CN115926140B - N, N-dibutyl polyether amine nonionic surfactant, preparation thereof, tetrabutylammonium hydroxide developer based on N, N-dibutyl polyether amine nonionic surfactant and preparation thereof - Google Patents
N, N-dibutyl polyether amine nonionic surfactant, preparation thereof, tetrabutylammonium hydroxide developer based on N, N-dibutyl polyether amine nonionic surfactant and preparation thereof Download PDFInfo
- Publication number
- CN115926140B CN115926140B CN202211669408.9A CN202211669408A CN115926140B CN 115926140 B CN115926140 B CN 115926140B CN 202211669408 A CN202211669408 A CN 202211669408A CN 115926140 B CN115926140 B CN 115926140B
- Authority
- CN
- China
- Prior art keywords
- dibutyl
- nonionic surfactant
- polyether amine
- tetrabutylammonium hydroxide
- developer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
N, N-dibutyl polyether amine nonionic surfactant, its preparation and tetrabutylammonium hydroxide developer based thereon. The invention belongs to the field of surfactants and the field of chip integrated circuit development processes. The invention aims to provide tetrabutylammonium hydroxide developer with potential commercial value and solve the technical problem of high surface tension of tetrabutylammonium hydroxide. The preparation process of the N, N-dibutyl polyether amine nonionic surfactant does not involve a metal catalyst and has higher reaction yield. The aqueous solution of tetrabutylammonium hydroxide is compounded to obtain the developing solution, and the developing solution has the characteristics of low surface tension, stable storage performance, excellent developing effect and huge future commercial prospect, and effectively reduces the problem of image collapse.
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, tetrabutylammonium hydroxide developer based on the same and a preparation method thereof.
Background
Development refers to a process in which a developing solution is used to react with photoresist in the middle and later stages of the photolithography process, so that the pattern of the reticle can be precisely projected onto the photoresist of the wafer. The developer is a chemical solvent for dissolving the soluble region of the photoresist caused by exposure, and can be generally divided into positive and negative developer. Wherein the positive tone developer is typically a strong base solution diluted with water. The conventional developing solution generally uses inorganic alkali KOH, but with the progress of technology, the design and manufacture of integrated circuits need to meet various complex process conditions, and the requirements on chemical impurities are more and more severe. Developing solution produced by using inorganic base such as KOH and the like is required after developmentRinsing the substrate with a large amount of water while not ensuring K + Can be thoroughly washed. The excessive residue of metal ions cannot meet some severe process conditions, such as increasing number of electronic components in a single manufacturing unit and narrowing line width, which are not neglected bottlenecks for restricting the development of the electronic industry. Thus organic bases such as tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and the like have been developed.
The organic alkali just overcomes the defect of KOH, has no metal ion residue after use, and is easy to decompose at high temperature. The main current product on the market is a developer made from TMAH, whereas a developer made from tetraethyl/tetrabutylammonium hydroxide is very rare for process and market reasons. However, as the requirements for line width and uniformity of the photolithography process are increasing, TMAH developer solution also gradually exposes problems. For example, when a conventional 2.38wt.% TMAH developer is used to manufacture fine patterns with a line width of 45nm or less, there is a problem in that the pattern is collapsed due to swelling, which is one of limitations of the TMAH developer in advanced semiconductor processes. If the semiconductor industry wants to develop to the nanometer level of fineness in the future, the developer composition must be continuously updated. Tetrabutylammonium hydroxide developer has been demonstrated to reduce swelling of the photoresist during development and to render the photoresist pattern surface less hydrophilic, thereby effectively reducing image collapse. Furthermore, tetrabutylammonium hydroxide has higher development sensitivity. Therefore, development of tetrabutylammonium hydroxide developer is necessarily a future trend choice.
However, tetrabutylammonium hydroxide developer has larger surface tension, and the tetrabutylammonium hydroxide developer alone cannot fully infiltrate the photoresist in an advanced process, so that poor developing effect with weak or no developing effect is caused, and finally, the yield of products is reduced. Therefore, it is generally necessary to add a surfactant to reduce the surface tension and expand the application range.
Polyether amine nonionic surfactants have been widely used in recent years due to their excellent surface properties, and the preparation methods thereof are mainly reductive amination, hydrolysis, leaving group, nitro end capping, and the like, but most of the reported methods are reductive amination, because of short reaction time, high conversion rate, and good selectivity.
Chinese patent CN114669302a discloses a process for preparing polyetheramines using gamma-Al 2 O 3 As a carrier, the supported metal catalyst is prepared by taking basic copper carbonate, basic nickel carbonate and basic cobalt carbonate as precursors of supported metals, and is successfully applied to the hydroamination reaction of polyether polyol.
Chinese patent CN12759758A discloses a method for preparing polyetheramine by batch catalytic amination, which comprises the following specific operations: polyether is used as a raw material by an intermittent method, and is subjected to reductive amination reaction with hydrogen and liquid ammonia in the presence of a supported nickel catalyst and a modification auxiliary agent to prepare the polyether amine.
Chinese patent CN114874431A discloses a method for preparing polyetheramine, which takes M2070 and paraformaldehyde as raw materials, hydrogen as a reducing agent and Ni-Cu-W/gamma-Al 2 O 3 The polyether amine is prepared by carrying out reductive amination reaction on the catalyst in a fixed bed.
However, the above methods all involve the use of metal catalysts, and the produced polyetheramine may have a risk of metal residue if used for the preparation of the developer, resulting in poor developing effect.
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 tetrabutylammonium hydroxide developer based on the nonionic surfactant and a preparation method thereof.
The invention aims at providing a preparation method of N, N-dibutyl polyether amine nonionic surfactant, which comprises the following steps of,
s1: sequentially adding polyether amine, n-butyraldehyde, hindered Lewis acid and hindered Lewis base into a high-pressure reaction kettle, adding a dissolving solution, purging with nitrogen and hydrogen respectively, and magnetically stirring for reaction under certain hydrogen pressure and temperature;
s2: naturally cooling to room temperature after the reaction is finished, removing solvent and impurities by rotary evaporation under reduced pressure, and then repeatedly extracting in petroleum ether for 3-4 times to obtain the N, N-dibutyl polyether amine nonionic surfactant.
As a preferred embodiment of the present invention, wherein the hindered Lewis acid in S1 is tris (pentafluorophenyl) boron.
As a preferred embodiment of the present invention, wherein the hindered Lewis base in S1 is N, N-dimethylaniline.
As a preferred embodiment of the present invention, 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).
As a preferable mode of the invention, the dissolving 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.
As a preferred embodiment of the present invention, wherein the polyetheramine in S1 is M2070.
The second object of the present invention is to provide an N, N-dibutyl polyether amine nonionic surfactant prepared by the above method, wherein the molecular structure of the N, N-dibutyl polyether amine nonionic surfactant is as follows:
the invention further aims to provide tetrabutylammonium hydroxide developer based on the N, N-dibutyl polyether amine nonionic surfactant, wherein the developer is prepared by compounding tetrabutylammonium hydroxide aqueous solution and N, N-dibutyl polyether amine nonionic surfactant aqueous solution.
As a preferable scheme of the invention, the content of tetrabutylammonium hydroxide in the developing solution is 3-12 wt.% and the content of the N, N-dibutyl polyether amine nonionic surfactant is 5-10 wt.%.
The invention aims at providing a preparation method of tetrabutylammonium hydroxide developer based on N, N-dibutyl polyether amine nonionic surfactant, which comprises the following steps:
tetrabutyl ammonium hydroxide, N-dibutyl polyether amine and water are mixed according to a certain proportion and then uniformly stirred, so as to obtain the developing solution.
As a preferable embodiment of the present invention, wherein 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 polyether amine nonionic surfactant and tetrabutylammonium hydroxide developer based on the N, N-dibutyl polyether amine nonionic surfactant, which have 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 base and the hindered Lewis base form activated hydrogen. The main reaction process is as follows: the amino group on M2070 and the carbonyl group on butyraldehyde firstly undergo an addition reaction to generate amino alcohol, the amino alcohol is dehydrated to generate imine, and finally the imine undergoes a hydrogenation reaction to obtain a target product, if hydrogen is taken as a reducing agent alone, the reaction activity is insufficient, the reaction conversion rate is low, and therefore, a hydrogenation catalyst is usually required to be additionally used. The invention selects the hindered Lewis acid alkali pair to replace common metal catalysts, such as platinum, palladium, nickel and the like, which are transition metal elements of the VIII family, to activate hydrogen, thereby avoiding the participation of metal and improving the conversion rate of the reaction. The report on the preparation of polyetheramine by activating hydrogen by using hindered Lewis acid alkali is relatively few at present, and the yield of the N, N-dibutyl polyetheramine nonionic surfactant prepared by the method is relatively high.
2. According to the invention, the N, N-dibutyl polyether amine nonionic surfactant and tetrabutylammonium hydroxide are compounded to prepare the developing solution, so that the problem of image collapse is effectively reduced, and the storage performance is stable. In addition, tetrabutylammonium hydroxide has higher development sensitivity and excellent development effect. Therefore, development of tetrabutylammonium hydroxide developer is necessarily a future trend of choice.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of M2070;
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of the N, N-dibutylpolyether amine nonionic surfactant obtained in example 1;
FIG. 3 is a flight mass spectrum of M2070;
FIG. 4 is a graph of the flight mass spectrum of the N, N-dibutylpolyether amine nonionic surfactant obtained in example 1.
Detailed Description
In order that the above-recited objects, features and advantages of the present invention will become more apparent, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways other than those described herein, and persons skilled in the art will readily appreciate that the present invention is not limited to the specific embodiments disclosed below.
Further, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic can be 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 polyether amine nonionic surfactant in the embodiment comprises the following steps:
s1: 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 are sequentially added into a high-pressure reaction kettle, dichloroethane is added as a dissolution solution, and after 3 times of purging with nitrogen and hydrogen, the mixture is magnetically stirred and reacted for 10 hours under the hydrogen pressure of 1.6MPa and the temperature of 130 ℃;
s2: and after the temperature of the reaction kettle is reduced to room temperature, collecting a product in a flask, removing a solvent and impurities by reduced pressure rotary evaporation, and then repeatedly extracting in petroleum ether for 3 times to obtain the N, N-dibutyl polyether amine nonionic surfactant with the yield of 96.9%.
Nuclear magnetic resonance hydrogen spectrum analysis of M2070 in fig. 1: 1 h NMR (400MHz,Deuterium Oxide) delta 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=6.2 hz, 27H), 1.06 (d, j=6.5 hz, 3H); the total number of hydrogen integrals in FIG. 1 is 189, where the peak at 3.42 is the leftmost terminal methyl peak of M2070, which can be used for calibration of new species.
Nuclear magnetic resonance hydrogen spectrum analysis of the N, N-dibutylpolyether amine nonionic surfactant obtained in example 1 in FIG. 2: 1 h NMR (400MHz,Deuterium Oxide) delta 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=6.2 hz, 29H), 1.09 (d, j=6.7 hz, 3H), 0.96-0.90 (m, 6H); in FIG. 2, the total hydrogen integral number is 205, the number of the hydrogen integral number is consistent with that of the target product, the peak at 3.40 is taken as a calibration peak, the characteristic peak of methyl at the rightmost side of the butyl carbon chain appears in the interval of 0.96-0.90, and the total hydrogen integral number is 6, and the number of the hydrogen integral number is consistent with that of the methyl.
From a comparison of the results of the nuclear magnetic resonance hydrogen spectrum analyses of the two substances, it can be confirmed that example 1 was indeed successful in preparing N, N-dibutylpolyether amine.
FIGS. 3 and 4 show the results of mass spectra of M2070 and N, N-dibutylpolyetheramine obtained in example 1, respectively, where M2070 was found to have a molecular weight of about 2000 in FIG. 3 and N, N-dibutylpolyetheramine was found to have a molecular weight of about 2112 in FIG. 4, 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 steps were the same as in example 1.
The yield of the obtained pure N, N-dibutyl polyether amine nonionic surfactant 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 steps were the same as in example 1.
The yield of the obtained N, N-dibutyl polyether amine nonionic surfactant is 97.2%.
Example 4:
the difference from example 1 is that: 15.4g (30 mmol) of tris (pentafluorophenyl) boron and 3.8mL (30 mmol) of N, N-dimethylanilinium were added to S1, with the remainder of the parameters and procedure being the same as in example 1.
The yield of the obtained N, N-dibutyl polyether amine nonionic surfactant is 85.2%.
Example 5:
the difference from example 1 is that: to S1 were added 20.5g (40 mmol) of tris (pentafluorophenyl) boron and 5.1mL (40 mmol) of N, N-dimethylaniline, the remaining parameters and steps being the same as in example 1.
The yield of the obtained N, N-dibutyl polyether amine nonionic surfactant 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 steps were the same as in example 1.
The yield of the final N, N-dibutyl polyether amine nonionic surfactant 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 steps were the same as in example 1.
The yield of the obtained N, N-dibutyl polyether amine nonionic surfactant 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 steps were the same as in example 1.
The yield of the obtained N, N-dibutyl polyether amine nonionic surfactant 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 steps were the same as in example 1.
The yield of the obtained N, N-dibutyl polyether amine nonionic surfactant is 96.4%.
Example 10:
the difference from example 1 is that: the reaction time in S1 was 8h, and the remaining parameters and steps were the same as in example 1.
The yield of the obtained pure N, N-dibutyl polyether amine nonionic surfactant is 87.3 percent.
Example 11:
the difference from example 1 is that: the reaction time in S1 was 12h, and the remaining parameters and steps were the same as in example 1.
The yield of the obtained N, N-dibutyl polyether amine nonionic surfactant is 97.8%.
Example 12:
the difference from example 1 is that: the solution in S1 was chloroform, and the other parameters and steps were the same as in example 1.
The yield of the obtained N, N-dibutyl polyether amine nonionic surfactant is 93.2%.
Example 13:
the difference from example 1 is that: the solution in S1 was methylene chloride, and the other parameters and steps were the same as in example 1.
The yield of the obtained N, N-dibutyl polyether amine nonionic surfactant is 86.7%.
Comparative example: unmodified polyetheramine (M2070) surfactant was used as a control group.
Detection test:
the surface tension of the comparative M2070 nonionic surfactant and the N, N-dibutyl polyether amine nonionic surfactant of example 1 were tested as follows:
surface tension test method: the surface tension of the surfactant with different concentrations is measured at 25.0+/-0.1 ℃ by using a BZY-2 type surface tensiometer through a platinum plate method, the instrument is calibrated by using ultrapure water before measurement, a vessel containing liquid is placed on a sample stage to be positioned right below the platinum plate, the reading of the instrument is zeroed, the sample stage is adjusted to enable the solution to slowly rise until the bottom of the platinum plate is just contacted with the surface of the solution, and the stable reading of the surface tensiometer is recorded. The platinum plate was washed, then repeated measurement was performed, continuous measurement was performed 3 times, and an average value was taken as a measurement result, and the error of the continuous measurement of two times was not more than 0.5mN/m. Experimental data are shown in table 1:
TABLE 1 surface tension test results
As is clear from Table 1, the surface tension of the unmodified polyetheramine M2070 nonionic surfactant was at least about 44mN/M, whereas the surface tension of the N, N-dibutylpolyetheramine nonionic surfactant of the present invention was at least about 30 mN/M. The results prove that the surface performance of the N, N-dibutyl polyether amine nonionic surfactant is greatly improved.
(II) the emulsification properties of the comparative M2070 nonionic surfactant and the N, N-dibutylpolyether amine nonionic surfactant of example 1 were tested as follows:
the testing 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 cylinder with a stopper, covering the stopper, keeping the temperature in a water bath at 25 ℃ for 5min, taking out and shaking up and down for 5 times, putting the cylinder into the water bath at 25 ℃ for standing for 1min, taking out and shaking up and down for 5 times, repeating the same steps for 5 times, standing, starting a stopwatch for timing, and recording the time required by separating 10mL of bottom water phase. The above steps were repeated three times to obtain an average value. The experimental data are shown in table 2.
TABLE 2 results of emulsion Performance test of surfactants
| M2070 | Example 1 | |
| Time to split water | 239s | 1085s |
Compared with the unmodified polyether amine M2070 surfactant, the water diversion time of the N, N-dibutyl polyether amine nonionic surfactant prepared in the embodiment 1 is obviously prolonged, and the emulsifying property of the embodiment 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 formulated;
then, 16wt.% of an aqueous solution of N, N-dibutyl polyetheramine nonionic surfactant is formulated;
step (2)
10kg of 16wt.% of N, N-dibutyl polyether amine nonionic surfactant aqueous solution and 10kg of 14wt.% of tetrabutylammonium hydroxide aqueous solution are mixed and continuously stirred until the solution is clear and transparent, thus obtaining the tetrabutylammonium hydroxide developer solution with the mass fraction of 7 wt.%.
The surface tension value of the developer of this example was measured by a surface tensiometer and was 37.4mN/m, and 100g of the developer of application example 1 was put in air, and the pH was measured once at intervals, and experiments found that the initial pH of the developer was 13.25, the pH after 72 hours in air was 12.74, and the pH after 168 hours was 11.34, indicating that the developer had good storage stability.
Spraying the developing solution on a photoresist test piece at 25 ℃ under constant pressure for 60 seconds, cleaning with ultrapure water, drying, and observing a developing pattern under a scanning electron microscope, wherein the result shows that the developing is good and no image collapse phenomenon exists.
Application example 2:
the difference from application example 1 is that: the concentration of the aqueous solution of the N, N-dibutyl polyether amine nonionic surfactant in the step (1) is 10wt.%, and the content of the N, N-dibutyl polyether amine nonionic surfactant in the developer is 5wt.%. The remaining parameters and steps are the same as in example 1.
The surface tension value of the developer of this example was measured by a surface tensiometer and was 40.38mN/m, and 100g of the developer of application example 2 was put in air, and the pH was measured once at intervals, and experiments found that the initial pH of the developer was 13.59, the pH after 72 hours in air was 12.15, and the pH after 168 hours was 10.98, indicating that the developer had good storage stability.
Spraying the developing solution on a photoresist test piece at 25 ℃ under constant pressure for 60 seconds, cleaning with ultrapure water, drying, and observing a developing pattern under a scanning electron microscope, wherein the result shows that the developing is good and no image collapse phenomenon exists.
Application example 3:
the difference from application example 1 is that: the concentration of the aqueous solution of the N, N-dibutyl polyether amine nonionic surfactant in the step (1) is 20wt.%, and the content of the N, N-dibutyl polyether amine nonionic surfactant in the developer is 10wt.%. The remaining parameters and steps are the same as in example 1.
The surface tension value of the developer of this example was 36mN/m by a surface tensiometer, and 100g of the developer of application example 3 was put in air, and the pH value was measured once at intervals, and the experiment found that the initial pH value of the developer was 13.14, the pH value after 72 hours in air was 12.46, and the pH value after 168 hours was 11.14, indicating that the developer had good storage stability.
Spraying the developing solution on a photoresist test piece at 25 ℃ under constant pressure for 60 seconds, cleaning with ultrapure water, and drying. 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 steps are the same as in example 1.
The surface tension value of the developer of this example was measured by a surface tensiometer and was 39.5mN/m, and 100g of the developer of application example 4 was put in air, and the pH was measured once at intervals, and experiments found that the initial pH of the developer was 13.08, the pH after 72 hours in air was 12.32, and the pH after 168 hours was 11.35, indicating that the developer had good storage stability.
Spraying the developing solution on a photoresist test piece at 25 ℃ under constant pressure for 60 seconds, cleaning with ultrapure water, and drying. 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 steps are the same as in example 1.
The surface tension value of the developer of this example was 36.4mN/m as measured by a surface tensiometer, and 100g of the developer of application example 5 was put in air, and the pH value was measured once at intervals, and the experiment found that the initial pH value of the developer was 13.79, the pH value after 72 hours in air was 12.25, and the pH value after 168 hours was 10.79, indicating that the developer had good storage stability.
Spraying the developing solution on a photoresist test piece at 25 ℃ under constant pressure for 60 seconds, cleaning with ultrapure water, and drying. And the result shows that the development is good and no image collapse phenomenon exists.
It should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted without departing from the spirit and scope of the technical solution of the present invention, which is intended to be covered in the scope of the claims of the present invention.
Claims (8)
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-butyraldehyde, hindered Lewis acid and hindered Lewis base into a high-pressure reaction kettle, adding a dissolving solution, purging with nitrogen and hydrogen respectively, and magnetically stirring for reaction under certain hydrogen pressure and temperature; the polyetheramine is M2070, the hindered Lewis acid is tris (pentafluorophenyl) boron, and the hindered Lewis base is N, N-dimethylaniline;
s2: naturally cooling to room temperature after the reaction is finished, removing solvent and impurities by rotary evaporation under reduced pressure, and then repeatedly extracting in petroleum ether for 3-4 times to obtain the N, N-dibutyl polyether amine nonionic surfactant.
2. The process of 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).
3. The method according to claim 1, wherein the solution in S1 is dichloroethane, chloroform or dichloromethane.
4. The method according to claim 1, wherein the hydrogen pressure in S1 is 1.2 to 1.8MPa, the temperature is 120 to 150 ℃ and the time is 8 to 12 hours.
5. The N, N-dibutyl polyether amine nonionic surfactant of any one of claims 1 to 4 having the molecular structure:
6. the tetrabutylammonium hydroxide developer solution based on the N, N-dibutyl polyether amine nonionic surfactant of claim 5, wherein the developer solution is compounded by tetrabutylammonium hydroxide aqueous solution and N, N-dibutyl polyether amine nonionic surfactant aqueous solution.
7. The developer according to claim 6, wherein the content of tetrabutylammonium hydroxide in the developer is 3 to 12wt.% and the content of the N, N-dibutylpolyether amine nonionic surfactant is 5 to 10wt.%.
8. The method for preparing tetrabutylammonium hydroxide developer solution based on the N, N-dibutyl polyether amine nonionic surfactant according to claim 6, which is characterized by comprising the following steps:
tetrabutyl ammonium hydroxide, N-dibutyl polyether amine and water are mixed according to a certain proportion and then uniformly stirred, so as to obtain the developing solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211669408.9A CN115926140B (en) | 2022-12-24 | 2022-12-24 | N, N-dibutyl polyether amine nonionic surfactant, preparation thereof, tetrabutylammonium hydroxide developer based on N, N-dibutyl polyether amine nonionic surfactant and preparation thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211669408.9A CN115926140B (en) | 2022-12-24 | 2022-12-24 | N, N-dibutyl polyether amine nonionic surfactant, preparation thereof, tetrabutylammonium hydroxide developer based on N, N-dibutyl polyether amine nonionic surfactant and preparation thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115926140A CN115926140A (en) | 2023-04-07 |
| CN115926140B true CN115926140B (en) | 2023-07-25 |
Family
ID=86550421
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211669408.9A Active CN115926140B (en) | 2022-12-24 | 2022-12-24 | N, N-dibutyl polyether amine nonionic surfactant, preparation thereof, tetrabutylammonium hydroxide developer based on N, N-dibutyl polyether amine nonionic surfactant and preparation thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115926140B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5912189A (en) * | 1998-05-12 | 1999-06-15 | The Lubrizol Corporation | Compositions containing reaction product of a cyclic compound containing both a nitrogen atom and a carbonyl group, an aldehyde or ketone, and an etheramine |
| CN111072462A (en) * | 2019-12-23 | 2020-04-28 | 长春长光宇航复合材料有限公司 | Bio-based bisphenol monomer, bio-based epoxy resin, composite material of bio-based bisphenol monomer and bio-based epoxy resin and preparation method of composite material |
| CN113402705A (en) * | 2020-03-16 | 2021-09-17 | 中国石油化工股份有限公司 | Polyether amine and preparation method and application thereof |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997030103A2 (en) * | 1996-02-15 | 1997-08-21 | The Dow Chemical Company | Preparation of polyetheramines and polyetheramine derivatives |
| CN102336903A (en) * | 2011-07-07 | 2012-02-01 | 中国石油化工集团公司 | Production process of aliphatic polyetheramine |
| EP2883862A1 (en) * | 2013-12-10 | 2015-06-17 | Basf Se | Method for manufacturing amines |
| CN107075067A (en) * | 2014-09-25 | 2017-08-18 | 巴斯夫欧洲公司 | Polyetheramine based on 1,3 glycol |
| CN107540562B (en) * | 2017-08-10 | 2020-04-28 | 江苏万盛大伟化学有限公司 | Preparation method of tertiary amino terminated polyether |
| CN111330642A (en) * | 2020-04-22 | 2020-06-26 | 江苏斯德瑞克化工有限公司 | Lewis acid-base pair catalyst, preparation method and method for catalytically synthesizing polyether |
| CN114874431B (en) * | 2022-06-13 | 2023-03-28 | 江南大学 | Preparation method of tertiary amine-terminated polyether type nonionic surfactant |
-
2022
- 2022-12-24 CN CN202211669408.9A patent/CN115926140B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5912189A (en) * | 1998-05-12 | 1999-06-15 | The Lubrizol Corporation | Compositions containing reaction product of a cyclic compound containing both a nitrogen atom and a carbonyl group, an aldehyde or ketone, and an etheramine |
| CN111072462A (en) * | 2019-12-23 | 2020-04-28 | 长春长光宇航复合材料有限公司 | Bio-based bisphenol monomer, bio-based epoxy resin, composite material of bio-based bisphenol monomer and bio-based epoxy resin and preparation method of composite material |
| CN113402705A (en) * | 2020-03-16 | 2021-09-17 | 中国石油化工股份有限公司 | Polyether amine and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115926140A (en) | 2023-04-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US8299303B2 (en) | Process for producing a concentrated solution for a photoresist-stripping liquid having low water content | |
| CN109069944A (en) | Purification devices, purification process, manufacturing device, the manufacturing method of medical fluid, container and medical fluid containing body | |
| JPH05148309A (en) | Method for purifying vinylphenol polymer for photoresist | |
| CN1457502A (en) | Process and apparatus for removing residues from microstructure of object | |
| KR102018121B1 (en) | Method for preparing composition for forming organic film | |
| CN115926140B (en) | N, N-dibutyl polyether amine nonionic surfactant, preparation thereof, tetrabutylammonium hydroxide developer based on N, N-dibutyl polyether amine nonionic surfactant and preparation thereof | |
| JP2006063079A (en) | Method for ring-hydrogenation of methylenedianiline | |
| EP3176811A1 (en) | Sacrificial film composition, method for preparing same, semiconductor device having voids formed using said composition, and method for manufacturing semiconductor device using said composition | |
| CN108864418B (en) | Aging crude oil demulsifier and preparation method thereof | |
| TW200905398A (en) | Photoresist base material and photoresist composition containing the same | |
| CN115926815B (en) | Low-surface-tension polyether amine nonionic surfactant, preparation thereof and application thereof in chip integrated circuit developer | |
| CN115058254A (en) | Carboxylate sulfonate surfactant and preparation method and application thereof | |
| CN105727827B (en) | Surfactant, its preparation method and application | |
| CN113304683B (en) | Glucosamide-terminated polyether surfactant, and preparation method and application thereof | |
| EP3505507A1 (en) | Method for purifying dihydroxynaphthalene | |
| CN114163334B (en) | Modified alicyclic amine curing agent and preparation method thereof | |
| US20210130923A1 (en) | Method for extracting and enriching gold with selenide | |
| CN106031854B (en) | A kind of anionic oligo surfactant and preparation method thereof | |
| CN107930698B (en) | Preparation method of catalyst and N1Preparation method of- (2-aminoethyl) -1, 2-ethylenediamine | |
| US10829439B2 (en) | Method for producing adipamide as intermediate for production of raw material for bio-based nylon | |
| CN113121148A (en) | Concrete foam stabilizer based on slow release technology and preparation method and application thereof | |
| CN113430069A (en) | Low-hydroxylamine water-based cleaning solution, and preparation method and application thereof | |
| CN112341338B (en) | Catalytic hydrogenation method for 4-nitrodiphenylamine and 4-nitrosodiphenylamine | |
| CN113354805B (en) | Modified polyether amine nonionic surfactant, and preparation method and application thereof | |
| CN114700078A (en) | Active metal-silicon dioxide catalyst and preparation method of tetramethyl diethylenetriamine |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |