CN109694472B - Functional polyether initiator, synthesis thereof and application thereof in polyether synthesis - Google Patents
Functional polyether initiator, synthesis thereof and application thereof in polyether synthesis Download PDFInfo
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- CN109694472B CN109694472B CN201811524831.3A CN201811524831A CN109694472B CN 109694472 B CN109694472 B CN 109694472B CN 201811524831 A CN201811524831 A CN 201811524831A CN 109694472 B CN109694472 B CN 109694472B
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2618—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen
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- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
- C07C209/78—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton from carbonyl compounds, e.g. from formaldehyde, and amines having amino groups bound to carbon atoms of six-membered aromatic rings, with formation of methylene-diarylamines
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C245/00—Compounds containing chains of at least two nitrogen atoms with at least one nitrogen-to-nitrogen multiple bond
- C07C245/02—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides
- C07C245/06—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides with nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings
- C07C245/08—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides with nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings with the two nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings, e.g. azobenzene
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- C10G33/00—Dewatering or demulsification of hydrocarbon oils
- C10G33/04—Dewatering or demulsification of hydrocarbon oils with chemical means
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/60—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing polyethers
- D06P1/607—Nitrogen-containing polyethers or their quaternary derivatives
Abstract
The invention discloses a functional polyether initiator, a synthesis method thereof and application thereof in polyether synthesis, belonging to the field of organic functional materials. The functional polyether initiator is novel multi-branched azobenzene polyether, and the main synthetic route comprises the synthesis of tetraphenylethane, the synthesis of p-nitrosobenzyl alcohol and the synthesis of tetra (4-hydroxymethyl azobenzene) ethane. The novel initiator is utilized to synthesize polyether with different structures, and the polyether has photoresponse performance and is expected to have wide application prospect in the fields of washing, demulsifying agents and the like.
Description
Technical Field
The invention relates to a functional polyether initiator, a synthesis method thereof and application thereof in polyether synthesis, belonging to the field of organic functional materials.
Background
With the development of artificial intelligence, people increasingly demand intelligent materials with functionality. The inherent advantages of the traditional material are maintained, and the new functionality and the corresponding property are endowed, so that the application of the material in the novel field is expanded.
The conventional polyether is generally obtained by polymerizing ethylene oxide or propylene oxide with different amounts by using aliphatic alcohol or aromatic alcohol as an initiator, and is widely applied in the fields of polyurethane synthesis, nonionic surfactants and the like. However, with the development of technology, the demand of downstream customers for special functional polyethers is increasing, and it is necessary to develop functional starters for polyether synthesis so as to impart new functionality to the product.
Azobenzene is an organic functional compound with photoisomerization performance, azobenzene molecules can be converted from a stable trans-structure into a metastable cis-structure under the irradiation of ultraviolet light, and can be returned from the cis-structure to the trans-structure under the conditions of darkness, visible light or heating. The change of the configuration of azobenzene can cause the change of the length, the energy and the like of molecules, thereby being reflected on the change of the ultraviolet absorption spectrum of the molecules. CN 107213843A reports a preparation method of azobenzene type nonionic surfactant, which changes the tightness degree of the arrangement of azobenzene molecules on the surface of a foam liquid film by utilizing the steric hindrance difference of cis-trans configuration through the photoisomerization of the azobenzene molecules, thereby realizing the effects of low concentration and high foam stability.
The multi-branched azobenzene polyalcohol is synthesized through molecular design and is used for polyether synthesis. Compared with the common polyether initiator, the molecule has photoresponse, and compared with the single-branch azobenzene molecule reported before, the photoresponse degree of the multi-branch structure molecule is higher and the speed is higher. The polyether polyol prepared based on the molecule has wide application prospects in the fields of washing, demulsifiers and the like, the existence of the photoresponsive molecule can be favorable for detecting the residual quantity of the polyether polyol in a solution, and the performance of a polyether product can be changed through illumination, so that the remote intelligent control is favorably realized.
Disclosure of Invention
In order to expand the application of polyether products in the field of intelligent response, a novel functional polyether initiator is synthesized and applied to polyether synthesis.
According to a first aspect of the present invention, there is provided a functional polyether initiator which is a novel hyperbranched azobenzene polyether having the following structural formula:
wherein, R is independently selected from hydrogen, halogen, C1-C4 alkyl, C1-4 alkoxy, C1-C4 acid group, preferably selected from F, Cl, Br, methyl, methoxy, carboxyl and the like, and n is an integer of 1-4.
The invention further provides a functional polyether, which has the following structural formula:
wherein, R is independently selected from hydrogen, halogen, C1-C4 alkyl, C1-4 alkoxy, C1-C4 acid group, preferably selected from F, Cl, Br, methyl, methoxy, carboxyl and the like, and n is an integer of 1-4.
a-0-200, b-0-200, at least one of a or b is not 0,
according to a third aspect of the present invention, there is provided a method for preparing the above functional polyether initiator, the method comprising:
(A) adding metered aniline or substituted aniline into a reaction kettle, adding acid to adjust the pH value of a system to be 1-6, replacing with nitrogen, adding glyoxal into the reaction kettle at the reaction temperature of 60-100 ℃ to react, neutralizing to be neutral, removing a solvent and unreacted aniline or substituted aniline in the system, cooling a solution after the solvent is removed to obtain a crude product of the tetra-aniline or substituted anilinoethane, and carrying out column chromatography separation and purification on the crude product to obtain the tetra-aniline or substituted anilinoethane;
(B) reacting 4-aminobenzyl alcohol or 4-amino R substituent benzyl alcohol with Oxone (Oxone) under the protection of nitrogen, filtering and washing a precipitate after the reaction, and drying to obtain p-nitroso benzyl alcohol or p-nitroso R substituent benzyl alcohol;
(C) reacting tetraphenylethane or tetra-substituted anilinoethane with p-nitrosobenzyl alcohol or p-nitrosoR substituted benzyl alcohol under the protection of nitrogen, adding water (such as distilled water) into the system after the reaction is finished to precipitate, filtering, collecting a filter cake, washing, drying in vacuum to obtain a crude product of tetra (4-hydroxymethyl azobenzene) ethane with different substituents, and carrying out column chromatography separation and purification on the crude product to obtain the tetra (4-hydroxymethyl azobenzene) ethane compounds with different substituents.
According to a fourth aspect of the present invention, there is provided a method for producing a functional polyether, further comprising, after the above steps (a) to (C):
(D) reacting tetra (4-hydroxymethyl azobenzene) ethane compounds with different substituents with ethylene oxide and/or propylene oxide in the presence of a catalyst.
The reaction of step (a) may be carried out in the presence of a solvent, preferably one or more of methanol, ethanol, t-butanol, toluene and the like, preferably methanol, and the amount of the solvent may be 0.2 to 2 times, preferably 0.33 to 0.5 times the amount of aniline used.
In step (a) of the above preparation method, the molar ratio of aniline or substituted aniline to glyoxal may be 1: 0.1-0.25, preferably 0.15-0.2.
In step (B), the molar ratio of 4-aminobenzyl alcohol or 4-amino R substituent benzyl alcohol to oxone complex salt may be 1: 2 to 4, preferably 2.2 to 2.5.
In step (C), the molar ratio of tetraphenylethane or tetrasubstituted anilinoethane to p-nitrosobenzyl alcohol or p-nitrosor substituted benzyl alcohol may be 1: 2-10, preferably 1: 4-4.5.
In the step (D), the mass ratio of the tetra (4-hydroxymethylazobenzene) ethane compound with different substituents to the ethylene oxide and/or propylene oxide may be 1: 1-20, preferably 1: 8-12. The ratio of ethylene oxide to propylene oxide may be arbitrary.
In one embodiment, the preparation of the functional polyether initiator and the functional polyether comprises the following steps:
1) and (3) synthesis of tetraphenylethane: adding metered aniline and solvent (the mass ratio of aniline to solvent is 1:0.2-1, preferably 1:0.33-0.5, the solvent can use methanol, ethanol, propanol, tert-butyl alcohol, toluene and the like, preferably methanol) into a reaction kettle, adding acid to adjust the pH of the system to 1-6, replacing nitrogen for three times, the reaction temperature is 60-100 ℃, adding glyoxal into the reaction kettle by using an advection pump, controlling the flow rate to be 1-5mL/min, continuing to react for 4-10 hours after the addition is finished, neutralizing to be neutral by using sodium bicarbonate or sodium carbonate, removing the solvent and unreacted aniline in the system under the conditions that the system temperature is 100-120 ℃ and the vacuum degree is-0.1 Mpa, and cooling the solution after the solvent is removed to obtain the crude product of the tetraphenylethane. The crude product is purified by column chromatography (silica gel is used as a stationary phase, CH)2Cl2Ethyl acetate as eluent) to obtain the product.
2) Synthesis of p-nitrosobenzyl alcohol: 1 equivalent of 4-aminobenzol was weighed out in a round-bottomed flask containing 100-1000mL of dichloromethane. 2-2.5 equivalents of Oxone complex salt (Oxone) were dissolved in 1000-3000mL of distilled water. Under the protection of nitrogen, the Oxone solution is dripped into a round-bottom flask and reacts for 2-6h at room temperature, and precipitates are separated out. And filtering the precipitate, repeatedly washing with water, and drying to obtain a crude product.
3) Synthesis of tetrakis (4-hydroxymethylazobenzene) ethane: 1 equivalent of tetraphenylethane and 4-4.5 equivalents of p-nitrosobenzyl alcohol are weighed and dissolved in a mixed solvent of glacial acetic acid (AcOH) and DMSO with the volume ratio of 1: 1. Reacting at 25-60 ℃ under the protection of nitrogenThe time is 24-90 h. After the reaction is finished, distilled water is added into the system, and a large amount of precipitate is separated out. And filtering, collecting a filter cake, repeatedly washing, and performing vacuum drying to obtain a crude product. The crude product is purified by column chromatography (silica gel is used as a stationary phase, CH)2Cl2MeOH as eluent) to give the product.
4) The synthetic route of the tetra (4-hydroxymethyl azobenzene) ethane polyether is a known conventional polyether synthetic process. The starter, the type of catalyst, the amount of catalyst used, the starter/EO/PO molar charge ratio, the reaction temperature, the reaction pressure can be reasonably determined by the person skilled in the art on the basis of the teaching of the present invention in combination with the prior art. Suitable catalysts include NaOH, KOH, Na, NaH, CHO3Na、CHO3K. Bimetallic catalysts, alkaline earth metal catalysts, phosphazene catalysts, lewis acid catalysts, and the like, with alkali metal catalysts being preferred. The amount of the catalyst is usually 0.02 to 1.0 wt%, preferably 0.05 to 0.5 wt%, based on the total weight of the initiator, ethylene oxide and propylene oxide to be added. The molar ratio of the initiator/EO/PO is 1/0-300/0-300, preferably 1/20-100/40-150. The reaction temperature is 80-160 deg.C, preferably 100-130 deg.C. The reaction pressure is in the range of-0.1 MPa to 0.6MPa, and the pressure is preferably controlled to be not higher than 0.4 MPa. With regard to the block sequence pattern of the block polyether, the design is made by changing the order of EO and/or PO feeding reaction. With respect to the synthesis of random copolyethers, copolyethers can be obtained by adding EO and PO in different mass ratios simultaneously.
The synthetic route of tetraphenylethane, for example aniline, is shown below:
the synthetic route for p-nitrosobenzyl alcohol is shown below:
the synthetic routes of tetra (4-hydroxymethyl azobenzene) ethane and tetra (4-hydroxymethyl azobenzene) ethane polyether are shown as follows:
a-0-200, b-0-200, at least one of a and b is not 0,
by replacing aniline with substituted aniline, such as aniline substituted with ortho-and meta-substituents (such as F, Cl, Br, methyl, methoxy, carboxyl, etc.), functional polyether initiator and functional polyether with other substituents on the benzene ring can be prepared.
The invention further provides the application of the functional polyether in the dyeing field or the crude oil demulsification field.
The specific method for preparing the functional polyether initiator comprises the following key parts: the raw material adopted for the synthesis of the tetraphenylethane is aniline, and other aromatic anilines containing ortho-position and meta-position substituents (such as F, Cl, Br, methyl, methoxy, carboxyl and the like) can also be synthesized into corresponding products by adopting the same route. The synthesis of the tetraphenylethane is catalyzed by controlling the pH of the system to be 1-6, and an acid without a double bond, such as hydrochloric acid, is generally selected. In the synthesis of the p-nitrosobenzyl alcohol, Oxone is used as an oxidant, the reaction is mild, the reaction process is convenient to control, and compared with a strong oxidant, fewer peroxide byproducts are generated by the Oxone reaction. The method is not limited to the use of 4-aminobenzol as a raw material, and other aniline derivatives containing ortho-position and meta-position substituents (such as F, Cl, Br, methyl, methoxy, carboxyl and the like) and containing hydroxyl groups, such as p-aminobenzyl alcohol, p-aminobenzyl alcohol and the like, can also be used for synthesizing corresponding products by adopting the method. The synthesis of the tetra (4-hydroxymethyl azobenzene) ethane uses a mixed solvent of glacial acetic acid and DMSO, and the DMSO does not participate in the reaction, but can increase the solubility of reactants, so that the two reactants are uniformly mixed, and the reaction speed is accelerated. The synthesis of polyether mainly controls the reaction temperature and the selection and dosage of the catalyst, and polyether with different EO/PO ratios and copolymerization structures is synthesized according to different product performance requirements.
Compared with the prior art, the invention has the following advantages:
1. the functional polyether initiator synthesized by the invention is a molecule with a novel structure, and is not reported at present. The synthesized molecules are azobenzene molecules with a multi-branch structure, and compared with single-branch azobenzene molecules, the molecules are higher in isomerization degree and more sensitive to light.
2. The synthesis route designed by the invention has mild reaction conditions and high yield, and particularly, the synthesis of p-nitrobenzol and tetra (4-hydroxymethyl azobenzene) ethane can be completed under the condition of being close to room temperature, and the reaction is safe.
3. The polyether product synthesized based on the novel initiator belongs to a functional product, and the performance of the polyether product can be adjusted through illumination, so that the performance remote control can be realized. Meanwhile, the indexes of solubility, residual quantity and the like of the polyether product in a solvent system can be quickly obtained through an ultraviolet absorption test, so that the polyether product can be favorably applied to the fields of crude oil demulsifiers, medicament dispersants and the like.
Detailed Description
The present invention will be further described with reference to the following examples.
By using1H NMR (Varian INOVA 500MHz) was further subjected to chemical structure testing of the prepared tetrakis (4-hydroxymethylazobenzene) ethane. The sample preparation method comprises the following steps: adding a small amount of dried azobenzene powder into a nuclear magnetic tube, adding deuterated dimethyl sulfoxide (DMSO-d6) for dissolving, and performing test characterization after uniform ultrasonic dispersion. Test range: 0 to 16 ppm.
The molecular weight of the prepared tetrakis (4-hydroxymethylazobenzene) ethane compounds was tested by high resolution mass spectrometry (Waters Xevo G2 QTof). A small amount of dried sample powder was taken and dissolved in methanol or acetonitrile for testing.
Example 1
1) And (3) synthesis of tetraphenylethane: adding 1kg of aniline and 0.5kg of methanol into a 3L reaction kettle, adding hydrochloric acid to adjust the pH of the system to 1, and replacing with nitrogenAnd thirdly, adding glyoxal into the reaction kettle by using a constant flow pump at the reaction temperature of 60 ℃, controlling the flow rate to be 1mL/min, and adding 93g of glyoxal. And (3) continuously reacting for 4 hours after the addition is finished, neutralizing the solution to be neutral by using sodium bicarbonate, removing the solvent and unreacted aniline in the system under the conditions that the system temperature is 100 ℃ and the vacuum degree is-0.1 Mpa, and cooling the solution after the solvent is removed to obtain a crude product of the tetraphenylethane. The crude product is purified by column chromatography (silica gel is used as a stationary phase, CH)2Cl2Ethyl acetate as eluent) to obtain the product.
2) Synthesis of p-nitrosobenzyl alcohol: 1000g of 4-aminobenzol was weighed out and dissolved in a round-bottomed flask containing 100mL of dichloromethane. 2 equivalents of Oxone were dissolved in 3000mL of distilled water. Under the protection of nitrogen, the Oxone solution is dripped into a round-bottom flask and reacts for 2 hours at room temperature, and precipitates are separated out. And filtering the precipitate, repeatedly washing with water, and drying to obtain a crude product.
3) Synthesis of tetrakis (4-hydroxymethylazobenzene) ethane: 600g of tetraphenylethane and 4 equivalents of p-nitrosobenzyl alcohol were weighed and dissolved in a mixed solvent of glacial acetic acid (AcOH) and DMSO at a volume ratio of 1: 1. And reacting at 25 ℃ for 24 hours under the protection of nitrogen. After the reaction is finished, distilled water is added into the system, and a large amount of precipitate is separated out. And filtering, collecting a filter cake, repeatedly washing, and performing vacuum drying to obtain a crude product. The crude product is purified by column chromatography (silica gel is used as a stationary phase, CH)2Cl2MeOH as eluent) to obtain the product of tetra (4-hydroxymethyl azobenzene) ethane (1H NMR(500MHz,DMSO-d6):δ＝8.06(d,8H；Ar-H),7.74ppm(d,8H；Ar-H),7.69ppm(d,4H；Ar-H),7.67ppm(d,4H；Ar-H),6.78ppm(d,8H；Ar-H),5.72ppm(s,Br,4H,OH),4.15ppm(s,8H；Ar-CH2),3.75ppm(s,2H；CH)。HRMS-ESI:m/z:870.3599(calcd.for[M+H]+,870.3605)。)。
4) Synthesis of tetrakis (4-hydroxymethylazobenzene) ethane polyether: A10L reactor equipped with a stirring, heating mantle and an internal water-cooled coil was charged with 856g of tetrakis (4-hydroxymethylazobenzene) ethane, 2.0g of NaOH (0.05 wt%), and the reactor was sealed. Replacing nitrogen for three times, starting stirring, heating to 100 ℃, dehydrating under-0.1 MPa, keeping the temperature at 100 ℃, slowly introducing ethylene oxide, keeping the reaction pressure less than 0.3MPa by controlling the introducing speed of the ethylene oxide, stopping feeding when the total amount of the ethylene oxide is 3520g, and carrying out aging reaction at 100 ℃ for 3 hours; the temperature was lowered to 90 ℃ and neutralized with acetic acid, and demonomerization was carried out at-0.1 MPa, and cooling was carried out to room temperature to obtain tetrakis (4-hydroxymethylazobenzene) ethane polyoxyethylene ether (hydroxyl value: 56.2mg KOH/g, PDI:1.08, viscosity: 1502cP @25 ℃ C.).
Example 2
1) Synthesis of tetrakis (3-fluoroanilino) ethane: adding 1.5kg of 3-fluoroaniline and 0.5kg of methanol into a 3L reaction kettle, adding hydrochloric acid to adjust the pH of the system to 3.5, carrying out nitrogen displacement for three times at the reaction temperature of 80 ℃, adding glyoxal into the reaction kettle by using a constant flow pump, controlling the flow rate to be 3mL/min, and adding 136g of glyoxal. And (3) continuing to react for 7 hours after the addition is finished, neutralizing the mixture to be neutral by using sodium bicarbonate, removing the solvent in the system under the conditions that the system temperature is 110 ℃ and the vacuum degree is minus 0.1Mpa, and cooling the solution after the solvent is removed to obtain a crude product of the tetra (3-fluoroanilino) ethane. The crude product is purified by column chromatography (silica gel is used as a stationary phase, CH)2Cl2Ethyl acetate as eluent) to obtain the product.
2) Synthesis of 2-fluoro-4-nitrosobenzyl alcohol: 1500g of 2-fluoro-4-aminobenzol were weighed out into a round-bottomed flask with 550mL of dichloromethane. 2.25 equivalents of Oxone were dissolved in 2000mL of distilled water. Under the protection of nitrogen, the Oxone solution is dripped into a round-bottom flask and reacts for 4 hours at room temperature, and precipitates are separated out. And filtering the precipitate, repeatedly washing with water, and drying to obtain a crude product.
3) Synthesis of tetrakis (2, 2' -difluoro-4-hydroxymethylazobenzene) ethane: 800g of tetrakis (3-fluoroanilino) ethane and 4.25 equivalents of 2-fluoro-4-nitrosobenzyl alcohol were weighed out and dissolved in a mixed solvent of glacial acetic acid (AcOH) and DMSO at a volume ratio of 1: 1. Reacting for 60 hours at 40 ℃ under the protection of nitrogen. After the reaction is finished, distilled water is added into the system, and a large amount of precipitate is separated out. And filtering, collecting a filter cake, repeatedly washing, and performing vacuum drying to obtain a crude product. The crude product is purified by column chromatography (silica gel is used as a stationary phase, CH)2Cl2MeOH as eluent) to give the product. (1H NMR(500MHz,DMSO-d6):δ＝8.09(dd,4H；Ar-H),7.94ppm(dd,4H；Ar-H),7.71-7.51ppm(m,8H；Ar-H),7.40ppm(dd,4H；Ar-H),7.35ppm(dd,4H；Ar-H),5.42ppm(s,Br,4H,OH),5.15ppm(s,2H；CH),4.45ppm(s,8H；Ar-CH2)。HRMS-ESI:m/z:1014.2911(calcd.for[M+H]+,1014.2915)。)。
4) Synthesis of tetrakis (2, 2' -difluoro-4-hydroxymethylazobenzene) ethane polyether: into a 15L reactor equipped with a stirring, heating mantle and an internal water-cooled coil were charged 856g of tetrakis (2, 2' -difluoro-4-hydroxymethylazobenzene) ethane, 19.11g CHO3Na (0.2 wt%), and the reaction kettle was sealed. Replacing nitrogen for three times, starting stirring, heating to 100 ℃, dehydrating under-0.1 MPa, heating to 115 ℃, slowly introducing propylene oxide, keeping the reaction pressure less than 0.4MPa by controlling the feeding speed of the propylene oxide, stopping feeding when 8700g of the propylene oxide is introduced in total, and carrying out aging reaction for 5 hours at 115 ℃; the temperature was lowered to 90 ℃ and neutralized with phosphoric acid, and the monomer was removed at-0.1 MPa, followed by cooling to room temperature to give tetrakis (2, 2' -difluoro-4-hydroxymethylazobenzene) ethane polyoxypropylene ether (hydroxyl value: 24.9mg KOH/g, PDI:1.07, viscosity: 2811cP @25 ℃ C.).
Example 3
1) Synthesis of tetrakis (3-methylanilino) ethane: adding 3kg of 3-methylaniline and 1kg of methanol into a 10L reaction kettle, adding hydrochloric acid to adjust the pH of the system to 6, replacing the nitrogen for three times, controlling the reaction temperature to be 100 ℃, adding glyoxal into the reaction kettle by using a constant flow pump, controlling the flow rate to be 5mL/min, and adding 325g of glyoxal in total. And (3) continuing to react for 10 hours after the addition is finished, neutralizing the mixture to be neutral by using sodium bicarbonate, removing the solvent in the system under the conditions that the system temperature is 120 ℃ and the vacuum degree is minus 0.1Mpa, and cooling the solution after the solvent is removed to obtain a crude product of the tetra (3-methylanilino) ethane. The crude product is purified by column chromatography (silica gel is used as a stationary phase, CH)2Cl2Ethyl acetate as eluent) to obtain the product.
2) Synthesis of 2-methyl-4-nitrosobenzyl alcohol: 2000g of 2-fluoro-4-aminobenzol was weighed out in a round-bottomed flask containing 1000mL of dichloromethane. 2.5 equivalents of Oxone were dissolved in 1000mL of distilled water. Under the protection of nitrogen, the Oxone solution is dripped into a round-bottom flask and reacts for 6 hours at room temperature, and precipitates are separated out. And filtering the precipitate, repeatedly washing with water, and drying to obtain a crude product.
3) Synthesis of tetrakis (2, 2' -dimethyl-4-hydroxymethylazobenzene) ethane: 1000g of tetrakis (3-methylanilino) ethane and 4.5 equivalents of 2-methyl-4-nitrosobenzyl alcohol were weighed out and dissolved in a mixed solvent of glacial acetic acid (AcOH) and DMSO at a volume ratio of 1: 1. Reacting for 90 hours at 60 ℃ under the protection of nitrogen. After the reaction is finished, distilled water is added into the system, and a large amount of precipitate is separated out. And filtering, collecting a filter cake, repeatedly washing, and performing vacuum drying to obtain a crude product. The crude product is purified by column chromatography (silica gel is used as a stationary phase, CH)2Cl2MeOH as eluent) to give the product. (1H NMR(500MHz,DMSO-d6):δ＝8.19(dd,4H；Ar-H),8.04ppm(dd,4H；Ar-H),7.81ppm(d,4H；Ar-H),7.71ppm(d,4H；Ar-H),7.51ppm(d,4H；Ar-H),7.41ppm(d,4H；Ar-H),5.32ppm(s,Br,4H,OH),5.05ppm(s,2H；CH),4.55ppm(s,8H；Ar-CH2),1.55ppm(s,24H；CH3)。HRMS-ESI:m/z:982.4905(calcd.for[M+H]+,982.4902)。)。
4) Synthesis of tetrakis (2, 2' -dimethyl-4-hydroxymethylazobenzene) ethane polyether: A15L reactor with stirring, heating mantle and internal water-cooled coil was charged with 856g of tetrakis (2, 2' -dimethyl-4-hydroxymethylazobenzene) ethane, 47.08g CHO3K (0.5 wt%), and the reaction kettle was sealed. Replacing with nitrogen for three times, starting stirring, heating to 100 ℃, dehydrating under-0.1 MPa, and then heating to 130 ℃. Mixing ethylene oxide and propylene oxide in a feeding tank, wherein the mass ratio of EO/PO is 60/40, then slowly introducing the mixture of ethylene oxide and propylene oxide, keeping the reaction pressure less than 0.4MPa by controlling the feeding speed, stopping feeding when the total amount of 8560g of ethylene oxide is introduced, and carrying out aging reaction for 3 hours at 130 ℃; the temperature was lowered to 90 ℃ and neutralized with lactic acid, and demonomerization was carried out at-0.1 MPa, and cooling was carried out to room temperature to give tetrakis (2, 2' -dimethyl-4-hydroxymethylazobenzene) ethane polyoxyethylene polyoxypropylene copolyether (hydroxyl value: 25.4mg KOH/g, PDI:1.08, viscosity: 2011cP @25 ℃ C.).
Application example 1
Application of tetra (4-hydroxymethyl azobenzene) ethane polyether in the field of dyeing.
0.2 wt% of tetra (4-hydroxymethyl azobenzene) ethane polyether (example 1), 0.8 wt% of sodium dodecyl sulfate, 10% of coating color paste, 5 wt% of acrylate adhesive and 84 wt% of deionized water are uniformly mixed to prepare a coloring agent, the mixture is uniformly stirred at room temperature to generate uniform foam, the foaming ratio is 14, the half-life period is 6.3min, the generated foam is rapidly coated on the surface of the fabric, the fabric coated with the coloring agent is rapidly placed into an oven to be dried, and the temperature is 80 ℃ for 10min, so that the dyed fabric with uniform color is obtained. The residual foam after dyeing can be rapidly destroyed by 365nm ultraviolet irradiation, the half-life period is only 40s, and the foam can be recycled.
Application example 2
The application of tetra (4-hydroxymethyl azobenzene) ethane polyether in the field of crude oil demulsification.
The demulsification test was carried out according to SY/T5821-. Weighing a certain amount of the crude oil demulsifier sample of example 1, quantitatively transferring the sample into a volumetric flask, diluting the sample to a scale with ethanol, and shaking up to make the mass of the crude oil demulsifier contained in each 100m L solution be 1 g. A sample of the crude oil emulsion was placed in a 100m L dehydration flask and heated to a certain temperature, and 100ppm of tetrakis (4-hydroxymethylazobenzene) ethane polyether was added to the dehydration flask. And (3) after screwing the bottle cap, placing the dehydration test bottle in a manual oscillation box, horizontally oscillating for 50-200 times, loosening the bottle cap after fully mixing uniformly, and placing the dehydration test bottle in a constant-temperature water bath again for standing and settling. The amount of wastewater discharged at different times was visually observed and recorded, and the ultraviolet absorption spectra of the oil phase and the aqueous phase were measured, respectively, to analyze the amounts of tetrakis (4-hydroxymethylazobenzene) ethane polyether in the aqueous phase and the oil phase to 80ppm and 20 ppm.
Claims (18)
1. A polyether initiator having the formula:
wherein, R is independently selected from hydrogen, halogen, C1-C4 alkyl, C1-4 alkoxy and C1-C4 acid group, and n is an integer of 1-4.
2. The polyether starter of claim 1 wherein each R is independently selected from F, Cl, Br, methyl, methoxy, carboxyl.
3. A polyether having the formula:
wherein, R is independently selected from hydrogen, halogen, C1-C4 alkyl, C1-4 alkoxy, C1-C4 acid group, and n is an integer of 1-4;
a-0-200, b-0-200, at least one of a and b being different from 0.
4. The polyether of claim 3, wherein each R is independently selected from F, Cl, Br, methyl, methoxy, carboxyl.
5. A process for preparing the polyether starter of claim 1 or 2, comprising:
(A) adding metered aniline or R-substituted aniline into a reaction kettle, adding acid to adjust the pH of a system to 1-6, replacing with nitrogen, adding glyoxal into the reaction kettle at the reaction temperature of 60-100 ℃ to react, neutralizing to neutrality, removing a solvent and unreacted aniline or R-substituted aniline in the system, cooling the solution after removing the solvent to obtain a crude product of tetraphenylethane or R-substituted tetraphenylethane, and purifying the crude product to obtain tetraphenylethane or R-substituted tetraphenylethane;
(B) reacting 4-aminobenzyl alcohol or R-substituted 4-aminobenzyl alcohol with potassium hydrogen persulfate composite salt under the protection of nitrogen, filtering and washing a precipitate after the reaction, and drying to obtain p-nitrosobenzyl alcohol or R-substituted p-nitrosobenzyl alcohol;
(C) reacting tetraphenylethane or R-substituted tetraphenylethane and p-nitrosobenzyl alcohol or R-substituted p-nitrosobenzyl alcohol under the protection of nitrogen, adding water into a system after the reaction is finished to separate out a precipitate, filtering, collecting a filter cake, washing, drying in vacuum to obtain a crude product, and purifying the crude product to obtain a polyether initiator;
wherein R is as defined in claim 1.
6. The production process according to claim 5, wherein the reaction of step (A) is carried out in a solvent in a mass ratio of aniline to solvent of 1: 0.2-1.
7. The preparation method according to claim 6, wherein the solvent is one or more selected from methanol, ethanol, propanol, tert-butanol and toluene, and the mass ratio of aniline to solvent is 1: 0.33-0.5.
8. The production method according to any one of claims 5 to 7,
in step (a) of the above production method, the molar ratio of aniline or R-substituted aniline to glyoxal is 1: 0.1-0.25; and/or
In the step (B), the molar ratio of the 4-aminobenzol or the R-substituted 4-aminobenzol to the oxone complex salt is 1: 2-4; and/or
In step (C), the molar ratio of tetraphenylethane or R-substituted tetraphenylethane to p-nitrosobenzyl alcohol or R-substituted p-nitrosobenzyl alcohol is 1: 2 to 10.
9. The production method according to claim 8,
in step (a) of the above production method, the molar ratio of aniline or R-substituted aniline to glyoxal is 1: 0.15 to 0.2; and/or
In the step (B), the molar ratio of the 4-aminobenzol or the R-substituted 4-aminobenzol to the oxone complex salt is 1: 2.2 to 2.5; and/or
In step (C), the molar ratio of tetraphenylethane or R-substituted tetraphenylethane to p-nitrosobenzyl alcohol or R-substituted p-nitrosobenzyl alcohol is 1: 3-5.
10. A process for preparing the polyether of claim 3 or 4, comprising:
(A) adding metered aniline or R-substituted aniline into a reaction kettle, adding acid to adjust the pH of a system to 1-6, replacing with nitrogen, adding glyoxal into the reaction kettle at the reaction temperature of 60-100 ℃ to react, neutralizing to neutrality, removing a solvent and unreacted aniline or R-substituted aniline in the system, cooling the solution after removing the solvent to obtain a crude product of tetraphenylethane or R-substituted tetraphenylethane, and purifying the crude product to obtain tetraphenylethane or R-substituted tetraphenylethane;
(B) reacting 4-aminobenzyl alcohol or R-substituted 4-aminobenzyl alcohol with potassium hydrogen persulfate composite salt under the protection of nitrogen, filtering and washing a precipitate after the reaction, and drying to obtain p-nitrosobenzyl alcohol or R-substituted p-nitrosobenzyl alcohol;
(C) reacting tetraphenylethane or R-substituted tetraphenylethane and p-nitrosobenzyl alcohol or R-substituted p-nitrosobenzyl alcohol under the protection of nitrogen, adding water into a system after the reaction is finished to separate out a precipitate, filtering, collecting a filter cake, washing, drying in vacuum to obtain a crude product, and purifying the crude product to obtain a polyether initiator;
(D) reacting a polyether initiator with ethylene oxide and/or propylene oxide in the presence of a catalyst;
wherein R is as defined in claim 3.
11. The production method according to claim 10, wherein the reaction of step (a) is carried out in a solvent, and the mass ratio of aniline to solvent is 1: 0.2-2.
12. The preparation method according to claim 11, wherein the solvent is one or more selected from methanol, ethanol, propanol, tert-butanol and toluene, and the mass ratio of aniline to solvent is 1: 0.33-0.5.
13. The production method according to any one of claims 10 to 12,
in step (a) of the above production method, the molar ratio of aniline or R-substituted aniline to glyoxal is 1: 0.1-0.25; and/or
In the step (B), the molar ratio of the 4-aminobenzol or the R-substituted 4-aminobenzol to the oxone complex salt is 1: 2-4; and/or
In step (C), the molar ratio of tetraphenylethane or R-substituted tetraphenylethane to p-nitrosobenzyl alcohol or R-substituted p-nitrosobenzyl alcohol is 1: 2 to 10.
14. The production method according to claim 13, wherein,
in step (a) of the above production method, the molar ratio of aniline or R-substituted aniline to glyoxal is 1: 0.15 to 0.2; and/or
In the step (B), the molar ratio of the 4-aminobenzol or the R-substituted 4-aminobenzol to the oxone complex salt is 1: 2.2 to 2.5; and/or
In step (C), the molar ratio of tetraphenylethane or R-substituted tetraphenylethane to p-nitrosobenzyl alcohol or R-substituted p-nitrosobenzyl alcohol is 1: 3-5.
15. The production method according to any one of claims 10 to 12, wherein in step (D), the mass ratio of the polyether initiator to ethylene oxide and/or propylene oxide is 1:1 to 20.
16. The production method according to any one of claims 10 to 12, wherein in step (D), the mass ratio of the polyether initiator to ethylene oxide and/or propylene oxide is 1: 8-12.
17. Use of the polyether starter of claim 1 or 2 for the preparation of polyethers.
18. Use of the polyethers according to claim 3 or 4 for the field of dyeing or the field of demulsification of crude oils.
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