CN117700715A - Application of boron carbon nitride catalyst in preparation of fatty alcohol polyether - Google Patents
Application of boron carbon nitride catalyst in preparation of fatty alcohol polyether Download PDFInfo
- Publication number
- CN117700715A CN117700715A CN202311603046.8A CN202311603046A CN117700715A CN 117700715 A CN117700715 A CN 117700715A CN 202311603046 A CN202311603046 A CN 202311603046A CN 117700715 A CN117700715 A CN 117700715A
- Authority
- CN
- China
- Prior art keywords
- boron
- carbon nitride
- catalyst
- fatty alcohol
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 58
- 229920000570 polyether Polymers 0.000 title claims abstract description 53
- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 44
- 150000002191 fatty alcohols Chemical class 0.000 title claims abstract description 39
- PPWPWBNSKBDSPK-UHFFFAOYSA-N [B].[C] Chemical compound [B].[C] PPWPWBNSKBDSPK-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 18
- 229910052796 boron Inorganic materials 0.000 claims abstract description 15
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims abstract description 14
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 14
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims abstract description 13
- 230000008569 process Effects 0.000 claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 16
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 150000002924 oxiranes Chemical class 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 239000003607 modifier Substances 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 6
- 239000012295 chemical reaction liquid Substances 0.000 claims description 5
- 238000007872 degassing Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 4
- 239000004327 boric acid Substances 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 3
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 3
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 3
- VGTPKLINSHNZRD-UHFFFAOYSA-N oxoborinic acid Chemical compound OB=O VGTPKLINSHNZRD-UHFFFAOYSA-N 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 238000002604 ultrasonography Methods 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims 2
- 229910052582 BN Inorganic materials 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000004321 preservation Methods 0.000 claims 1
- 229910021645 metal ion Inorganic materials 0.000 abstract description 10
- 239000002253 acid Substances 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- DLGYNVMUCSTYDQ-UHFFFAOYSA-N azane;pyridine Chemical compound N.C1=CC=NC=C1 DLGYNVMUCSTYDQ-UHFFFAOYSA-N 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 25
- 238000001816 cooling Methods 0.000 description 11
- -1 polyoxypropylene chain Polymers 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 229920000056 polyoxyethylene ether Polymers 0.000 description 9
- 229940051841 polyoxyethylene ether Drugs 0.000 description 9
- 229920001451 polypropylene glycol Polymers 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 238000010992 reflux Methods 0.000 description 6
- 208000005156 Dehydration Diseases 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000018044 dehydration Effects 0.000 description 5
- 238000006297 dehydration reaction Methods 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 1
- RVGRUAULSDPKGF-UHFFFAOYSA-N Poloxamer Chemical compound C1CO1.CC1CO1 RVGRUAULSDPKGF-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000012653 anionic ring-opening polymerization Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005815 base catalysis Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Polyethers (AREA)
Abstract
The invention belongs to the technical field of polyether synthesis, and discloses application of a boron carbon nitride catalyst in preparation of fatty alcohol polyether. The boron-carbon nitride catalyst is applied to the preparation of the aliphatic alcohol polyether, and not only has rich alkaline sites such as pyridine nitrogen and the like on carbon nitride, but also introduces acid centers into the framework of the carbon nitride by doping boron, and the introduction of boron in the thermal shrinkage process can increase the specific surface area of the catalyst and ensure that the catalyst activity is higher. More importantly, the boron carbon nitride catalyst does not contain metal elements, avoids the carry-in of metal ions, reduces the residue of the metal ions, and improves the pH stability of the fatty alcohol polyether. The aliphatic alcohol polyether prepared by the boron-carbon nitride catalyst has the advantages of strong stability, light color, good usability, reasonable preparation process, simple operation, high reaction efficiency and short reaction period.
Description
Technical Field
The invention belongs to the technical field of polyether synthesis, and particularly relates to application of a boron carbon nitride catalyst in preparation of fatty alcohol polyether.
Background
The aliphatic alcohol polyether belongs to one of nonionic surfactants and has excellent diffusion, permeation, emulsification, washing and wetting properties. In the synthesis of general aliphatic alcohol polyethers, most of them are hydroxyl-terminated polyethers obtained by anionic ring-opening polymerization of ethylene oxide, propylene oxide and an active hydrogen-containing initiator in the presence of alkali metal hydroxide catalysts such as KOH and NaOH. Neutralization adsorption is usually carried out by using acid after the reaction is finished, which makes the residues of salts and metal ions in the polyether product unavoidable; and aliphatic alcohol block polyethers prepared using alkali metal hydroxide catalysts tend to have small amounts of unsaturated double bonds at the ends of the polymer as the propylene oxide homo-chains grow. The residual metal ions give the hydrogen of the tertiary carbon atoms on the small number of unsaturated double bonds and on the polyoxypropylene chain units an instability, which in the hot state leads to the polyether forming free acids under the action of traces of water and oxygen, which leads to a decrease in the pH of the product. In addition to alkali metal hydroxide catalysis, solid acid catalysts such as DMC catalysts are also commonly used in the market at present, but DMC catalysts cannot completely avoid the introduction of metal ions, and the pH stability of polyether products is still poor, which greatly influences the downstream application of the products. Therefore, there is a need to optimize the existing catalysts, reduce the residual metal ions in polyether products, and prepare fatty alcohol polyether with strong pH stability.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems in the prior art described above. For this purpose, the invention proposes the use of a boron carbon nitride catalyst for the preparation of fatty alcohol polyethers. The aliphatic alcohol polyether is prepared by using the boron carbon nitride catalyst, so that the catalytic activity can be improved, the residue of metal ions in the polyether product can be effectively avoided, and the aliphatic alcohol polyether with strong pH stability is prepared.
The invention provides application of a carbon boronitride catalyst in preparation of fatty alcohol polyether.
The boron carbon nitride catalyst is composed of three elements of carbon, nitrogen and boron, and is also called boron doped carbon nitride, boron modified carbon nitride and the like. The boron carbon nitride catalyst has a unique structure and is widely applied to photocatalytic reactions. The invention provides the application to the preparation of the fatty alcohol polyether for the first time, and researches show that the preparation of the fatty alcohol polyether by using the boron carbon nitride catalyst can not only improve the catalytic activity and the reaction efficiency, but also effectively avoid the substitution of metal ions, so that the prepared fatty alcohol polyether has excellent pH stability.
Preferably, the preparation method of the boron carbon nitride catalyst comprises the following steps:
and dissolving the carbon nitride precursor in a solvent, adding a boron-containing modifier for reaction, crystallizing the reaction liquid after the reaction is finished, and roasting to obtain the boron-carbon nitride catalyst.
Preferably, the carbon nitride precursor comprises at least one of cyanamide, dicyandiamide, melamine, urea, thiourea.
Preferably, the solvent is at least one selected from ethanol, ethylene glycol, glycerol, and water;
preferably, the boron-containing modifier is at least one of boric acid, metaboric acid and boric anhydride.
Preferably, the boron-containing modifier is added in an amount of 33.5wt.% to 147wt.% of the carbon nitride precursor;
preferably, the reaction is a reflux reaction, and the reflux reaction is carried out for 3-5 hours at 40-60 ℃.
Preferably, the temperature of the crystallization is 50-80 ℃.
Preferably, the roasting process is a step-heating roasting process, the initial temperature is 300-500 ℃, the temperature is 10-30 ℃ in each step, the temperature is kept for 0.1-2h, and 3-20 steps are carried out.
Preferably, the roasting process is followed by cooling, impurity removal and drying.
More specifically, the preparation method of the boron carbon nitride catalyst comprises the following steps:
dissolving a carbon nitride precursor in a solvent, adding a boron-containing modifier, and then carrying out reflux reaction for 3-5h at 40-60 ℃; evaporating and crystallizing the reaction solution at 50-80 ℃ after the reaction is finished, and grinding the crystallized solid into powder; and roasting the powder, cooling, washing impurities with ethanol, and drying at 60-80 ℃ to obtain the boron-carbon nitride catalyst.
The invention also provides a preparation method of the fatty alcohol polyether.
Specifically, the preparation method of the fatty alcohol polyether comprises the following steps:
the fatty alcohol reacts with the epoxide in the presence of a carbon boronitride catalyst to form a fatty alcohol polyether.
Preferably, a process for the preparation of a fatty alcohol polyether comprises the steps of:
mixing fatty alcohol with a boron carbon nitride catalyst, sealing and carrying out ultrasonic treatment, dropwise adding epoxide for reaction, and degassing and filtering after the reaction is finished to prepare the fatty alcohol polyether.
The fatty alcohol is mixed with the boron-containing carbon nitride catalyst before the reaction, the boron-containing carbon nitride catalyst is in a lamellar stripping state by ultrasonic treatment, the lamellar stripping state is looser than that of a heterogeneous particle catalyst, and the catalytic activity and the filtering rate are faster.
Preferably, the fatty alcohol is an aliphatic alcohol having a chain of 8 to 22 carbon atoms.
Preferably, the carbon boronitride catalyst is added in an amount of 0.01% -2% of the total amount of the aliphatic alcohol polyether.
Preferably, the fatty alcohol is dehydrated prior to mixing with the carbon boronitride catalyst; further preferably, the dehydration treatment comprises the following steps: dehydrating at 80-110deg.C and-0.095-0.098 Mpa for 10-40min.
Preferably, the time of the ultrasonic treatment is 0.5-5h; further preferably, the time of the ultrasound is 1-3 hours.
Preferably, the epoxide is ethylene oxide and/or propylene oxide, such as ethylene oxide/propylene oxide blocks, including ethylene oxide-then-propylene oxide blocks and ethylene oxide-then-ethylene oxide blocks, ethylene oxide-propylene oxide mixtures, and the like.
Preferably, the temperature of the reaction is from 90 to 125 ℃.
Compared with the prior art, the invention has the beneficial effects that:
(1) The boron-carbon nitride catalyst is applied to the preparation of the aliphatic alcohol polyether, and not only has rich alkaline sites such as pyridine nitrogen and the like on carbon nitride, but also introduces acid centers into the framework of the carbon nitride by doping boron, and the introduction of boron in the thermal shrinkage process can increase the specific surface area of the catalyst and ensure that the catalyst activity is higher. More importantly, the boron carbon nitride catalyst does not contain metal elements, avoids the carry-in of metal ions, reduces the residue of the metal ions, and improves the pH stability of the fatty alcohol polyether.
(2) According to the preparation method of the fatty alcohol polyether, the boron carbon nitride catalyst and the initiator are subjected to ultrasonic stripping, so that more active sites of the boron carbon nitride catalyst can be generated, the catalytic activity is improved, unsaturated bonds generated in the epoxy compound reaction are reduced, and the stability (thermal stability, pH stability and application stability) of the prepared fatty alcohol polyether is further improved. In addition, the ultrasonic stripping ensures that the boron carbon nitride catalyst is in a lamellar stripping state in the polyether, so that the boron carbon nitride catalyst is looser than a heterogeneous particle catalyst, has a faster filtration rate, and is beneficial to recycling after reaction.
(3) The preparation method of the fatty alcohol polyether provided by the invention has the advantages of reasonable process, simplicity in operation, short reaction period, strong stability, light color and good usability.
Detailed Description
In order to make the technical solutions of the present invention more apparent to those skilled in the art, the following examples will be presented. It should be noted that the following examples do not limit the scope of the invention.
The starting materials, reagents or apparatus used in the following examples are all available from conventional commercial sources or may be obtained by methods known in the art unless otherwise specified.
Examples 1-3 describe the preparation of carbon boronitride catalysts 1-3 for use in the preparation of aliphatic alcohol polyethers.
Example 1
A method for preparing a boron carbon nitride catalyst, comprising the following steps:
(1) Dissolving 7.5g of urea in 100ml of ethanol, and uniformly stirring;
(2) Adding 2.48g of boric acid into the solution (1), and carrying out reflux reaction for 4 hours at 70 ℃;
(3) Evaporating and crystallizing the reaction liquid in the step (2) at 80 ℃, and grinding the crystallized solid into powder;
(4) Placing the powder in the step (3) into a crucible with a cover, placing the crucible into a muffle furnace for roasting, wherein the initial temperature is 400 ℃ (the heating rate is 10 ℃/min), the temperature gradients are 20 ℃, and each temperature gradient is kept for 2 hours (namely, five temperature gradients are respectively kept for 2 hours at the stages of 420, 440, 460, 480 and 500 ℃);
(5) After cooling, impurities were washed with ethanol and dried at 70 ℃ for 24 hours to obtain carbon boronitride catalyst 1.
Example 2
A method for preparing a boron carbon nitride catalyst, comprising the following steps:
(1) 3.36g of dicyandiamide and 4.12g of melamine are dissolved in 100ml of ethanol and stirred uniformly;
(2) Adding 4.11g of boric anhydride into the solution (1), and carrying out reflux reaction for 3 hours at 55 ℃;
(3) Evaporating and crystallizing the reaction liquid in the step (2) at 65 ℃, and grinding the crystallized solid into powder;
(4) Placing the powder in the step (3) into a crucible with a cover, placing the crucible into a muffle furnace for roasting, wherein the initial temperature is 300 ℃ (the heating rate is 15 ℃/min), the temperature gradients are 30 ℃, and each temperature gradient is kept for 0.5h, and 6 temperature gradients are used (namely, the temperature is kept for 0.5h at the temperature of 330 ℃, 360 ℃, 390, 420, 450 and 480 ℃ respectively);
(5) After cooling, the impurities are washed away by ethanol, and the boron carbon nitride catalyst 2 is obtained after drying for 24 hours at 60 ℃.
Example 3
A method for preparing a boron carbon nitride catalyst, comprising the following steps:
(1) 2.37g of cyanamide, 5.28g of urea and 1.61 of thiourea are dissolved in 100ml of ethanol and stirred uniformly;
(2) Adding 6.88g of boric acid and 1.37g of metaboric acid into the solution (1), and carrying out reflux reaction for 3h at 55 ℃;
(3) Evaporating and crystallizing the reaction liquid in the step (2) at 75 ℃, and grinding the crystallized solid into powder;
(4) Placing the powder in the step (3) into a crucible with a cover, placing the crucible into a muffle furnace for roasting, wherein the initial temperature is 400 ℃ (the heating rate is 15 ℃/min), the temperature gradient is 10 ℃, and the temperature of each temperature gradient is kept for 1h, and the total temperature of 10 temperature gradients is 10;
(5) After cooling, the impurities were washed with ethanol and dried at 80℃for 24 hours to give carbon boronitride catalyst 3.
Example 4 provides a specific method for preparing fatty alcohol polyethers using boron carbon nitride catalysts.
Example 4
The preparation method of the n-dodecanol polyoxypropylene polyoxyethylene ether comprises the following steps:
(1) Dehydrating 186g of n-dodecanol at 90 ℃ under-0.098 Mpa for 20min;
(2) Mixing dehydrated n-dodecanol with 0.3g of boron carbon nitride catalyst 1, and sealing and ultrasonic treatment for 1.5 hours;
(3) Immediately putting the mixture subjected to ultrasonic treatment into a reaction kettle, placing nitrogen for three times, heating to 120 ℃, dropwise adding 657g of propylene oxide, ensuring that the pressure is less than or equal to 0.35Mpa, reacting at 120-122 ℃, and preserving heat at 120 ℃ until the pressure is not reduced any more after the propylene oxide is dropwise added; 657g of ethylene oxide is added dropwise, the pressure is ensured to be less than or equal to 0.35Mpa, the reaction temperature is 120-122 ℃, and the temperature is kept for 1h at 120 ℃ after the ethylene oxide is added dropwise until the pressure is not reduced any more;
(4) Cooling to 100deg.C, vacuumizing to-0.098 MPa, and degassing for 10min;
(5) Cooling to 70 ℃ and filtering to obtain the n-dodecanol polyoxypropylene polyoxyethylene ether.
Comparative example 1
The preparation method of the n-dodecanol polyoxypropylene polyoxyethylene ether comprises the following steps:
(1) 186g of n-dodecanol and 0.3g of sodium hydroxide are put into a reaction kettle, nitrogen is placed for 3 times, and dehydration is carried out for 1h under the conditions of 90 ℃ and minus 0.098 Mpa;
(2) After dehydration, heating to 120 ℃, dropwise adding 657g of propylene oxide, ensuring that the pressure is less than or equal to 0.35Mpa, reacting at 120-122 ℃, and preserving heat at 120 ℃ for 3 hours after the propylene oxide is completely added until the pressure is not reduced; 657g of ethylene oxide is added dropwise, the pressure is ensured to be less than or equal to 0.35Mpa, the reaction temperature is 120-122 ℃, and the temperature is kept for 1h at 120 ℃ after the ethylene oxide is added dropwise until the pressure is not reduced any more;
(3) Cooling to 100deg.C, vacuumizing to-0.098 MPa, and degassing for 10min;
(4) Cooling to 70 ℃, adding 0.45g of acetic acid for neutralization, and obtaining the n-dodecanol polyoxypropylene polyoxyethylene ether.
Comparative example 2
The preparation method of the n-dodecanol polyoxypropylene polyoxyethylene ether comprises the following steps:
(1) 186g of n-dodecanol and 0.3g of sodium hydroxide are put into a reaction kettle, nitrogen is placed for 3 times, and dehydration is carried out for 1h under the conditions of 90 ℃ and minus 0.098 Mpa;
(2) After dehydration, heating to 120 ℃, dropwise adding 657g of propylene oxide, ensuring that the pressure is less than or equal to 0.35Mpa, reacting at 120-122 ℃, and preserving heat at 120 ℃ for 3 hours after the propylene oxide is completely added until the pressure is not reduced; 657g of ethylene oxide is added dropwise, the pressure is ensured to be less than or equal to 0.35Mpa, the reaction temperature is 120-122 ℃, and the temperature is kept for 1h at 120 ℃ after the ethylene oxide is added dropwise until the pressure is not reduced any more;
(3) Cooling to 100deg.C, vacuumizing to-0.098 MPa, and degassing for 10min;
(4) Cooling to 70 ℃, adding 0.7g of phosphoric acid for neutralization, adding 0.45g of adsorbent for adsorption for 30min, and filtering to obtain the n-dodecanol polyoxypropylene polyoxyethylene ether.
The hydroxyl value (unit mgKOH/g) of the n-dodecanol polyoxypropylene polyoxyethylene ether prepared in example 4 and comparative examples 1 and 2 was measured, the appearance of the sample was observed, and the dropping time of PO (propylene oxide) during the preparation was recorded. The n-dodecanol polyoxypropylene polyoxyethylene ether prepared in example 4 and comparative examples 1 and 2 was sealed, left at room temperature (25.+ -. 3 ℃) for 7, 14 and 21 days, and then prepared into a 10% aqueous solution for pH value test, and compared with the pH value of the n-dodecanol polyoxypropylene polyoxyethylene ether just prepared. The results are shown in Table 1.
TABLE 1
In general, the reaction rate of PO (propylene oxide) is far slower than that of EO (ethylene oxide) in the reaction process, so that the PO reaction stage determines the reaction speed, and it is clear from the above table that, under the condition that the catalyst usage is the same and the reaction is guaranteed to be sufficiently carried out, the reaction speed of example 4 is faster, although the product appearance, the hydroxyl value is close to that of the base catalysis product index, the pH stability of the aliphatic alcohol polyether prepared in example 4 is significantly better than that of comparative examples 1 and 2, and the pH value is almost unchanged after the aliphatic alcohol polyether is left at room temperature for 21 days.
Examples 5 to 12
Examples 5-12 provide 8 specific examples of the preparation of fatty alcohol polyethers using carbon boronitride catalysts.
The fatty alcohol dosage in examples 5-12 was 1mol, specific process parameters table 2:
TABLE 2
The main indices of the fatty alcohol polyethers prepared in examples 5 to 12 are shown in Table 3:
TABLE 3 Table 3
As can be seen from Table 3, for different types of fatty alcohol initiators and different epoxide addition modes, the hydroxyl values of the fatty alcohol polyether prepared by the embodiment of the invention are basically consistent with the designed molecular weight, and the method is proved to be capable of effectively synthesizing polyethers with various functional structures, and the pH value of the fatty alcohol polyether is almost unchanged without obvious reduction phenomenon when the pH value is monitored for 21 days, so that the fatty alcohol polyether prepared by the embodiment of the invention is proved to have excellent pH stability.
The foregoing examples illustrate only a few embodiments of the invention and are described in detail herein without thereby limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (10)
1. The application of boron carbon nitride catalyst in preparing fatty alcohol polyether.
2. The use according to claim 1, characterized in that the preparation method of the carbon boron nitride catalyst comprises the following steps:
and dissolving the carbon nitride precursor in a solvent, adding a boron-containing modifier for reaction, crystallizing the reaction liquid after the reaction is finished, and roasting to obtain the boron-carbon nitride catalyst.
3. The use according to claim 2, wherein the carbon nitride precursor comprises at least one of cyanamide, dicyandiamide, melamine, urea, thiourea; and/or
The solvent is at least one selected from ethanol, ethylene glycol, glycerol and water.
4. Use according to claim 2 or 3, wherein the boron-containing modifier is at least one of boric acid, metaboric acid, boric anhydride.
5. Use according to claim 2 or 3, wherein the calcination process is a stepwise elevated temperature calcination with an initial temperature of 300-500 ℃, an elevated temperature of 10-30 ℃ per stage, and a heat preservation time of 0.1-2h, for 3-20 stages.
6. A process for the preparation of a fatty alcohol polyether, comprising the steps of:
the fatty alcohol reacts with the epoxide in the presence of a carbon boronitride catalyst to form a fatty alcohol polyether.
7. The method of manufacturing according to claim 6, comprising the steps of:
mixing fatty alcohol with a boron carbon nitride catalyst, sealing and carrying out ultrasonic treatment, dropwise adding epoxide for reaction, and degassing and filtering after the reaction is finished to prepare the fatty alcohol polyether.
8. The method according to claim 7, wherein the carbon boronitride catalyst is added in an amount of 0.01% -2% of the total amount of the aliphatic alcohol polyether.
9. The method of claim 7, wherein the time of the ultrasound is 0.5-5 hours.
10. The preparation method according to any one of claims 7 to 9, characterized in that the epoxide is ethylene oxide and/or propylene oxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311603046.8A CN117700715A (en) | 2023-11-28 | 2023-11-28 | Application of boron carbon nitride catalyst in preparation of fatty alcohol polyether |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311603046.8A CN117700715A (en) | 2023-11-28 | 2023-11-28 | Application of boron carbon nitride catalyst in preparation of fatty alcohol polyether |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117700715A true CN117700715A (en) | 2024-03-15 |
Family
ID=90154335
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311603046.8A Pending CN117700715A (en) | 2023-11-28 | 2023-11-28 | Application of boron carbon nitride catalyst in preparation of fatty alcohol polyether |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117700715A (en) |
-
2023
- 2023-11-28 CN CN202311603046.8A patent/CN117700715A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1976887B (en) | Method of preparing alkoxylation catalysts and their use in alkoxylation processes | |
| CN114276281B (en) | Light-colored cardanol polyoxyethylene ether ammonium sulfate anionic surfactant and preparation method and application thereof | |
| CN106243344B (en) | A kind of continuous open loop production technology of epoxy radicals end-blocking polyethers | |
| CN105061750A (en) | High-double bond content allyl polyether production method | |
| CA1086313A (en) | Process for the preparation of cellulose alkyl ethers | |
| CN105268482B (en) | The preparation method of fatty acid methyl ester alkoxylating catalyst | |
| CN107935826A (en) | Good fatty alcohol block polyether of a kind of low-temperature stability and its preparation method and application | |
| CN117700715A (en) | Application of boron carbon nitride catalyst in preparation of fatty alcohol polyether | |
| CN106084197A (en) | A kind of preparation method of narrow ditribution polyethers | |
| CN114940752B (en) | Catalyst for epoxy ring-opening polymerization and preparation method and application thereof | |
| CN114437335B (en) | Synthesis method of wide molecular weight distribution fatty alcohol polyether defoamer | |
| CN114874429A (en) | Polyether macromonomer synthesis method, polyether macromonomer and application | |
| CN114621097A (en) | Method for preparing 2, 4-difluoroaniline through catalytic hydrogenation of 2, 4-difluoronitrobenzene | |
| CN102174186A (en) | Catalyst for preparing polyalkyl glycol allyl amyl ether and preparation method thereof | |
| CN106582744A (en) | Preparation method of catalyst capable of increasing yield of maleic anhydride prepared through n-butane oxidation | |
| CN101392053B (en) | Method for preparing composite catalyst applied to alkylene oxide ring-expansion polymerization and use | |
| CN105732731B (en) | Method for preparing light-colored alkyl glycoside product | |
| EP2281796A1 (en) | Method for producing polyoxyalkylene alkyl ether | |
| CN112851554A (en) | Preparation method of guanidine nitrate | |
| CN113772726B (en) | Preparation method for producing sodium antimonate by using glycol antimony distilled slag | |
| CN109369349A (en) | The preparation method of bis- (3- methylphenoxy) ethane of 1,2- | |
| CN117225415B (en) | Copper-silicon catalyst for catalyzing ethylene glycol and primary alcohol to synthesize long-chain o-glycol in coupling mode, and preparation method and application thereof | |
| CN115536829B (en) | Synthesis method of fatty acid monoethanolamide polyoxyethylene ether | |
| CN113980045B (en) | Method for synthesizing lithium difluoro (oxalato) borate by one-step method | |
| CN112206831B (en) | Catalyst for fatty acid methyl ester ethoxylation, preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |