 to 12wt.% and the N, N-dibutylpolyetheramine nonionic surfactant in an amount of 5 to 10wt.%.
10. The method of preparing tetrabutylammonium hydroxide developer based on N, N-dibutyl polyetheramine nonionic surfactant according to claim 8, characterized by the following steps:
tetrabutylammonium hydroxide, N-dibutyl polyether amine and water are mixed according to a certain proportion and then stirred uniformly to obtain the developing solution.
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