阅读说明：本技术 一种新型疏水组合物 (Novel hydrophobic composition ) 是由 董飞 黄伟 安东尼·K·达西 曹添 于 2018-06-11 设计创作，主要内容包括：本发明公开了一种新型疏水组合物,由氢键受体A与氢键供体B组合而成,其特征在于,氢键受体A选自季铵盐、聚硅氧烷季铵盐、单萜醇类化合物、酰胺类化合物中的一种或多种的混合物,氢键供体B选自聚醚、硅聚醚、羟基硅油中的一种或多种的混合物；本发明的新型疏水组合物具有表面张力低、疏水程度高、粘度范围广、选择性好、外观透明易于后续应用的优点,可以广泛的应用于工业生产过程中,作为萃取剂、无机材料合成用溶剂、消泡剂行业等。(The invention discloses a novel hydrophobic composition, which is formed by combining a hydrogen bond acceptor A and a hydrogen bond donor B, and is characterized in that the hydrogen bond acceptor A is selected from one or a mixture of more of quaternary ammonium salt, polysiloxane quaternary ammonium salt, monoterpene alcohol compounds and amide compounds, and the hydrogen bond donor B is selected from one or a mixture of more of polyether, silicon polyether and hydroxyl silicone oil; the novel hydrophobic composition has the advantages of low surface tension, high hydrophobic degree, wide viscosity range, good selectivity, transparent appearance and easy subsequent application, and can be widely applied to industrial production processes as an extracting agent, a solvent for inorganic material synthesis, a defoaming agent industry and the like.)

1. a novel hydrophobic composition is formed by combining a hydrogen bond acceptor A and a hydrogen bond donor B, and is characterized in that the hydrogen bond acceptor A is selected from one or a mixture of more of quaternary ammonium salt, polysiloxane quaternary ammonium salt, monoterpene alcohol compounds and amide compounds, and the hydrogen bond donor B is selected from one or a mixture of more of polyether, silicon polyether and hydroxyl silicone oil;

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

R¹R²R³R⁴NR⁵ Ⅰ

In the general structural formula I, R¹Selected from linear alkyl groups having a carbon number of 1 to 18,

R²、R³、R⁴selected from linear alkyl groups having a carbon number of from 4 to 18,

R⁵Selected from Cl or Br;

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

MD_a(MeRSiO)_bM Ⅱ

in the general formula II, M is chain link Me₃SiO_1/2D is a chain link Me₂SiO_2/2，

Me is methyl, 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 the structural formula is as follows:

-CH₂CH₂CH₂R⁶R⁷R⁸NCl Ⅱ—Ⅰ

General structural formula II-IIn, R⁶、R⁷、R⁸Selected from linear alkyl groups having a carbon number of 1 to 8;

The monoterpene alcohol compound is monocyclic monoterpene alcohol compound selected from menthol, terpineol, perillyl alcohol, and carveol

The amide-based substances have the following structural formula III:

R⁹—NH—CO—R¹⁰ Ⅲ，

wherein R is⁹、R¹⁰The same or different, selected from linear alkyl, branched alkyl, aminoalkyl, cycloalkyl, aralkyl with carbon number of 1 to 8; the structural general formula IV of the polyether is as follows:

R¹¹(OCH₂CH₂)_m(OCH₂CHCH₃)_nOH Ⅳ

In the general structural formula IV, R¹¹Is a straight chain or branched alkyl group with a carbon number of 1-6, an alkenyl group, a cycloalkyl group,

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

The structural general formula V of the silicon polyether is as follows:

In the general structural formula V, Me is methyl,

x and y are polymerization degrees, x is an integer of 1 to 100, y is an integer of 1 to 50,

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

-CH₂CH₂CH₂(OCH₂CH₂)_c(OCH₂CHCH₃)_dOH Ⅴ—Ⅰ

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

the general structural formula VI of the hydroxyl silicone oil is as follows:

HOMe₂Si(OSiMe₂)_eOSi Me₂OH Ⅵ

In the general structural formula VI, Me is methyl, and e is an integer of 10-100.

2. The novel hydrophobic composition of claim 1 wherein the hydrogen bond acceptor a is present in an amount of 17% to 50% and the hydrogen bond donor B is present in an amount of 50% to 83% of the total mass of the novel hydrophobic composition.

3. The novel hydrophobic composition of claim 1 wherein the hydrogen bond acceptor a is a single species, preferably a quaternary ammonium salt and a polysiloxane quaternary ammonium salt.

4. The novel hydrophobic composition of claim 3 wherein the hydrogen bond acceptor A is a single species, preferably a quaternary ammonium salt.

5. The novel hydrophobic composition of claim 1 wherein the hydrogen bond donor B is a single species, preferably a hydroxy silicone oil and a silicone polyether.

6. The novel hydrophobic composition of claim 5 wherein the hydrogen bond donor B is a single species, preferably a hydroxy silicone oil.

7. the hydrophobic composition of claim 1 wherein R is in the quaternary ammonium salt¹Linear alkyl groups having a carbon number of 8 to 18 are preferred.

8. The hydrophobic composition of claim 1 wherein R is in the quaternary ammonium salt²、R³、R⁴Linear alkyl groups having a carbon number of 8 to 18 are preferred.

9. The novel hydrophobic composition of claim 1,In the amide compound, R⁹、R¹⁰The carbon number is preferably 4 to 8.

10. The novel hydrophobic composition as claimed in claim 1, wherein in the general structural formula V of the silicon polyether, x is preferably an integer of 10 to 40, and y is preferably an integer of 10 to 20.

11. The novel hydrophobic composition of claim 1 wherein in the general polyether structure, m is preferably an integer from 2 to 10 and n is preferably an integer from 15 to 50.

12. The novel hydrophobic composition of claim 1 wherein in the general formula of the hydroxyl group, e is preferably an integer from 20 to 60.

13. A process for the preparation of the novel hydrophobic composition according to claim 1, characterized in that it comprises the following steps:

1) Standing the hydrogen bond acceptor A in an oven at 100-110 ℃ for 1-3 h, and removing water in the system;

2) Mixing and sealing the hydrogen bond acceptor A without water and the hydrogen bond donor B, keeping the temperature in a water bath, stirring for 0.5-2 h, and reacting until a mixture system is completely transparent;

3) and keeping the temperature for 0.5-1.5 h to obtain the transparent clear hydrophobic composition.

14. The method for preparing the novel hydrophobic composition according to claim 1, wherein the temperature of the water bath in the step 2) and the step 3) is 20 to 90 ℃.

15. Use of the novel hydrophobic composition as claimed in claim 1 for the preparation of defoamers.

16. the novel hydrophobic composition of claim 1 applied to a chemical reaction process as a reaction medium to replace traditional organic solvents.

17. The novel hydrophobic composition of claim 1 applied to separation processes in synthetic chemistry as an extractant.

Technical Field

The 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 through hydrogen bond acting force.

Background

The hydrogen bond receptor refers to a component for accepting hydrogen bonds, and mainly comprises quaternary ammonium salt (such as choline chloride), zwitterion (such as betaine) and the like; the hydrogen bond donor refers to a component which provides a hydrogen bond, and mainly includes urea, thiourea, carboxylic acids (phenylacetic acid, malic acid, citric acid, succinic acid, etc.), polyols (ethylene glycol, glycerol, butylene glycol, xylitol, etc.), amino acids, saccharides (glucose, fructose) trifluoroacetamide, and the like.

Most of the compositions combined by hydrogen bond acceptor and hydrogen bond donor are hydrophilic, and the compositions are mainly combined by hydrophilic hydrogen bond acceptor and hydrophilic hydrogen bond donor.

for example, CN103193711 introduces an ionic liquid with negative monovalent halogen as anion and a transition metal halide salt as hydrogen bond acceptor, and a multi-hydrogen bond compound (one or more of acetamide, N-methylurea, N' -dimethylurea, N-dimethylurea, urea, thiourea, caprolactam, benzamide, trifluoroacetamide, ethylene glycol, glycerol, xylitol, sorbitol, catechol, resorcinol, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, malic acid, tartaric acid, citric acid, tetracetic acid, phthalic acid, and isophthalic acid) as hydrogen bond donor.

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

CN106567110A describes that a composition is obtained by uniformly mixing a quaternary ammonium salt and a polyol.

CN106435672A describes a composition prepared based on choline chloride and malic acid.

CN106119815A describes a composition prepared from quaternary ammonium salt, urea, acetamide, glycol and glycerol. CN104059232A describes a composition prepared using acetic anhydride and choline chloride.

CN104596056A describes a method for preparing a composition by reacting a quaternary ammonium compound with a mixture of dicarboxylic acids.

CN103752132A describes a composition prepared by using quaternary ammonium salt (choline chloride) and hydrogen bonding matrix compound (phenol, butylene glycol, propylene glycol, diethylene glycol, triethylene glycol).

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

CN105367074A describes a composition prepared by using quaternary ammonium salt ionic liquid, absolute ethyl alcohol and isohexane glycol.

US2009247432(a1) describes the preparation of compositions using quaternary ammonium salts and amides, alcohols. Such hydrogen bonded compositions are also hydrophobic.

Osch D J G P V, Zubeir L F, Bruinhorst A V D, et al hydrophobic Deep Euprotective Solvents [ J ] Green Chemistry 2015,17(9):4518-4521 is the first article to describe such hydrophobic compositions prepared using methyltrioctylammonium chloride, methyltrioctylammonium bromide, tetrabutylammonium chloride, etc. with capric acid.

Ribeiro B D, Florindo C, Iff L C, et al, menthol-based European Mixtures hydrobic Low Viscosities Solvents [ J ]. Acs Sustainable Chemistry & Engineering,2015,3(10):150910100559005. Hydrophobic Low Viscosity compositions prepared with menthol with acetic acid, lauric acid, etc. are described.

Hydrophotobic Deep eukaryotic solvent pro show in large paper index more stable September 19,2016 describes the preparation of such Hydrophobic compositions using varying ratios of capric acid and lidocaine.

terreshatov E E, Boltoeva M Y, Folden C M.First evidence of metal transfer in hydrophic deputyic and low-transfer-temporal compositions of iron (II) extraction from hydrochloric and oxyacid [ J ] Green Chemistry,2016,18(17):4616-4622. the use of tetraheptylammonium chloride, menthol and lauric acid, capric acid, oleic acid, ibuprofen (ibuprofen) is described for the preparation of such hydrophobic compositions.

Cao J, Yang M, Cao F, et al, Tailor-large hydrophilic hydrophobic solutions for purifying acids from Ginko Biloba, leaves [ J ]. Journal of Cleaner Production,2017,152: 399-.

The hydrophobic compositions have the advantages of large surface tension, limited hydrophobic degree and small viscosity range, and the appearance is mostly light yellow to brown, thereby influencing the effect and range of subsequent application of the hydrophobic compositions.

Disclosure of Invention

In view of the above problems, the present invention is directed to a novel hydrophobic composition comprising a quaternary ammonium salt and a derivative thereof and a hydrogen bond-containing polymer bonded by hydrogen bonding force, and a method for preparing the same.

In order to achieve the purpose, the technical scheme adopted by the invention is as follows: a novel hydrophobic composition is formed by combining a hydrogen bond acceptor A and a hydrogen bond donor B, wherein the hydrogen bond acceptor A is selected from one or a mixture of more of quaternary ammonium salt, polysiloxane quaternary ammonium salt, monoterpene alcohol compounds and amide compounds, and the hydrogen bond donor B is selected from one or a mixture of more of polyether, silicon polyether and hydroxyl silicone oil.

The quaternary ammonium salt in the composition has the following structural general formula I:

R¹R²R³R⁴NR ⁵Ⅰ

In the general formula I, R¹Selected from linear alkyl groups having a carbon number of 1 to 18, R²、R³、R⁴Selected from linear alkyl groups having a carbon number of from 4 to 18, R⁵Selected from Cl or Br.

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

MD_a(MeRSiO)_bM Ⅱ

In the general formula II, M is chain link Me₃SiO_1/2D is a chain link Me₂SiO_2/2Me is methyl, 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 the structural formula is as follows:

-CH₂CH₂CH₂R⁶R⁷R⁸NCl Ⅱ—Ⅰ

Structural general formula IIIn I, R⁶、R⁷、R⁸Selected from linear alkyl groups having a carbon number of 1 to 8.

The monoterpene alcohol compound in the invention is a monocyclic monoterpene alcohol compound, and is selected from menthol, terpineol, perillyl alcohol and carveol.

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

R⁹—NH—CO—R¹⁰ Ⅲ

Wherein R is⁹、R¹0 are the same or different and are selected from linear alkyl, branched alkyl, aminoalkyl, cycloalkyl, aralkyl groups having a carbon number of 1 to 8.

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

R⁹(OCH₂CH₂)_m(OCH₂CHCH₃)_nOH Ⅳ

In the general structural formula IV, R⁹Is a straight chain or branched chain alkyl, alkenyl or cycloalkyl with 1-6 carbon atoms, m is an integer of 1-50, and n is an integer of 10-100.

The structural general formula V of the silicon polyether is as follows:

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

-CH₂CH₂CH₂(OCH₂CH₂)_c(OCH₂CHCH₃)_dOH Ⅴ—Ⅰ

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

The general structural formula VI of the hydroxyl silicone oil is as follows:

HOMe₂Si(OSiMe₂)_eOSi Me₂OH Ⅵ

In the general structural formula VI, Me is methyl, and e is an integer of 10-100.

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

In the novel hydrophobic composition, when the hydrogen bond acceptor A is a single substance, quaternary ammonium salt is preferred, polysiloxane quaternary ammonium salt is less preferred, and monoterpene alcohol compounds and amide compounds are less preferred.

In the novel hydrophobic composition, when the hydrogen bond donor B is a single substance, hydroxyl silicone oil is preferred, silicon polyether is less preferred, and polyether is less preferred.

In the quaternary ammonium salt of the invention, R¹Linear alkyl groups having a carbon number of 8 to 18 are preferred.

In the quaternary ammonium salt of the invention, R²、R³、R⁴Straight chain alkyl groups with a carbon number of 8 to 18 are preferred.

in the amide compound of the invention, R⁹、R¹⁰the carbon number is preferably 4 to 8;

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

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

In the general structural formula VI of the hydroxyl silicone oil, e is preferably an integer of 20-60.

The preparation method of the novel hydrophobic composition provided by the invention comprises the following steps:

1) Standing the hydrogen bond acceptor A in an oven at 100-110 ℃ for 1-3 h, and removing water in the system;

2) mixing and sealing the hydrogen bond acceptor A without water and the hydrogen bond donor B, keeping the temperature in a water bath, stirring for 0.5-2 h, and reacting until a mixture system is completely transparent;

3) And keeping the temperature for 0.5-1.5 h to obtain the transparent clear hydrophobic composition.

The temperature of the water bath heat preservation in the step 2) and the step 3) is 20-90 ℃, when the temperature is lower than 20 ℃, the preparation time of the composition is prolonged, and when the temperature is higher than 90 ℃, the appearance color of the composition becomes dark, which is not beneficial to subsequent application.

the novel hydrophobic composition can be directly applied to industrial production as an antifoaming agent, and can also be used as a synthetic raw material of the antifoaming agent, such as an emulsifier and a carrier of a mineral oil antifoaming agent.

The novel hydrophobic composition of the present invention can be applied to chemical reaction processes as a reaction medium to replace conventional organic solvents.

the novel hydrophobic compositions of the present invention can be applied to separation processes in synthetic chemistry as extractants.

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

Drawings

FIG. 1 is a graphical representation of the results of a surface tension test of a composition according to an embodiment of the present invention;

FIG. 2 is a graphical representation of the results of a water content test of a composition according to an embodiment of the present invention;

FIG. 3 is a graph showing the results of a water content test of an oil phase after mixing a composition with water in an embodiment of the present invention;

FIG. 4 is a graphical representation of the results of viscosity testing of compositions in accordance with an embodiment of the present invention;

FIG. 5 is a graph showing appearance results of compositions in examples of the present invention;

FIG. 6 is a graph showing the results of the application example in the embodiment of the present invention.

Wherein "- -" in FIGS. 2, 3, 4, 5 indicates that the formulation did not form a stable hydrophobic composition and could not be tested accordingly.

Detailed Description

The invention is described in further detail below with reference to the following description of the drawings and the detailed description.

Compared with the compositions of the same type, the novel hydrophobic composition prepared by the invention has low surface tension, high hydrophobic degree (low water content, low water content of oil phase after being mixed with water), good selectivity (wide viscosity range), colorless, transparent and clear appearance. Comparative tests were conducted as follows.

1. Surface tension test of the composition: the test was carried out using a BP100 dynamic surface tensiometer from KRUSS.

2. Testing the water content of the composition: testing using a karl fischer moisture meter;

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

Mixing 4g of the composition with 4g of distilled water, putting into a 10mL centrifuge tube, and rotating at 3000rpm for 30 min; the water content of the supernatant was measured using a karl fischer moisture meter.

4. Viscosity test of the composition: the viscosity was measured using a DV2TLVTJ0 viscometer from BROOKFIELD.

5. Composition appearance test: visual inspection was carried out.

The results of the performance tests are shown in fig. 1-5.

The application performance of the novel hydrophobic composition prepared by the invention is tested as follows:

1. The defoaming agent is applied to the defoaming agent industry, the defoaming and foam inhibiting performance is tested by referring to the national standard GB/T26527-2011, the defoaming and foam inhibiting performance is tested by a shaking bottle method in sodium dodecyl benzene sulfonate, and the lower the foam height is, the better the defoaming and foam inhibiting performance is.

2. when the method is applied to chemical reaction organic solvents, referring to the method of patent CN104059232A example 1, the higher the product yield, the better the application performance.

3. By using the chemical separation extractant, referring to the method in example 2 in patent CN104593056A, the higher the desulfurization rate is, the better the separation effect is.