WO2019237401A9 - Novel hydrophobic composition - Google Patents

Abstract

A hydrophobic composition, composed of a hydrogen bond acceptor A and a hydrogen bond donor B; the hydrogen bond acceptor A is one or a mixture of more than one selected from among quaternary ammonium salt, polysiloxane quaternary ammonium salt, a monoterpene alcohol compound, and an amide compound, while the hydrogen bond donor B is one or a mixture of more than one selected from among a polyether, silicone polyether, and hydroxy silicone oil. The hydrophobic composition may be applied in the fields of extractants, solvents for inorganic material synthesis, anti-foaming agents, and so on.

Description

A new type of hydrophobic composition Technical field

The present invention relates to the field of fine chemical products, in particular to a novel hydrophobic composition formed by combining a hydrogen bond acceptor and a hydrogen bond donor with a hydrogen bond force.

Background technique

Hydrogen bond acceptor refers to the components that accept hydrogen bonds, mainly quaternary ammonium salts (such as choline chloride), zwitterions (such as betaine), etc.; hydrogen bond donors refer to components that provide hydrogen bonds, There are mainly urea, thiourea, carboxylic acids (phenylacetic acid, malic acid, citric acid, succinic acid, etc.), polyols (ethylene glycol, glycerol, butylene glycol, xylitol, etc.), amino acids, sugars (glucose , Fructose) trifluoroacetamide and so on.

Most of the compositions that are combined by hydrogen bond acceptor and hydrogen bond donor with hydrogen bond force are hydrophilic, and the composition is mainly formed by the combination of hydrophilic hydrogen bond acceptor and hydrophilic hydrogen bond donor. .

For example, CN103193711 introduces ionic liquids with negative monovalent halogen as anion and transition metal halide salts as hydrogen bond acceptors, and multiple hydrogen bond compounds (acetamide, N-methylurea, N,N'-dimethylurea, N , N-dimethylurea, urea, thiourea, caprolactam, benzamide, trifluoroacetamide, ethylene glycol, glycerin, xylitol, sorbitol, catechol, resorcinol, oxalic acid, propylene One or more of diacid, succinic acid, glutaric acid, adipic acid, maleic acid, malic acid, tartaric acid, citric acid, succinic acid, phthalic acid, isophthalic acid) as hydrogen Key donor.

CN101560187A introduces the use of tetrabutylammonium bromide or choline chloride mixed with imidazole and heated to obtain a homogeneous colorless liquid.

CN106567110A introduces the use of quaternary ammonium salt and polyhydric alcohol to uniformly mix to obtain a composition.

CN106435672A introduces a composition based on choline chloride and malic acid.

CN106119815A introduces a combination of quaternary ammonium salt and urea, acetamide, ethylene glycol and glycerol. CN104059232A introduces a composition prepared by using acetic anhydride and choline chloride.

CN104596056A introduces a composition prepared by reacting a quaternary ammonium compound with a dicarboxylic acid mixture.

CN103752132A introduces a composition prepared by using quaternary ammonium salt (choline chloride) and hydrogen bond matrix compounds (phenol, butanediol, propylene glycol, diethylene glycol, triethylene glycol).

CN106928055A introduces a composition prepared by using choline chloride, salicylic acid and acetic anhydride.

CN105367074A introduces a composition prepared using quaternary ammonium salt ionic liquid, absolute ethanol, and isohexanediol.

US2009247432(A1) introduces the use of quaternary ammonium salts, amides, and alcohols to prepare compositions. This type of composition combined by hydrogen bonding force is also hydrophobic.

Osch D J G P V, Zubeir L F, Bruinhorst A V D, et al. Hydrophobic Deep Eutectic Solvents: Water-Immiscible Extractants[J]. Green Chemistry, 2015, 17(9): 4518-4521. The article introducing this kind of hydrophobic composition uses methyl trioctyl ammonium chloride, methyl trioctyl ammonium bromide, tetrabutyl ammonium chloride, etc. and decanoic acid to prepare this kind of hydrophobic composition.

Ribeiro B D, Florindo C, If L C, et al. Menthol-based Eutectic Mixtures: Hydrophobic Low Viscosity Solvents[J]. Acs Sustainable Chemistry Engineering, 2015, 3(10): 150910100559005. Introduced the use of menthol and acetic acid. , Lauric acid and other hydrophobic low-viscosity compositions.

Hydrophobic Deep Eutectic Solvents promise to play key role in making paper industry More sustainable September 19, 2016 introduced the use of capric acid and lidocaine in different ratios to prepare such hydrophobic compositions.

Tereshatov E, Boltoeva M Y, Folder C M. First evidence of metal transfer into hydrophobic deep eutectic and low-transition-temperature mixtures:indium extraction from hydrochloric and oxalic acids[J].GreenChemistry, 2016,18 4616-4622. Introduced the use of tetraheptylammonium chloride, menthol and lauric acid, capric acid, oleic acid, ibuprofen (ibuprofen) to prepare this type of hydrophobic composition.

Cao J, Yang M, Cao F, et al. Tailor-made hydrophobic deep eutectic solvents for cleaner extraction of polyprenyl acetates from Ginkgo biloba, leaves[J]. Journal of Cleaner Production, 2017, 152:399-405. Introduction of use Methyl trioctyl ammonium chloride and fatty alcohols, fatty acids prepare this kind of hydrophobic composition.

The above-mentioned hydrophobic composition has a relatively large surface tension, a limited degree of hydrophobicity, and a small viscosity range. At the same time, the appearance is mostly light yellow to brown, which affects the subsequent application effect and scope of this type of hydrophobic composition.

Summary of the invention

In view of the above-mentioned problems, the purpose of the present invention is to provide a novel hydrophobic composition formed by combining a quaternary ammonium salt and its derivatives and a hydrogen bond-containing polymer with hydrogen bond force and a preparation method thereof.

In order to achieve the above objective, the technical solution adopted by the present invention is as follows: a novel hydrophobic composition, which is composed of a hydrogen bond acceptor A and a hydrogen bond donor B. The hydrogen bond acceptor A is selected from the group consisting of quaternary ammonium salts and silicone A mixture of one or more of alkyl quaternary ammonium salts, monoterpene alcohol compounds, and amide compounds, and the hydrogen bond donor B is selected from a mixture of one or more of polyethers, silicone polyethers, and hydroxy silicone oils.

The general structural formula I of the quaternary ammonium salt in the composition of the present invention is as follows:

R ¹ R ² R ³ R ⁴ NR ⁵ Ⅰ

In the general formula I, R ^{1 is} selected from a linear alkyl group having 1 to 18 carbons, R ² , R ³ , and R ^{4 are} selected from a linear alkyl group having 4 to 18 carbons, and R ^{5 is} selected from Cl or Br .

The general formula II of the polysiloxane quaternary ammonium salt in the composition of the present invention is as follows:

MD _a (MeRSiO) _b M Ⅱ

In the general formula II, M is a chain link Me ₃ SiO _1/2 , D is a chain link Me ₂ SiO _2/2 , Me is a methyl group, a is an integer from 10 to 100, and b is an integer from 1 to 20; R It is a quaternary ammonium salt group II—I, and its general structure is as follows:

-CH ₂ CH ₂ CH ₂ R ⁶ R ⁷ R ⁸ NCl Ⅱ—Ⅰ

In the general formula II-I, R ⁶ , R ⁷ and R ^{8 are} selected from linear alkyl groups having 1 to 8 carbon atoms.

The monoterpene alcohol compound in the present invention is a monocyclic monoterpene alcohol compound selected from the group consisting of menthol, terpineol, perillyl alcohol, and carvol.

The structural formula III of the amide substance in the present invention is as follows:

R ⁹ —NH—CO—R ¹⁰ Ⅲ

Wherein R ^9, R ¹ 0 the same or different, are selected from linear alkyl group having a carbon number of 1-8, branched chain alkyl, aminoalkyl, cycloalkyl, aralkyl.

The general structural formula IV of the polyether in the present invention is as follows:

R ⁹ (OCH ₂ CH ₂ ) _m (OCH ₂ CHCH ₃ ) _n OH Ⅳ

In the general structural formula IV, R ⁹ is a linear or branched alkyl group, an alkene group, or a cycloalkyl group having a carbon number of 1 to 6, m is an integer of 1 to 50, and n is an integer of 10 to 100.

The general formula V of the silicon polyether structure of the present invention is as follows:

In the general structural formula V, Me is a methyl group, x and y are the degree of polymerization, x is an integer from 1 to 100, y is an integer from 1 to 50, and P is selected from methyl and polyether groups VI-I, at least One P is a polyether group, and the general structure of the polyether group V—I is as follows:

-CH ₂ CH ₂ CH ₂ (OCH ₂ CH ₂ ) _c (OCH ₂ CHCH ₃ ) _d OH Ⅴ—Ⅰ

In the general structural formula V-I, c and d are the degree of polymerization, c is an integer of 1-10, and d is an integer of 10-50.

The general structural formula VI of the hydroxy silicone oil of the present invention is as follows:

HOMe ₂ Si(OSiMe ₂ ) _e OSiMe ₂ OH Ⅵ

In the general structural formula VI, Me is a methyl group, and e is an integer from 10 to 100.

In the novel hydrophobic composition of the present invention, the amount of hydrogen bond acceptor A is 17%-50% of the total mass of the novel hydrophobic composition, and the amount of hydrogen bond donor B is 50%-50% of the total mass of the novel hydrophobic composition. 83%.

In the novel hydrophobic composition of the present invention, when the hydrogen bond acceptor A is a single substance, quaternary ammonium salts are preferred, polysiloxane quaternary ammonium salts are second preferred, and monoterpene alcohol compounds and amide compounds are more preferred.

In the novel hydrophobic composition, when the hydrogen bond donor B is a single substance, hydroxy silicone oil is preferred, silicone polyether is second preferred, and polyether is more preferred.

^{R 1} in the quaternary ammonium salt of the present invention is preferably a linear alkyl group having 8 to 18 carbon atoms.

In the quaternary ammonium salt of the present invention, R ² , R ³ , and R ^{4 are} preferably linear alkyl groups having 8-18 carbon atoms.

^{The carbon numbers of R 9} and R ¹⁰ in the amide compound of the present invention are preferably 4 to 8;

In the general formula V of the silicon polyether structure of the present invention, x is preferably an integer of 10-40, and y is preferably an integer of 10-20.

In the general formula IV of the polyether structure of the present invention, m is preferably an integer of 2-10, and n is preferably an integer of 15-50.

In the general formula VI of the hydroxy silicone oil of the present invention, e is preferably an integer of 20-60.

The preparation method of the novel hydrophobic composition provided by the present invention is as follows:

1) Put the hydrogen bond acceptor A in an oven at 100～110℃ for 1～3h to remove the water in the system;

2) Mix and seal the hydrogen bond acceptor A and the hydrogen bond donor B from which moisture has been removed, and stir in a water bath for 0.5 to 2 hours until the mixture system is completely transparent;

3) After the heat preservation is continued for 0.5 to 1.5 hours, a transparent, clear and hydrophobic composition is obtained.

The temperature of the water bath in steps 2) and 3) of the present invention is 20-90°C. When the temperature is lower than 20°C, the preparation time of the composition is prolonged, and when the temperature is higher than 90°C, the appearance of the composition becomes darker. , Is not conducive to subsequent applications.

The novel hydrophobic composition of the present invention can be used directly as a defoamer in an industrial production process, and can also be used as a synthetic raw material for a defoamer, such as an emulsifier and a carrier of a mineral oil defoamer.

The novel hydrophobic composition of the present invention can be applied to a chemical reaction process as a reaction medium instead of traditional organic solvents.

The novel hydrophobic composition of the present invention can be applied to the separation process in synthetic chemistry as an extractant.

The advantages of the invention are that the novel hydrophobic composition of the invention has the advantages of low surface tension, high degree of hydrophobicity, wide viscosity range, good selectivity, transparent appearance and easy subsequent application, and can be widely used in industrial production processes.

Description of the drawings

Figure 1 is a schematic diagram of the surface tension test results of the composition in the embodiment of the present invention;

Figure 2 is a schematic diagram of the test results of the water content of the composition in an embodiment of the present invention;

Figure 3 is a schematic diagram of the test results of the oil phase water content after the composition is mixed with water in an embodiment of the present invention;

4 is a schematic diagram of the results of the viscosity test of the composition in the embodiment of the present invention;

5 is a schematic diagram of the appearance results of the composition in the embodiment of the present invention;

FIG. 6 is a schematic diagram of the result of applying the embodiment in the embodiment of the present invention.

Among them, the "--" in Figures 2, 3, 4, and 5 means that the formula does not form a stable hydrophobic composition and cannot be tested accordingly.

detailed description:

The present invention will be further described in detail below in conjunction with the description of the drawings and the specific embodiments.

Compared with the same type of composition, the novel hydrophobic composition prepared by the present invention has lower surface tension, higher degree of hydrophobicity (low water content, low oil phase water content after mixing with water), and good selectivity (wide The viscosity range), colorless, transparent and clear appearance. The following comparison tests are carried out respectively.

1. The composition surface tension test: use KRUSS's BP100 dynamic surface tension meter to test.

2. Composition moisture content test: use Karl Fischer moisture meter to test;

3. The water content test of the oil phase after the composition is mixed with water:

Mix 4 g of the composition and 4 g of distilled water into a 10 mL centrifuge tube, and rotate at 3000 rpm for 30 minutes; use a Karl Fischer moisture meter to test the water content in the upper liquid.

4. Composition viscosity test: use BROOKFIELD's DV2TLVTJ0 viscometer to test.

5. Composition appearance test: visual inspection.

The results of the performance test are shown in Figure 1-5.

Application performance test of the novel hydrophobic composition prepared by the present invention:

1. Used in the defoaming agent industry, refer to the national standard GB/T 26527-2011 to test its anti-foaming performance, and test its anti-foaming performance in the sodium dodecylbenzene sulfonate shake flask method. The lower the foam height, the The better the anti-foaming performance.

2. For organic solvents for chemical reactions, refer to the method in Example 1 of Patent CN104059232A. The higher the product yield, the better the application performance.

3. Using chemical separation extractant, refer to the method in Example 2 in patent CN104593056A. The higher the desulfurization rate, the better the separation effect.

Example 1: Place a ceramic tray containing tetraoctyl ammonium bromide in an oven at 100°C for 3 hours, take it out and cool it to room temperature in a glass desiccator, accurately weigh 50g of dried tetraoctyl ammonium bromide and place it in _{Put 50g polyether CH 3} (OCH ₂ CH ₂ ) ₂ (OCH ₂ CHCH ₃ ) ₁₅ OH into a 250mL four-necked flask, seal it, keep it in a water bath at 90℃ and stir for 0.5h, until the system is transparent, continue to keep it warm and stirring at 90℃ 0.5h, a transparent and clear hydrophobic composition M1 is formed.

Example 2: Place the ceramic tray containing tetraoctylammonium bromide in an oven at 100℃ for 3h, take it out and cool it to room temperature in a glass desiccator, accurately weigh 50g of dried tetraoctylammonium bromide and place it in Into a 250mL four-necked flask, put 50g of silicone polyether (CH ₃ ) ₃ SiO(Me ₂ SiO) ₁₀ {(Me(CH ₂ CH ₂ CH ₂ (OCH ₂ CH ₂ )(OCH ₂ CHCH ₃ ) ₁₀ OH)SiO } ₁₀ Si(CH ₃ ) ₃ , sealed, kept in a water bath at 90°C and stirred for 0.5h. After the system became transparent, kept stirring at 90°C for 0.5h to form a transparent, clear and hydrophobic composition M2.

Example 3: Place the ceramic tray containing tetraoctylammonium bromide in an oven at 100°C for 3h, take it out and cool it to room temperature in a glass desiccator, accurately weigh 50g of dried tetraoctylammonium bromide and place it in Put 50g of hydroxy silicone oil HOMe ₂ Si(OSiMe ₂ ) ₂₀ OSiMe ₂ OH into a 250mL four-necked flask, seal it, keep it in a water bath at 90℃ and stir for 0.5h. After the system is transparent, keep it at 90℃ and stir for 0.5h to form a Transparent clear hydrophobic composition M3.

Example 4: Place the ceramic tray containing tetraoctadecylammonium chloride in an oven at 110℃ for 1h, take it out and cool it to room temperature in a glass desiccator, accurately weigh 40g of dried tetraoctadecylammonium chloride and place it in Put 60g of hydroxy silicone oil HOMe ₂ Si(OSiMe ₂ ) ₆₀ OSiMe ₂ OH into a 250mL four-necked flask, seal it, keep it in a water bath at 20℃ and stir for 1.5h. After the system is transparent, keep it at 20℃ and stir for 1.5h to form a Transparent clear hydrophobic composition M4.

Example 5: Place a _{ceramic tray containing MD 10} (Me(CH ₂ CH ₂ CH ₂ (C ₈ H ₁₇ ) ₃ NCl)SiO)M in an oven at 110°C for 1 hour, then take it out and place it in a glass desiccator to cool to At room temperature, accurately weigh 40g of dried MD ₁₀ (Me(CH ₂ CH ₂ CH ₂ (C ₈ H ₁₇ ) ₃ NCl)SiO)M into a 250mL four-necked flask, and then put in 60g of hydroxy silicone oil HOMe ₂ Si(OSiMe ₂ ) ₆₀ OSiMe ₂ OH, sealed, kept in a water bath at 20°C and stirred for 1.5h. After the system is transparent, keep holding and stirring at 20°C for 1.5h to form a transparent, clear and hydrophobic composition M5.

Example 6: Put _{the ceramic tray containing (CH 3} CH ₂ ) ₂ N-CH ₂ -CO-NH-{Ph(CH ₃ ) ₂ } in an oven at 110°C for 1 hour, then take it out and place it in a glass desiccator for cooling To room temperature, accurately weigh 40g of dried (CH ₃ CH ₂ ) ₂ N-CH ₂ -CO-NH-{Ph(CH ₃ ) ₂ } into a 250mL four-necked flask, and then put in 60g of hydroxy silicone oil HOMe ₂ Si (OSiMe ₂ ) ₆₀ OSiMe ₂ OH, sealed, heat preservation and stirring in a water bath at 20°C for 1.5 hours, and after the system is transparent, continue heat preservation and stirring at 20°C for 1.5 hours to form a transparent, clear and hydrophobic composition M6.

Example 7: Place the ceramic tray containing menthol in an oven at 110°C for 1 hour, take it out and cool it to room temperature in a glass desiccator, accurately weigh 40g of dried menthol and place it in a 250mL four-necked flask, and then put it in 60g of hydroxy silicone oil HOMe ₂ Si(OSiMe ₂ ) ₆₀ OSiMe ₂ OH, sealed, kept in a water bath at 20°C and stirred for 1.5h, and after the system became transparent, kept stirring at 20°C for 1.5h to form a transparent, clear and hydrophobic composition M7.

Example 8: Place a ceramic tray containing tetraoctyl ammonium bromide and polysiloxane quaternary ammonium salt MD ₁₀₀ (Me(CH ₂ CH ₂ CH ₂ (CH ₃ ) ₃ NCl) SiO) ₂₀ M at 100°C Let the oven stand for 3 hours, take it out and cool it to room temperature in a glass desiccator, accurately weigh out 30g of dried tetraoctylammonium chloride and 20g of dried MD ₁₀₀ (Me(CH ₂ CH ₂ CH ₂ (CH ₃ ) ₃ NCl )SiO) ₂₀ M is placed in a 250mL four-necked flask, then 50g polyether CH ₃ (OCH ₂ CH ₂ ) ₂ (OCH ₂ CHCH ₃ ) ₁₅ OH is put in, sealed, kept in a water bath at 90℃ and stirred for 0.5h until the system is transparent Afterwards, the temperature was kept at 90° C. and stirring was continued for 0.5 h to form a transparent, clear and hydrophobic composition M8.

Example 9: Place a ceramic tray containing tetraoctylammonium bromide and terpineol in an oven at 100°C for 3h, take it out and cool it to room temperature in a glass desiccator, and accurately weigh 20g of dried tetraoctyl chloride Put ammonium chloride and 30g dried terpineol in a 250mL four-necked flask, and then put 50g silicone polyether (CH ₃ ) ₃ SiO(Me ₂ SiO) ₁₀ {(Me(CH ₂ CH ₂ CH ₂ (OCH ₂ CH ₂ )(OCH ₂ CHCH ₃ ) ₁₀ OH)SiO} ₁₀ Si(CH ₃ ) ₃ , sealed, keep in a water bath at 90℃ and stir for 0.5h. After the system is transparent, keep stirring at 90℃ for 0.5h to form a transparent and clear Hydrophobic composition M9.

Example 10: Put a ceramic tray containing tetraoctylammonium bromide and amides CH ₃ (CH ₂ ) ₃ -CO-NH-Ph in an oven at 100°C for 3 hours, then take it out and place it in a glass desiccator to cool to At room temperature, accurately weigh 15g of dried tetraoctylammonium chloride and 35g of dried CH ₃ (CH ₂ ) ₃ -CO-NH-Ph into a 250mL four-necked flask, and then put in 50g of hydroxy silicone oil HOMe ₂ Si( OSiMe ₂ ) ₂₀ OSiMe ₂ OH, sealed, kept in a water bath at 90° C. and stirred for 0.5 h. After the system became transparent, the system was kept at 90° C. and stirred for 0.5 h to form a transparent, clear and hydrophobic composition M10.

Example 11: Put MD ₁₀ (Me(CH ₂ CH ₂ CH ₂ (C ₈ H ₁₇ ) ₃ NCl) SiO) M, amides

The ceramic tray of CH ₃ (CH ₃ CH ₂ CH)-CO-NH-CH ₂ -{CH(CH ₂ ) ₄ } is placed in an oven at 110°C for 1 hour, then taken out and placed in a glass desiccator to cool to room temperature, and weighed accurately 10g dried MD ₁₀ (Me(CH ₂ CH ₂ CH ₂ (C ₈ H ₁₇ ) ₃ NCl)SiO)M, 30g dried CH ₃ (CH ₃ CH ₂ CH)-CO-NH-CH ₂ -( Put CH(CH ₂ ) ₄ } in a 250mL four-necked flask, then put in 60g of hydroxy silicone oil HOMe ₂ Si(OSiMe ₂ ) ₆₀ OSiMe ₂ OH, 20g, seal, keep in a water bath at 20℃ and stir for 1.5h, until the system is transparent, Continue to heat and stir for 1.5 hours at 20°C to form a transparent, clear and hydrophobic composition M11.

Example 12: Place _{the ceramic tray containing (CH 3} CH ₂ ) ₂ N-CH ₂ -CO-NH-{Ph(CH ₃ ) ₂ } and carvol in an oven at 110°C for 1 hour, take it out and place it on The glass desiccator was cooled to room temperature, and accurately weighed 20g of dried (CH ₃ CH ₂ ) ₂ N-CH ₂ -CO-NH-{Ph(CH ₃ ) ₂ }, 20g of dried carvol and placed it in 250 mL of four Put 60g of hydroxy silicone oil HOMe ₂ Si(OSiMe ₂ ) ₆₀ OSiMe ₂ OH into the open-mouth flask, seal it, keep it in a water bath at 20℃ and stir for 1.5h. After the system is transparent, keep it at 20℃ and stir for 1.5h to form a transparent and clear Hydrophobic composition M12.

Example 13: Add menthol, tetradecylammonium chloride, MD ₅₀ (Me(CH ₂ CH ₂ CH ₂ (C ₃ H ₇ ) ₃ NCl) SiO) ₁₀ M, CH ₃ (CH ₂ ) _3- The ceramic tray of CO-NH-(CH ₂ ) ₃ CH ₃ is placed in an oven at 110°C for 1 hour, taken out and placed in a glass desiccator to cool to room temperature, and accurately weighed out 10g dried menthol and 10g dried MD ₅₀ ( Me(CH ₂ CH ₂ CH ₂ (C ₃ H ₇ ) ₃ NCl)SiO) ₁₀ M, 10g dried tetradecylammonium chloride, 10g dried CH ₃ (CH ₂ ) ₃ -CO-NH-( Put CH ₂ ) ₃ CH ₃ in a 250mL four-necked flask, then put in 60g of hydroxy silicone oil HOMe ₂ Si(OSiMe ₂ ) ₆₀ OSiMe ₂ OH, seal, keep in a water bath at 20℃ and stir for 1.5h, until the system is transparent, continue at 20℃ Heat preservation and stirring for 1.5 hours to form a transparent and clear hydrophobic composition M13.

Example 14: Place the ceramic tray containing tetraoctylammonium bromide in an oven at 100℃ for 3h, take it out and cool it to room temperature in a glass desiccator, accurately weigh 50g of dried tetraoctylammonium chloride and place it in Put into a 250mL four-necked flask, then put 25g polyether CH ₃ (OCH ₂ CH ₂ ) ₂ (OCH ₂ CHCH ₃ ) ₁₅ OH, 25g silicone polyether (CH ₃ ) ₃ SiO(Me ₂ SiO) ₄₀ {(Me(CH ₂ CH ₂ CH ₂ (OCH ₂ CH ₂ ) ₁₀ (OCH ₂ CHCH ₃ ) ₅₀ OH)SiO} ₂₀ Si(CH ₃ ) ₃ Seal, keep in a water bath at 90℃ and stir for 0.5h, until the system is transparent, continue to keep the temperature at 90℃ Stir for 0.5h to form a transparent and clear hydrophobic composition M14.

Example 15: Place the ceramic tray containing tetraoctylammonium bromide in an oven at 100℃ for 3h, take it out and cool it to room temperature in a glass desiccator, accurately weigh 50g of dried tetraoctylammonium chloride and place it in Into a 250mL four-necked flask, put 20g silicone polyether (CH ₃ ) ₃ SiO(Me ₂ SiO) ₁₀ {(Me(CH ₂ CH ₂ CH ₂ (OCH ₂ CH ₂ )(OCH ₂ CHCH ₃ ) ₁₀ OH)SiO } ₁₀ Si(CH ₃ ) ₃ , 30g of hydroxy silicone oil HOMe ₂ Si(OSiMe ₂ ) ₄₀ OSiMe ₂ OH sealed, kept in a water bath at 90°C and stirred for 0.5h, until the system is transparent, continue to keep holding and stirring at 90°C for 0.5h to form a Transparent clear hydrophobic composition M15.

Example 16: Place the ceramic tray containing tetraoctylammonium bromide in an oven at 100℃ for 3h, take it out and cool it to room temperature in a glass desiccator, accurately weigh 50g of dried tetraoctylammonium chloride and place it in _{Put 15g of hydroxy silicone oil HOMe 2} Si(OSiMe ₂ ) ₂₀ OSiMe ₂ OH, 35g polyether CH ₃ (CH ₂ ) ₅ (OCH ₂ CH ₂ ) ₁₀ (OCH ₂ CHCH ₃ ) ₅₀ OH into a 250mL four-necked flask, and seal it, Heat and stir in a water bath at 90°C for 0.5h. After the system is transparent, continue to heat and stir at 90°C for 0.5h to form a transparent, clear and hydrophobic composition M16.

Example 17: The ceramic tray containing tetraoctyl ammonium bromide was placed in an oven at 100°C for 3 hours, then taken out and placed in a glass desiccator to cool to room temperature, and 50 g of dried tetraoctyl ammonium chloride was accurately weighed and placed in 250 mL Into a four-necked flask, 15g polyether CH ₃ (OCH ₂ CH ₂ ) ₂ (OCH ₂ CHCH ₃ ) ₁₅ OH, 15g silicone polyether (CH ₃ ) ₃ SiO(Me ₂ SiO) ₂₀ {(Me(CH ₂₎ CH ₂ CH ₂ (OCH ₂ CH ₂ ) ₅ (OCH ₂ CHCH ₃ ) ₃₀ OH)SiO} ₁₅ Si(CH ₃ ) ₃ , 20g hydroxy silicone oil HOMe ₂ Si(OSiMe ₂ ) ₃₀ OSiMe ₂ OH sealed, water bath at 90℃ After the system is kept and stirred for 0.5 h, after the system is transparent, the temperature is kept at 90° C. and the stirring is continued for 0.5 h to form a transparent, clear and hydrophobic composition M17.

Example 18: Place the ceramic tray containing tetralauryl ammonium chloride in an oven at 105°C for 2 hours, take it out and cool it to room temperature in a glass desiccator, accurately weigh out 17g of dried tetralauryl ammonium chloride and place it in Put into a 250mL four-necked flask, then put 83g of hydroxy silicone oil HOMe ₂ Si(OSiMe ₂ ) ₅₀ OSiMe ₂ OH, seal it, keep it in a water bath at 60℃ and stir for 1h, until the system is transparent, continue to keep it warm and stir for 1h at 60℃ to form a transparent and clear Hydrophobic composition M18.

Example 19: Place the ceramic tray containing tetradecylammonium bromide in an oven at 108°C for 1.2h, take it out and cool it to room temperature in a glass desiccator, accurately weigh 25g of dried tetradecylammonium bromide and place it _{Put 75g polyether (CH 3} ) ₂ CH ₂ CH(OCH ₂ CH ₂ ) ₅ (OCH ₂ CHCH ₃ ) ₃₀ OH into a 250mL four-necked flask, seal it, keep it in a 40℃ water bath and stir for 1.3h until the system is transparent Afterwards, the temperature was kept at 40°C and stirred for 1.2 hours to form a transparent, clear and hydrophobic composition M19.

Example 20: Place the ceramic tray containing tetraoctyl ammonium chloride in an oven at 103°C for 2.5 hours, take it out and cool it to room temperature in a glass desiccator, accurately weigh out 45g of dried tetraoctyl ammonium chloride and place it Put into a 250mL four-necked flask, then put 55g of silicone polyether (CH ₃ ) ₃ SiO(Me ₂ SiO) ₃₀ {(Me(CH ₂ CH ₂ CH ₂ (OCH ₂ CH ₂ )(OCH ₂ CHCH ₃ ) ₁₀ OH) SiO} ₁₈ Si(CH ₃ ) ₃ , sealed, kept in a water bath at 50° C. and stirred for 1.5 hours. After the system is transparent, continue to keep warm and agitate at 50° C. for 1 hour to form a transparent, clear and hydrophobic composition M20.

Example 21: Place the ceramic tray containing methyl trioctyl ammonium chloride in an oven at 105°C for 2 hours, take it out and cool it to room temperature in a glass desiccator, and accurately weigh out 17 g of dried tetralauryl ammonium chloride Put it in a 250mL four-necked flask, then put in 83g of hydroxy silicone oil HOMe ₂ Si(OSiMe ₂ ) ₅₀ OSiMe ₂ OH, seal it, keep it in a water bath at 60℃ and stir for 1h. After the system is transparent, keep it at 60℃ and keep stirring for 1h to form a Transparent clear hydrophobic composition M21.

Example 22: Place the ceramic tray containing methyltributylammonium bromide in an oven at 108°C for 1.2h, take it out and cool it to room temperature in a glass desiccator, and accurately weigh 25g of the dried tetradecyl bromide Ammonium was placed in a 250mL four-necked flask, and then 75g polyether (CH ₃ ) ₂ CH ₂ CH(OCH ₂ CH ₂ ) ₅ (OCH ₂ CHCH ₃ ) ₃₀ OH was put into it, sealed, and kept in a water bath at 40°C and stirred for 1.3 hours to After the system was transparent, the temperature was kept at 40°C and stirred for 1.2 hours to form a transparent, clear and hydrophobic composition M22.

Example 23: Place the ceramic tray containing tetrapentylammonium chloride in an oven at 103°C for 2.5h, take it out and cool it to room temperature in a glass desiccator, accurately weigh out 45g of dried tetraoctylammonium chloride and place it Put into a 250mL four-necked flask, then put 55g silicone polyether (CH ₃ ) ₃ SiO(Me ₂ SiO) ₃₀ {(Me(CH ₂ CH ₂ CH ₂ (OCH ₂ CH ₂ )(OCH ₂ CHCH ₃ ) ₁₀ OH) SiO} ₁₈ Si(CH ₃ ) ₃ , sealed, kept in a water bath at 50° C. and stirred for 1.5 hours. After the system became transparent, the system was kept at 50° C. and stirred for 1 hour to form a transparent, clear and hydrophobic composition M23.

Example 24: Put _{the ceramic tray containing (CH 3} CH ₂ ) ₂ N-CH ₂ -CO-NH-{Ph(CH ₃ ) ₂ } in an oven at 102°C for 2.5 hours, then take it out and place it in a glass desiccator Cool to room temperature, accurately weigh 20g of dried (CH ₃ CH ₂ ) ₂ N-CH ₂ -CO-NH-{Ph(CH ₃ ) ₂ } into a 250mL four-necked flask, and then put in 80g of hydroxy silicone oil HOMe ₂ Si(OSiMe ₂ ) ₃₅ OSiMe ₂ OH, sealed, kept in a water bath at 35° C. and stirred for 1.5 hours. After the system became transparent, the system was kept at 35° C. and stirred for 1.5 hours to form a transparent, clear and hydrophobic composition M24.

Example 25: Put _{the ceramic tray containing CH 3} (CH ₂ ) ₆ -CO-NH-(CH ₂ ) ₄ CH ₃ in an oven at 102 ℃ for 2.5 hours, take it out and cool it to room temperature in a glass desiccator, accurately Weigh 35g of dried CH ₃ (CH ₂ ) ₆ -CO-NH-(CH ₂ ) ₄ CH ₃ into a 250 mL four-neck flask, and then put in 65g polyether CH ₂ =CHCH ₂ (OCH ₂ CH ₂ ) ₈ (OCH ₂ CHCH ₃ ) ₄₀ OH, sealed, kept in a water bath at 65°C and stirred for 1.5 hours. After the system became transparent, the system was kept at 65°C and kept stirring for 1.5 hours to form a transparent, clear and hydrophobic composition M25.

Example 26: Place _{the ceramic tray containing CH 3} (CH ₂ ) ₅ -CO-NH-Ph in an oven at 107°C for 2 hours, take it out and cool it to room temperature in a glass desiccator, and accurately weigh 22 g of the dried CH ₃ (CH ₂ ) ₅ -CO-NH-Ph is placed in a 250mL four-necked flask, and then 78g silicone polyether {HO(CH ₃ CHCH ₂ O) ₄₀ (CH ₂ CH ₂ O) ₃ CH ₂ CH ₂ CH ₂ Si(Me) ₂ O}(Si(Me) ₂ O) ₃₀ Si(Me) ₃ , sealed, keep in a water bath at 45℃ and stir for 1.5h. After the system is transparent, continue to keep the temperature and stir for 1.5h at 45℃ to form a transparent Clarifies the hydrophobic composition M26.

Example 27: Place _{the ceramic tray containing CH 3} -CO-NH-CH ₂ CH ₃ in an oven at 102°C for 2.5 hours, take it out and cool it to room temperature in a glass desiccator, and accurately weigh 20 g of the dried CH ₃ -CO-NH-CH ₂ CH _{3 was} placed in a 250mL four-necked flask, and then put 80g of hydroxy silicone oil HOMe ₂ Si(OSiMe ₂ ) ₃₅ OSiMe ₂ OH, sealed, kept in a 35℃ water bath and stirred for 1.5h, until the system was transparent, Continue to heat and stir at 35°C for 1.5 hours to form a transparent, clear and hydrophobic composition M27.

Example 28: Put _{the ceramic tray containing (CH 3} ) ₂ CH-CO-NH-(CH ₂ ) ₂ CH ₃ in an oven at 102°C for 2.5 hours, take it out and place it in a glass desiccator to cool to room temperature, weigh it accurately Take 35g of dried (CH ₃ ) ₂ CH-CO-NH-(CH ₂ ) ₂ CH ₃ into a 250mL four-necked flask, then put in 65g polyether CH ₂ =CHCH ₂ (OCH ₂ CH ₂ ) ₈ (OCH ₂ CHCH ₃ ) ₄₀ OH, sealed, kept in a water bath at 65°C and stirred for 1.5h. After the system is transparent, continue to keep warm and stirring at 65°C for 1.5h to form a transparent, clear and hydrophobic composition M28.

Example 29: Place _{the ceramic tray containing CH 3} -CO-NH-CH ₃ in an oven at 107°C for 2 hours, take it out and cool it to room temperature in a glass desiccator, and accurately weigh 22 g of the dried CH ₃ -CO- NH-CH _{3 was} placed in a 250mL four-necked flask, and then 78g silicone polyether {HO(CH ₃ CHCH ₂ O) ₄₀ (CH ₂ CH ₂ O) ₃ CH ₂ CH ₂ CH ₂ Si(Me) ₂ O}( (Me) ₂ SiO) ₃₀ Si(Me) ₃ , sealed, kept in a water bath at 45°C and stirred for 1.5h. After the system is transparent, continue to heat and stir at 45°C for 1.5h to form a transparent, clear and hydrophobic composition M29.

Example 30: Place the ceramic tray containing tetraoctylammonium bromide in an oven at 100°C for 3h, take it out and cool it to room temperature in a glass desiccator, accurately weigh 30g of dried tetraoctylammonium bromide and place it in Into a 250mL four-necked flask, put 70g of silicone polyether {HO(CH ₃ CHCH ₂ O) ₁₅ (CH ₂ CH ₂ O) ₈ CH ₂ CH ₂ CH ₂ Si(Me) ₂ O}((Me) ₂ SiO) ₄₅ {HO(CH ₃ CH ₂ CH ₂ O) ₁₅ (CH ₂ CH ₂ O) ₈ CH ₂ CH ₂ CH ₂ Si(Me) ₂ }, seal, keep in a water bath at 90℃ and stir for 0.5h, until the system is transparent, Continue to heat and stir at 90°C for 0.5h to form a transparent, clear and hydrophobic composition M30.

Example 31: Place the ceramic tray containing the polysiloxane quaternary ammonium salt MD ₁₀ (Me(CH ₂ CH ₂ CH ₂ (C ₈ H ₁₇ ) ₃ NCl)SiO)M in an oven at 100°C for 2 hours, and take it out Place it in a glass desiccator to cool to room temperature, accurately weigh out 32g of the dried polysiloxane quaternary ammonium salt MD ₁₀ (Me(CH ₂ CH ₂ CH ₂ (C ₈ H ₁₇ ) ₃ NCl)SiO)M and place it in 250 mL of quaternary ammonium salt MD 10 (Me(CH 2 CH 2 CH 2 (C 8 H 17) 3 NCl)SiO)M Into the mouth flask, then put 68g of silicone polyether {HO(CH ₃ CHCH ₂ O) ₄₀ (CH ₂ CH ₂ O) ₃ CH ₂ CH ₂ CH ₂ Si(Me) ₂ O}((Me) ₂ SiO) ₂₅ { (Me(CH ₂ CH ₂ CH ₂ (OCH ₂ CH ₂ ) ₃ (OCH ₂ CHCH ₃ ) ₄₀ OH)SiO} ₁₈ Si(CH ₃ ) ₃ , sealed, keep in a water bath at 85℃ and stir for 0.5h, until the system is transparent , And continue to keep heat and stir at 85°C for 0.5h to form a transparent, clear and hydrophobic composition M31.

Example 32: Place the ceramic tray containing menthol in an oven at 100°C for 2h, take it out and cool it to room temperature in a glass desiccator, accurately weigh 44g of dried menthol and place it in a 250mL four-necked flask, and then put it in 56g silicone polyether {HO(CH ₃ CHCH ₂ O) ₂₅ (CH ₂ CH ₂ O) ₆ CH ₂ CH ₂ CH ₂ Si(Me) ₂ O)((Me) ₂ SiO) ₃₅ {(Me(CH ₂ CH ₂ CH ₂ (OCH ₂ CH ₂ ) ₆ (OCH ₃ CHCH ₃ ) ₂₅ OH)SiO) ₁₂ {HO(CH ₃ CHCH ₂ O) ₂₅ (CH ₂ CH ₂ O) ₆ CH ₂ CH ₂ CH ₂ Si(Me) ₂ }, sealed, kept in a water bath at 75°C and stirred for 1.5h. After the system is transparent, continue to keep warm and stirring at 75°C for 1h to form a transparent, clear and hydrophobic composition M32.

Example 33: Place the ceramic tray containing tetraoctyl ammonium bromide in an oven at 100°C for 3 hours, take it out and cool it to room temperature in a glass desiccator, accurately weigh 30 g of dried tetraoctyl ammonium bromide and place it in Into a 250mL four-necked flask, put 70g of silicone polyether {HO(CH ₃ CHCH ₂ O) ₁₅ (CH ₂ CH ₂ O) ₈ CH ₂ CH ₂ CH ₂ Si(Me) ₂ O}((Me) ₂ SiO) ₄₅ {HO(CH ₃ CH ₂ CH ₂ O) ₁₅ (CH ₂ CH ₂ O) ₈ CH ₂ CH ₂ CH ₂ Si(Me) ₂ }, seal, keep in a water bath at 90℃ and stir for 0.5h, until the system is transparent, Continue to heat and stir at 90°C for 0.5h to form a transparent, clear and hydrophobic composition M33.

Example 34: Place the ceramic tray containing the polysiloxane quaternary ammonium salt MD ₁₀ (Me(CH ₂ CH ₂ CH ₂ (C ₈ H ₁₇ ) ₃ NCl)SiO)M in an oven at 100°C for 2 hours, and take it out Place it in a glass desiccator to cool to room temperature, accurately weigh 32g of the dried polysiloxane quaternary ammonium salt MD ₁₀ (Me(CH ₂ CH ₂ CH ₂ (C ₈ H ₁₇ ) ₃ NCl)SiO)M into 250mL Into the mouth flask, then put 68g of silicone polyether {HO(CH ₃ CHCH ₂ O) ₄₀ (CH ₂ CH ₂ O) ₃ CH ₂ CH ₂ CH ₂ Si(Me) ₂ O}((Me) ₂ SiO) ₂₅ { (Me(CH ₂ CH ₂ CH ₂ (OCH ₂ CH ₂ ) ₃ (OCH ₂ CHCH ₃ ) ₄₀ OH)SiO} ₁₈ Si(CH ₃ ) ₃ , sealed, keep in a water bath at 85℃ and stir for 0.5h, until the system is transparent , 85 ℃ continue to heat and stir for 0.5h to form a transparent and clear hydrophobic composition M34.

Example 35: Place the ceramic tray containing menthol in an oven at 100°C for 2h, take it out and cool it to room temperature in a glass desiccator, accurately weigh 44g of dried menthol and place it in a 250mL four-necked flask, and then put it in 56g silicone polyether {HO(CH ₃ CHCH ₂ O) ₂₅ (CH ₂ CH ₂ O) ₆ CH ₂ CH ₂ CH ₂ Si(Me) ₂ O)((Me) ₂ SiO) ₃₅ {(Me(CH ₂ CH ₂ CH ₂ (OCH ₂ CH ₂ ) ₆ (OCH ₃ CHCH ₃ ) ₂₅ OH)SiO) ₁₂ {HO(CH ₃ CHCH ₂ O) ₂₅ (CH ₂ CH ₂ O) ₆ CH ₂ CH ₂ CH ₂ Si(Me) ₂ }, seal, heat and stir in a water bath at 75°C for 1.5 hours. After the system is transparent, continue to heat and stir at 75°C for 1 hour to form a transparent, clear and hydrophobic composition M35.

Example 36: Place the ceramic tray containing tetralauryl ammonium chloride in an oven at 105°C for 2 hours, take it out and cool it to room temperature in a glass desiccator, accurately weigh 18g of dried tetralauryl ammonium chloride and place it in Put into a 250mL four-necked flask, then put in 82g of hydroxy silicone oil HOMe ₂ Si(OSiMe ₂ ) ₅₅ OSiMe ₂ OH, seal it, keep it in a water bath at 60℃ and stir for 1h. After the system is transparent, keep it at 60℃ and stir for 1h to form a transparent and clear Hydrophobic composition M36.

Example 37: Place a ceramic tray containing polysiloxane quaternary ammonium salt MD ₃₀ (Me(CH ₂ CH ₂ CH ₂ (C ₈ H ₁₇ ) ₃ NCl) SiO) ₈ M in an oven at 105° C. and let stand for 1.5 hours , Take it out and cool to room temperature in a glass desiccator, accurately weigh 24g of dried polysiloxane quaternary ammonium salt MD ₃₀ (Me(CH ₂ CH ₂ CH ₂ (C ₈ H ₁₇ ) ₃ NCl)SiO) ₈ M Put 76g of hydroxy silicone oil HOMe ₂ Si(OSiMe ₂ ) ₄₅ OSiMe ₂ OH into a 250mL four-necked flask, seal it, keep it in a water bath at 60℃ and stir for 1h. After the system is transparent, keep it at 60℃ and stir for 1h to form a transparent Clarifies the hydrophobic composition M37.

Example 38: Put a _{ceramic tray containing (CH 3} CH ₂ ) ₂ N-CH ₂ -CO-NH-{Ph(CH ₃ ) ₂ } in an oven at 102°C for 2.5 hours, then take it out and place it in a glass desiccator Cool to room temperature, accurately weigh 20g of dried (CH ₃ CH ₂ ) ₂ N-CH ₂ -CO-NH-{Ph(CH ₃ ) ₂ } into a 250mL four-necked flask, and then put in 80g of hydroxy silicone oil HOMe ₂ Si(OSiMe ₂ ) ₂₅ OSiMe ₂ OH, sealed, kept in a water bath at 35° C. and stirred for 1.5 h. After the system is transparent, the system was kept at 35° C. and stirred for 1.5 h to form a transparent, clear and hydrophobic composition M38.

Example 39: Place the ceramic tray containing Tetralauryl Ammonium Chloride in an oven at 105°C for 2h, take it out and cool it to room temperature in a glass desiccator, accurately weigh 18g of the dried Tetralauryl Ammonium Chloride and place it in Put into a 250mL four-necked flask, then put 82g of hydroxy silicone oil HOMe ₂ Si(OSiMe ₂ ) ₁₀ OSiMe ₂ OH, seal it, keep it in a water bath at 60℃ and stir for 1h. After the system is transparent, keep it warm and stir for 1h at 60℃ to form a transparent and clear Hydrophobic composition M39.

Example 40: Place a ceramic tray containing polysiloxane quaternary ammonium salt MD ₃₀ (Me(CH ₂ CH ₂ CH ₂ (C ₈ H ₁₇ ) ₃ NCl) SiO) ₈ M in an oven at 105° C. and let stand for 1.5 hours , Take it out and cool to room temperature in a glass desiccator, accurately weigh 24g of dried polysiloxane quaternary ammonium salt MD ₃₀ (Me(CH ₂ CH ₂ CH ₂ (C ₈ H ₁₇ ) ₃ NCl)SiO) ₈ M Put 76g of hydroxy silicone oil HOMe ₂ Si(OSiMe ₂ ) ₁₀₀ OSiMe ₂ OH into a 250mL four-necked flask, seal it, keep it in a water bath at 60℃ and stir for 1h. After the system is transparent, keep it at 60℃ and stir for 1h to form a transparent Clarifies the hydrophobic composition M40.

Example 41: Put _{the ceramic tray containing (CH 3} CH ₂ ) ₂ N-CH ₂ -CO-NH-{Ph(CH ₃ ) ₂ } in an oven at 102°C for 2.5 hours, then take it out and place it in a glass desiccator Cool to room temperature, accurately weigh 20g of dried (CH ₃ CH ₂ ) ₂ N-CH ₂ -CO-NH-{Ph(CH ₃ ) ₂ } into a 250mL four-necked flask, and then put in 80g of hydroxy silicone oil HOMe ₂ Si(OSiMe ₂ ) ₈₀ OSiMe ₂ OH, sealed, kept in a water bath at 35° C. and stirred for 1.5 hours. After the system became transparent, the system was kept warm and stirred for 1.5 hours at 35° C. to form a transparent, clear and hydrophobic composition M41.

Example 42: Place the ceramic tray containing Tetralauryl Ammonium Chloride in an oven at 105°C for 2 hours, take it out and cool it to room temperature in a glass desiccator, accurately weigh 18g of the dried Tetralauryl Ammonium Chloride and place it in Put into a 250mL four-necked flask, then put in 82g of hydroxy silicone oil HOMe ₂ Si(OSiMe ₂ ) ₁₅ OSiMe ₂ OH, seal it, keep it in a water bath at 60℃ and stir for 1h. After the system is transparent, keep it warm and stir for 1h at 60℃ to form a transparent and clear Hydrophobic composition M42.

Application Example 1—Apply to defoamer; prepare hydrophobic composition M1 using the method of Example 1, refer to the standard GB/T 26527-2011 to test the defoaming performance of hydrophobic composition M1; the results obtained are shown in Figure 6 .

Application Example 2—Apply to chemical reactions as an organic solvent; use the method of Example 3 to prepare the hydrophobic composition M3 as an organic solvent for chemical reactions, and refer to the method of Example 1 of patent CN104059232A to prepare acetylated modified lignosulfonate; The results obtained are shown in Figure 6.

Application Example 3—Apply to chemical separation as an extractant: use the method of Example 4 to prepare the hydrophobic composition M4 as an extractant for diesel desulfurization. Refer to the method in Example 2 of Patent CN104593056A for experimentation and testing; the results obtained As shown in Figure 6.

Comparative Example 1—Example 1: The ceramic tray containing tetraoctylammonium bromide was placed in an oven at 100°C for 3 hours, and then placed in a glass desiccator to cool to room temperature, and 50g of dried tetraoctylammonium bromide was accurately weighed. Put the base ammonium bromide in a 250mL four-necked flask, then put in 50g of octanol, seal it, keep it in a water bath at 90℃ and stir for 0.5h. After the system is transparent, keep it at 90℃ and stir for 0.5h to form a transparent, clear and hydrophobic composition. M43.

Comparative Example 2—Comparative Example of Example 4: Place the ceramic tray containing tetraoctadecylammonium chloride in an oven at 110°C for 1 hour, take it out and cool it to room temperature in a glass desiccator, and accurately weigh 40g of dried 48g Put the alkyl ammonium chloride in a 250mL four-necked flask, then put in 60g of lauric acid, seal it, keep it in a water bath at 20℃ and stir for 1.5h. After the system is transparent, keep heating and stirring at 20℃ for 1.5h to form a transparent, clear and hydrophobic combination物M44.

Comparative Example 3—Comparative Example of Example 8: Place the ceramic tray containing choline chloride in an oven at 100°C for 3 hours, take it out and cool it to room temperature in a glass desiccator, and accurately weigh 50g of the dried choline chloride The base was placed in a 250mL four-necked flask, then 50g of glycerin was put into it, sealed, and kept in a water bath at 90°C and stirred for 0.5h. After the system became transparent, the mixture was kept kept at 90°C and stirred for 0.5h to form a transparent, clear hydrophobic composition M45.

Comparative Example 4—Comparative Example of Example 17: Place the ceramic tray containing benzyltriethylammonium chloride in an oven at 100°C for 3 hours, take it out and cool it to room temperature in a glass desiccator, and accurately weigh 50g after drying Place the benzyltriethylammonium chloride in a 250mL four-necked flask, then put 50g of ethylene glycol, seal it, and keep it in a water bath at 90℃ and stir for 0.5h. When the system is transparent, keep it at 90℃ and stir for 0.5h to form a A transparent and clear hydrophobic composition M46.

Comparative Example 6—Comparative Example of Example 27: Place the ceramic tray containing methyltributylammonium chloride in an oven at 102°C for 2.5h, take it out and cool it to room temperature in a glass desiccator, and accurately weigh 20g to dry The latter methyl tributyl ammonium chloride was placed in a 250mL four-necked flask, and then 80g of acetamide was put into it, sealed, and kept in a water bath at 35°C and stirred for 1.5h. After the system became transparent, kept at 30°C and stirred for 1.5h to form a A transparent and clear hydrophobic composition M47.

Comparative Example 7—Comparative Example of Example 33: _{The ceramic tray containing MD 10} (Me(CH ₂ CH ₂ CH ₂ (CH ₃ ) ₃ NCl)SiO)M was placed in an oven at 100°C and allowed to stand for 3 hours. The glass desiccator was cooled to room temperature, accurately weighed 30g of dried MD ₁₀ (Me(CH ₃ CHCH2(CH ₃ ) ₃ NCl)SiO)M into a 250mL four-necked flask, and then put 70g of urea, sealed, Heat and stir in a water bath at °C for 0.5h. After the system is transparent, continue to heat and stir at 90 °C for 0.5h to form a transparent, clear and hydrophobic composition M48.

Comparative Example 8—Comparative Example of Example 39: _{A ceramic tray containing MD 50} (Me(CH ₂ CH ₂ CH ₂ (CH ₃ ) ₂ (C ₂ H ₅ )NCl) SiO) ₂₀ M was placed at 105°C Let the oven stand for 1h, take it out and cool it to room temperature in a glass desiccator, accurately weigh 18g of dried MD ₅₀ (Me(CH ₃ CHCH2(CH ₃ ) ₃ NCl) ₅ SiO)M into a 250mL four-necked flask, then Put in 82 g of sorbitol, seal it, keep it in a water bath at 60°C and stir for 1 hour. After the system is transparent, continue to keep it at 60°C and stir for 1 hour to form a transparent, clear and hydrophobic composition M49.

Comparative Example 9—Comparative Example of Example 41: _{A ceramic tray containing MD 100} (Me(CH ₂ CH ₂ CH ₂ (C ₈ H ₁₇ ) ₃ NCl)SiO) ₁₀ M was placed in an oven at 102° C. and allowed to stand for 2.5 hours Take it out and cool it to room temperature in a glass desiccator, accurately weigh 20g of dried MD ₁₀₀ (Me(CH ₃ CHCH2(C ₈ H ₁₇ ) ₅ NCl) ₁₀ SiO)M into a 250mL four-necked flask, and then put in 80g The catechol was sealed and kept in a water bath at 35°C and stirred for 1.5h. After the system became transparent, the system was kept at 35°C and kept stirring for 1.5h to form a transparent, clear and hydrophobic composition M50.

Comparative Example 10—Comparative Example of Example 35: Place the ceramic tray containing tetraoctadecylammonium chloride in an oven at 105°C for 2h, take it out and cool it to room temperature in a glass desiccator, and accurately weigh 56g of dried 48g Alkylammonium chloride was placed in a 250mL four-necked flask, then 44g of malonic acid was put into it, sealed, and kept in a water bath at 40℃ and stirred for 1.5h. After the system became transparent, it was kept at 40℃ and stirred for 1h to form a transparent, clear and hydrophobic Liquid M51.

Comparative Example 11: M52 was prepared with reference to patent CN101560187A (prepared by imidazole and tetrabutylammonium bromide).

Comparative Example 12: M53 (prepared by choline chloride and malic acid) was prepared with reference to patent CN106435672A.

Comparative Example 13: Refer to patent CN104059232A to prepare M54 (choline chloride and acetic anhydride preparation).

Comparative Example 14: M55 (prepared by choline chloride and salicylic acid) was prepared with reference to patent CN106928055A.

Comparative Example 16—Comparative example of hydrogen bond acceptor dosage, corresponding to Example 24

Place the ceramic tray containing (CH ₃ CH ₂ ) ₂ N-CH ₂ -CO-NH-{Ph(CH ₃ ) ₂ } in an oven at 102°C for 2.5 hours, take it out and cool it to room temperature in a glass desiccator, Accurately weigh 16g of dried (CH ₃ CH ₂ ) ₂ N-CH ₂ -CO-NH-{Ph(CH ₃ ) ₂ } into a 250mL four-neck flask, and then put 84g of hydroxy silicone oil HOMe ₂ Si(OSiMe ₂ ) ₃₅ OSiMe ₂ OH, sealed, kept in a water bath at 35°C and stirred for 1.5h. After the system is transparent, continue to keep holding and stirring at 35°C for 1.5h to form a turbid composition M56.

Comparative Example 17—Comparative example of the amount of hydrogen bond acceptor, corresponding to Example 30

Place the ceramic tray containing tetraoctylammonium bromide in an oven at 100℃ for 3h, take it out and cool it to room temperature in a glass desiccator, accurately weigh 55g of dried tetraoctylammonium bromide and place it in a 250mL four-neck flask And then put 45g of silicone polyether {HO(CH ₃ CHCH ₂ O) ₁₅ (CH ₂ CH ₂ O) ₈ CH ₂ CH ₂ CH ₂ Si(Me) ₂ O}((Me) ₂ SiO) ₄₅ {HO( CH ₃ CHCH ₂ O) ₁₅ (CH ₂ CH ₂ O) ₈ CH ₂ CH ₂ CH ₂ Si(Me) ₂ }, sealed, kept in a water bath at 90°C and stirred for 0.5h, until the system is transparent, continue to keep holding and stirring at 90°C for 0.5 h, a turbid composition M57 is formed.

Comparative Example 18—Comparative Example of Synthesis Temperature, Corresponding to Example 36

Place the ceramic tray containing Tetralauryl Ammonium Chloride in an oven at 105°C for 2 hours, take it out and cool it to room temperature in a glass desiccator, accurately weigh out 18g of the dried Tetralauryl Ammonium Chloride and place it in a 250mL four-neck flask Then put in 82g of hydroxy silicone oil HOMe ₂ Si(OSiMe ₂ ) ₅₅ OSiMe ₂ OH, seal it, keep it in a water bath at 15℃ and stir for 1h. After the system is transparent, keep it at 15℃ and stir for 1h to form a solid-liquid mixed composition M58 .

Comparative Example 19—Comparative Example of Synthesis Temperature, Corresponding to Example 4

Place the ceramic tray containing tetraoctadecylammonium chloride in an oven at 110℃ for 1h, take it out and cool it to room temperature in a glass desiccator, accurately weigh 40g of dried tetraoctadecylammonium chloride and place it in a 250mL four-neck flask Then put in 60g of hydroxy silicone oil HOMe ₂ Si(OSiMe ₂ ) ₆₀ OSiMe ₂ OH, seal, heat and stir in a water bath at 95°C for 1.5h. After the system is transparent, continue to heat and stir at 95°C for 1.5h to form a clear hydrophobic composition M59.

Application of comparative example 1-for defoaming agent: use the method of comparative example 1 to prepare the hydrophobic composition M43, refer to the standard GB/T 26527-2011 to test the anti-foaming performance of the hydrophobic composition M43; the results are shown in Figure 6 .

Application Comparative Example 2—Apply to a chemical reaction as an organic solvent: After referring to the hydrophobic composition in Example 1 of the patent CN104059232A, the hydrophobic composition is used to prepare the acetylated modified lignosulfonate; the results obtained are shown in the figure 6 shown.

Application Comparison 3—Apply to chemical separation as an extractant: refer to the method in Example 2 of Patent CN104593056A to prepare a hydrophobic composition, and then use it for diesel desulfurization and test the desulfurization rate; the results obtained are shown in FIG. 6.

It should be noted that the above are only preferred embodiments of the present invention and are not used to limit the scope of protection of the present invention. Any combination or equivalent transformation made on the basis of the above embodiments belongs to the scope of protection of the present invention.

Claims (17)

1. A new type of hydrophobic composition composed of hydrogen bond acceptor A and hydrogen bond donor B, characterized in that the hydrogen bond acceptor A is selected from quaternary ammonium salts, polysiloxane quaternary ammonium salts, monoterpene alcohols A mixture of one or more of the compound and amide compound, and the hydrogen bond donor B is selected from one or more of polyether, silicone polyether, and hydroxy silicone oil;

   The general structural formula I of the quaternary ammonium salt is as follows:

   R ¹ R ² R ³ R ⁴ NR ⁵ Ⅰ

   In the general formula I, R ^{1 is} selected from linear alkyl groups having 1 to 18 carbon atoms,

   R ² , R ³ , and R ^{4 are} selected from linear alkyl groups having 4 to 18 carbon atoms,

   R ^{5 is} selected from Cl or Br;

   The general formula II of the polysiloxane quaternary ammonium salt is as follows:

   MD _a (MeRSiO) _b M Ⅱ

   In the general formula II, M is the chain link Me ₃ SiO _1/2 , and D is the chain link Me ₂ SiO _2/2 ,

   Me is a methyl group, a is an integer of 10-100, and b is an integer of 1-20;

   R is a quaternary ammonium salt group II—I, and its general structure is as follows:

   -CH ₂ CH ₂ CH ₂ R ⁶ R ⁷ R ⁸ NCl Ⅱ—Ⅰ

   In the general formula II-I, R ⁶ , R ⁷ , and R ^{8 are} selected from linear alkyl groups having 1 to 8 carbon atoms;

   Monoterpene alcohol compounds are monocyclic monoterpene alcohol compounds, selected from the group consisting of menthol, terpineol, perillyl alcohol, and carvolamide. The structural formula III is as follows:

   R ⁹ —NH—CO—R ¹⁰ Ⅲ

   Wherein R ⁹ and R ^{10 are the} same or different, and are selected from linear alkyl, branched alkyl, aminoalkyl, cycloalkyl, and aralkyl having 1 to 8 carbon atoms;

   The general structural formula IV of polyether is as follows:

   R ¹¹ (OCH ₂ CH ₂ ) _m (OCH ₂ CHCH ₃ ) _n OH Ⅳ

   In the general formula IV, R ¹¹ is a straight or branched chain alkyl group, alkene group, or a cycloalkyl group with a carbon number of 1 to 6,

   m is an integer of 1-50, n is an integer of 10-100;

   The general formula V of the silicone polyether structure is as follows:

   

   In the general structural formula V, Me is a methyl group,

   x and y are the degree of polymerization, x is an integer from 1 to 100, and y is an integer from 1 to 50,

   P is selected from methyl and polyether groups, at least one P is a polyether group, and the general structure of the polyether group V-I is as follows:

   -CH ₂ CH ₂ CH ₂ (OCH ₂ CH ₂ ) _c (OCH ₂ CHCH ₃ ) _d OH Ⅴ—Ⅰ

   In the general structural formula V-I, c and d are the degree of polymerization, c is an integer from 1 to 10, and d is an integer from 10 to 50; the general structural formula of hydroxy silicone oil is as follows:

   HOMe ₂ Si(OSiMe ₂ ) _e OSiMe ₂ OH Ⅵ

   In the general structural formula VI, Me is a methyl group, and e is an integer from 10 to 100.
2. The novel hydrophobic composition according to claim 1, wherein the amount of hydrogen bond acceptor A in the novel hydrophobic composition is 17%-50% of the total mass of the novel hydrophobic composition, and the hydrogen bond donor The amount of B is 50% to 83% of the total mass of the new hydrophobic composition.
3. The novel hydrophobic composition according to claim 1, wherein in the novel hydrophobic composition, when the hydrogen bond acceptor A is a single substance, quaternary ammonium salts and polysiloxane quaternary ammonium salts are preferred.
4. The novel hydrophobic composition according to claim 3, wherein in the novel hydrophobic composition, when the hydrogen bond acceptor A is a single substance, a quaternary ammonium salt is preferred.
5. The novel hydrophobic composition according to claim 1, wherein in the novel hydrophobic composition, when the hydrogen bond donor B is a single substance, hydroxy silicone oil and silicone polyether are preferred.
6. The novel hydrophobic composition according to claim 5, wherein in the novel hydrophobic composition, when the hydrogen bond donor B is a single substance, hydroxy silicone oil is preferred.
7. The novel hydrophobic composition according to claim 1, wherein R ¹ in the quaternary ammonium salt is preferably a linear alkyl group having 8 to 18 carbon atoms.
8. The novel hydrophobic composition of claim 1, wherein R ² , R ³ , and R ⁴ in the quaternary ammonium salt are preferably linear alkyl groups having 8 to 18 carbon atoms.
9. The novel hydrophobic composition according to claim 1, wherein the ^{carbon number of R 9} and R ¹⁰ in the amide compound is preferably 4 to 8.
10. The novel hydrophobic composition according to claim 1, wherein, in the general formula V of the siloxane polyether structure, x is preferably an integer of 10-40, and y is preferably an integer of 10-20.
11. The novel hydrophobic composition according to claim 1, wherein in the general formula of the polyether structure, m is preferably an integer of 2-10, and n is preferably an integer of 15-50.
12. The novel hydrophobic composition according to claim 1, wherein in the general formula of the hydroxyl structure, e is preferably an integer of 20-60.
13. A preparation method of the novel hydrophobic composition according to claim 1, wherein the preparation method is as follows:

    1) Put the hydrogen bond acceptor A in an oven at 100～110℃ for 1～3h to remove the water in the system;

    2) Mix and seal the hydrogen bond acceptor A and the hydrogen bond donor B from which moisture has been removed, and stir in a water bath for 0.5 to 2 hours until the mixture system is completely transparent;

    3) After the heat preservation is continued for 0.5 to 1.5 hours, a transparent, clear and hydrophobic composition is obtained.
14. The preparation method of the novel hydrophobic composition according to claim 1, wherein the temperature of the water bath in said step 2) and step 3) is 20-90°C.
15. The use of the novel hydrophobic composition of claim 1 in the preparation of defoamers.
16. The novel hydrophobic composition according to claim 1 is applied to a chemical reaction process as a reaction medium instead of traditional organic solvents.
17. The novel hydrophobic composition according to claim 1 is applied to the separation process in synthetic chemistry as an extractant.

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