CN116284738A - Polyether amine and preparation method and application thereof - Google Patents
Polyether amine and preparation method and application thereof Download PDFInfo
- Publication number
- CN116284738A CN116284738A CN202310055661.3A CN202310055661A CN116284738A CN 116284738 A CN116284738 A CN 116284738A CN 202310055661 A CN202310055661 A CN 202310055661A CN 116284738 A CN116284738 A CN 116284738A
- Authority
- CN
- China
- Prior art keywords
- polyether
- amine
- molecular weight
- polyether amine
- alkyl
- 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
- 229920000570 polyether Polymers 0.000 title claims abstract description 93
- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 91
- 150000001412 amines Chemical class 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- -1 alkyl phenolic resin Chemical compound 0.000 claims abstract description 24
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 22
- 239000005011 phenolic resin Substances 0.000 claims abstract description 17
- 239000003599 detergent Substances 0.000 claims abstract description 15
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 5
- 239000003054 catalyst Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 13
- 238000009826 distribution Methods 0.000 claims description 11
- 229910003322 NiCu Inorganic materials 0.000 claims description 8
- 239000003999 initiator Substances 0.000 claims description 7
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 229920005989 resin Polymers 0.000 claims description 6
- 239000011347 resin Substances 0.000 claims description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Substances O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 4
- 239000004973 liquid crystal related substance Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 2
- 238000005913 hydroamination reaction Methods 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 abstract description 10
- 238000004176 ammonification Methods 0.000 abstract description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- 239000000084 colloidal system Substances 0.000 description 6
- 229920001451 polypropylene glycol Polymers 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- JLSMYRQOSYIOCE-UHFFFAOYSA-N 4-dodecylphenol;formaldehyde Chemical compound O=C.CCCCCCCCCCCCC1=CC=C(O)C=C1 JLSMYRQOSYIOCE-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical compound CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N 4-nonylphenol Chemical compound CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- ISAVYTVYFVQUDY-UHFFFAOYSA-N 4-tert-Octylphenol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(O)C=C1 ISAVYTVYFVQUDY-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 238000011020 pilot scale process Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 125000002924 primary amino group Chemical class [H]N([H])* 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- 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
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/321—Polymers modified by chemical after-treatment with inorganic compounds
- C08G65/325—Polymers modified by chemical after-treatment with inorganic compounds containing nitrogen
- C08G65/3255—Ammonia
-
- C—CHEMISTRY; METALLURGY
- 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
- C08G65/2603—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 oxygen
- C08G65/2606—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 oxygen containing hydroxyl groups
- C08G65/2612—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 oxygen containing hydroxyl groups containing aromatic or arylaliphatic hydroxyl groups
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L10/00—Use of additives to fuels or fires for particular purposes
- C10L10/18—Use of additives to fuels or fires for particular purposes use of detergents or dispersants for purposes not provided for in groups C10L10/02 - C10L10/16
-
- C—CHEMISTRY; METALLURGY
- 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
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterized by the type of post-polymerisation functionalisation
- C08G2650/04—End-capping
Abstract
The invention discloses polyether amine and a preparation method and application thereof, and belongs to the technical field of synthesis of gasoline detergents. The polyether amine with the following structural formula is prepared by taking alkyl phenolic resin polyether as a raw material through hydro-ammonification reaction; the polyether amine structure contains a plurality of alkyl groups and benzene rings, and has extremely strong oil solubility; the polyether amine structure also contains a plurality of amine groups, so that the amine value of the polyether amine is higher. Therefore, when the polyether amine prepared by the invention is used as a main agent of a gasoline detergent, the polyether amine has good detergent dispersing performance.
Description
Technical Field
The invention belongs to the technical field of synthesis of gasoline detergents, and particularly relates to polyether amine and a preparation method and application thereof.
Background
Polyetheramines are a class of polyolefin compounds having a soft polyether backbone, terminated with primary or secondary amine groups. The amine terminal of polyether amine is a hydrophilic group, and when the polyether terminal contains a super-strong oil-soluble group and a special framework structure, the polyether amine can have extremely strong oil solubility, so that the specific performance is shown.
The polyether amine can be used as an effective component of the gasoline detergent, plays roles in cleaning and dispersing, and is a recognized fourth-generation gasoline detergent. The polyether amine is added into the motor gasoline, so that the generation of sediments in a fuel system can be inhibited, and the generated oxidized sediments can be rapidly dispersed and removed, thereby ensuring the normal exertion of the dynamic property of an automobile engine and improving the combustion performance of fuel; the CH and CO pollutants in the automobile exhaust are greatly reduced, so that the effects of purifying urban air, reducing automobile maintenance cost and saving oil are achieved.
Chinese patent CN101225332A discloses a polyether amine used as a main agent of a gasoline detergent and a preparation method thereof, wherein alkylphenol polyoxypropylene ether and amine compounds are used as raw materials, raney nickel is used as a catalyst in an intermittent kettle reactor, the reaction temperature is 180-280 ℃, the reaction pressure is 4-21MPa, and the polyether amine is prepared by hydro-ammoniation. The method has the problems of high reaction pressure, intermittent reaction, low production efficiency, high production cost and unstable product quality.
Chinese patent CN106336506B discloses a polyether amine as a gasoline detergent and a synthesis method thereof, polyether and para-amino halogenated benzene are used as raw materials, alkali and a phase transfer catalyst are added to react for 1-4 hours at 65-90 ℃, and then the polyether is obtained through extraction by an organic solvent, washing and drying, filtration and reduced pressure distillation of filtrate. The method can introduce chlorine, alkali metal and other impurity elements, and also needs extraction, water washing, reduced pressure distillation and other purification processes, so that the method has the problems of complex process, difficult treatment of three wastes and the like.
To solve the deficiencies of the prior art, we have sought an ideal solution.
Disclosure of Invention
The invention aims to: the invention aims at overcoming the defects of the prior art and provides polyether amine and a preparation method and application thereof. The polyether amine structure contains a plurality of alkyl groups and benzene rings, and has extremely strong oil solubility; the polyether amine structure also contains a plurality of amine groups, so that the amine value of the polyether amine is higher. Therefore, when the polyether amine is used as a main agent of the gasoline detergent, the polyether amine has good detergent dispersion performance, and the problems of the polyether amine for the gasoline detergent are partially solved.
The technical scheme is as follows: the aim of the invention is achieved by the following technical scheme:
the invention provides polyetheramine having the following structural formula:
wherein, the liquid crystal display device comprises a liquid crystal display device,
n, x, y, z are integers greater than or equal to 0;
R 1 、R 2 …R n+2 each independently selected from alkyl groups having a carbon chain length of from 4 to 15;
R′ 1 、R′ 2 …R′ n+2 each independently selected from- (C) 2 H 4 )-、-(C 3 H 6 ) -or- (C) 4 H 8 )-。
The invention also provides a preparation method of the polyether amine with the structural formula, and the polyether amine is prepared by taking alkyl phenolic resin polyether as a raw material and carrying out hydro-ammoniation reaction.
The reaction equation is shown below:
the alkyl phenolic resin polyether is selected as the raw material, and contains a plurality of groups with extremely strong oil solubility, namely alkyl and benzene rings, so that the prepared polyether amine has extremely strong oil solubility, can be rapidly dissolved and dispersed into gasoline, and further fully plays the cleaning and dispersing performances. In addition, as can be seen from the reaction equation, the alkyl phenolic resin polyether has (n+1) hydroxyl groups, and can generate (n+1) amino groups by reacting with ammonia, so that the polyether amine obtained by the reaction has excellent cleaning and dispersing performance.
In order to improve the oil solubility of polyetheramine, a preferred embodiment of the present invention is that the alkylphenol-formaldehyde resin polyether is a polyether obtained by reacting one or a mixture of several of ethylene oxide, propylene oxide and butylene oxide with an alkylphenol-formaldehyde resin as an initiator, more preferably propylene oxide and butylene oxide.
Further preferably, the alkyl phenol-formaldehyde resin polyether is prepared by reacting an alkyl phenol-formaldehyde resin as an initiator with propylene oxide and butylene oxide.
Further preferably, the alkyl phenol resin has an alkyl carbon chain length of from 4 to 15 and an average molecular weight of from 500 to 2000.
Still further, the alkyl phenol resin has an alkyl carbon chain length of from C6 to 12 and an average molecular weight of from 500 to 1500.
In order to improve the polyetheramine properties, it is preferred that the alkylphenol polyethers have an average molecular weight of 600 to 5000, a molecular weight distribution of less than 3.0 and a K content of less than 50ppm. Further preferably, the alkyl phenol formaldehyde polyether has an average molecular weight of 600 to 3000, a molecular weight distribution of less than 2.5 and a K content of less than 30ppm. The higher the average molecular weight of the alkyl phenolic resin polyether is, the better the oil solubility is, but the higher the molecular weight is, the higher the viscosity is, and the hydro-ammoniation reaction is affected; the narrower the molecular weight distribution, the better the performance of the polyetheramine; k ions affect the selectivity of the hydro-amination.
Preferably, the hydro-ammonification reaction is performed in a fixed bed reactor, which is filled with a supported catalyst.
In order to enhance the catalytic effect, it is further preferable that the supported catalyst is a NiCu supported catalyst.
The invention also provides application of the polyether amine with the structural formula as a main agent of the gasoline detergent.
The technology not mentioned in the present invention refers to the prior art.
The beneficial effects are that:
(1) The invention takes alkyl phenolic resin polyether as a raw material, and polyether amine is prepared by hydro-ammonification reaction; the polyether amine structure contains a plurality of alkyl groups and benzene rings, so that the prepared polyether amine has extremely strong oil solubility and can be quickly dissolved and dispersed into an oil-soluble system. In addition, the polyether amine structure of the invention also contains a plurality of amine groups, so that the polyether amine has higher amine value. The polyether amine values of the invention are higher than that of the imported sample, and the unwashed colloid content and the washed colloid content are lower than those of the imported sample, which shows that the clean dispersion performance of the polyether amine prepared by the invention is superior to that of the imported sample.
(2) The polyether amine with the specific structure can be continuously prepared in a fixed bed reactor, and is favorable for operation stability and reaction safety.
Detailed Description
The technical scheme of the present invention is described in detail below through specific examples, but the scope of the present invention is not limited to the examples.
Raw materials:
alkyl phenolic resin is prepared by adopting a preparation method of Chinese patent CN 103910839B;
the preparation method of the NiCu supported catalyst comprises the following steps: niCuAl nitric acid solution is used as raw material, na 2 CO 3 The solution is a precipitator, a NiCuAl precipitation precursor is prepared by coprecipitation at 85 ℃, and then cylindrical NiCu supported catalyst (with the diameter of 3mm and the height of 3 mm) is prepared by drying, granulating, roasting and tabletting, wherein the Ni content is 25% and the Cu content is 2%;
liquid ammonia, nanjing specialty gases Co., ltd., industrial grade, 99.999%; hydrogen, 99.999% of Nanjing long specialty gases, inc., industrial grade.
Instrument: and a fixed bed pilot scale evaluation device, wherein the catalyst filling amount is 200ml,350 ℃ and 15MPa.
The number average molecular weight and molecular weight distribution of the polyethers and polyetheramines were determined by Waters gel chromatograph Alliance e2695GPC equipped with 2414 differential refractive detector host and Waters styragel HR, HR3 and HR4 columns with tetrahydrofuran as the mobile phase.
The amine number of the polyetheramine was determined using the American Standard ASTMD 2074-07.
Vehicle gasoline detergency test (gasoline engine inlet valve deposit experiment) according to the standard of GB 19592-2019 vehicle gasoline detergent, an L-2 vehicle gasoline detergency tester (Lanzhou View petrochemical Instrument Co., ltd.) is used for testing the content of unwashed colloid and washed colloid on a spray plate, and the oil sample ratio is as follows: 300ml of 92# gasoline + 600. Mu.l of scorch retarder + 20. Mu.l of polyether amine sample were tested at 175 ℃.
The preparation and refining of the polyether in the invention are conventional technical means in the field, and the invention can be seen from the prior art to the point where the invention is not fully described.
Example 1
The p-tert-octyl phenolic resin with the average molecular weight of 556 is taken as an initiator, KOH is taken as a catalyst, the dosage is three thousandths of the mass of polyether, the reaction temperature is 140-160 ℃, the pressure is 0-0.6MPa, and the obtained crude polyether is refined to remove K to obtain p-tert-octyl phenolic resin polyoxypropylene ether with the average molecular weight of 698, the molecular weight distribution of 2.5 and the K content of 26 ppm.
The tert-octyl phenolic resin polyoxypropylene ether (polyether) is subjected to hydro-ammonification reaction in a fixed bed reactor filled with NiCu supported catalyst, and the polyether is NH 3 :H 2 The molar ratio is 1:8:10, the reaction temperature is 270 ℃, and the reaction pressure is 6.5MPa, so that the polyether amine sample 1 is obtained.
Example 2
The method comprises the steps of taking p-hexyl phenolic resin with average molecular weight of 1462 as an initiator, KOH as a catalyst, using three thousandths of polyether mass, reacting with propylene oxide at the reaction temperature of 140-160 ℃ and the pressure of 0-0.6MPa, and refining the obtained crude polyether to remove K to obtain p-hexyl phenolic resin polyoxypropylene ether with average molecular weight of 2869, molecular weight distribution of 1.7 and K content of 2 ppm.
The polyether is subjected to hydro-ammonification reaction in a fixed bed reactor filled with NiCu supported catalyst, and the polyether is NH 3 :H 2 The molar ratio is 1:8:10, the reaction temperature is 270 ℃, and the reaction pressure is 6.5MPa, so that the polyether amine sample 2 is obtained.
Example 3
The p-dodecyl phenol formaldehyde resin with the average molecular weight of 866 is taken as an initiator, KOH is taken as a catalyst, the dosage is three thousandths of the mass of polyether, the catalyst reacts with epoxybutane, the reaction temperature is 140-160 ℃, the pressure is 0-0.6MPa, and the obtained crude polyether is refined to remove K, so that the p-dodecyl phenol formaldehyde resin polyoxybutylene ether with the average molecular weight of 1562, the molecular weight distribution of 1.6 and the K content of 12ppm is prepared.
The p-tert-dodecyl phenol formaldehyde resin polyoxybutylene ether (polyether) is filled with NiCu supported catalystThe hydro-ammonification reaction is carried out in a fixed bed reactor of the catalyst, and the polyether is NH 3 :H 2 The molar ratio is 1:8:10, the reaction temperature is 270 ℃, and the reaction pressure is 6.5MPa, so that the polyether amine sample 3 is obtained.
Example 4
The method comprises the steps of taking a mixture of p-nonylphenol resin and p-tert-octylphenol resin with an average molecular weight of 1246 as an initiator, KOH as a catalyst, and the dosage of three thousandths of the weight of polyether, reacting with propylene oxide at a reaction temperature of 140-160 ℃ and a pressure of 0-0.6MPa, and refining the obtained crude polyether to remove K to obtain the mixed alkyl phenol resin polyoxypropylene ether with an average molecular weight of 2126, a molecular weight distribution of 1.4 and a K content of 6 ppm.
The mixed alkyl phenolic resin polyoxypropylene ether (polyether) is subjected to hydro-ammoniation reaction in a fixed bed reactor filled with NiCu supported catalyst, and the polyether is NH 3 :H 2 The molar ratio is 1:8:10, the reaction temperature is 270 ℃, and the reaction pressure is 6.5MPa, so that the polyether amine sample 4 is obtained.
Amine number and gasoline engine intake valve deposit tests were performed on polyetheramine sample 1, polyetheramine sample 2, polyetheramine sample 3, and polyetheramine sample 4 prepared in examples 1-4.
Comparative example 1
The U.S. hounsmei polyetheramine FL1000 was selected as comparative example 1 for amine number and gasoline engine intake valve deposit testing.
Comparative example 2
Polyether amine (GP 9201) from Wuhan Pa Pu An technology Co., ltd was used as comparative example 2 for amine number and gasoline engine intake valve deposit tests.
Table 1 shows the polyether amine values of examples 1-4 and comparative examples 1-2 and the results of gasoline engine intake valve deposit tests.
Table 1 test results
| Sample of | Amine number | Unwashed gum (mg) | Post-cleaning gum (mg) |
| Polyether amine sample 1 | 1.02 | 7.2 | 0.3 |
| Polyether amine sample 2 | 0.94 | 9.6 | 0.5 |
| Polyether amine sample 3 | 0.98 | 8.0 | 0.3 |
| Polyether amine sample 4 | 1.01 | 6.9 | 0.2 |
| Import sample FL1000 | 0.92 | 10.2 | 0.8 |
| Domestic sample GP9201 | 54.4 | 12.4 | 1.4 |
As can be seen from Table 1, the polyether amine samples prepared in examples 1-4 all had amine values higher than the imported sample FL1000, and the unwashed gum content and the washed gum content were lower than the imported sample, which indicates that the clean dispersion properties of the polyether amine samples prepared in accordance with the present invention were better than the imported sample.
The domestic sample GP9201 has higher amine value because the structure of the domestic sample GP9201 has larger difference with that of the polyether amine of the embodiment and the imported sample; the polyether amine has a plurality of structures and wide amine value distribution, but the polyether amine suitable for being used as the gasoline detergent is quite few, so that the polyether amine is not only required to have high amine value, but also required to have good oil solubility. From Table 1, the content of unwashed colloid and the content of colloid after washing of the domestic sample are higher than those of the samples and imported samples of the examples, which is probably because the domestic sample has poor oil solubility, is difficult to uniformly disperse in an oil-soluble system, and affects the cleaning dispersion performance.
As described above, although the present invention has been shown and described with reference to certain preferred embodiments, it is not to be construed as limiting the invention itself. Various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. A polyetheramine having the structural formula:
wherein, the liquid crystal display device comprises a liquid crystal display device,
n, x, y, z are integers greater than or equal to 0;
R 1 、R 2 …R n+2 each independently selected from alkyl groups having a carbon chain length of from 4 to 15;
R′ 1 、R′ 2 …R′ n+2 each independently selected from- (C) 2 H 4 )-、-(C 3 H 6 ) -or- (C) 4 H 8 )-。
2. The method for preparing the polyether amine according to claim 1, wherein the polyether amine is prepared by taking alkyl phenolic resin polyether as a raw material and carrying out hydro-ammoniation reaction.
3. The preparation method according to claim 2, wherein the alkylphenol-formaldehyde resin polyether is prepared by reacting an alkylphenol-formaldehyde resin as an initiator with one or a mixture of several of ethylene oxide, propylene oxide or butylene oxide.
4. A process according to claim 3, wherein the alkyl phenol-formaldehyde resin has an alkyl carbon chain length of from C4 to 15 and an average molecular weight of from 500 to 2000.
5. The process of claim 4, wherein the alkyl phenol-formaldehyde resin has an alkyl carbon chain length of from 6 to 12 and an average molecular weight of from 500 to 1500.
6. The process of claim 2 wherein the alkylphenol polyether has an average molecular weight of 600 to 5000, a molecular weight distribution of less than 3.0 and a k content of less than 50ppm.
7. The process of claim 6 wherein the alkylphenol polyether has an average molecular weight of 600 to 3000, a molecular weight distribution of less than 2.5 and a k content of less than 30ppm.
8. The process according to claim 2, wherein the hydro-amination reaction is carried out in a fixed bed reactor, which is filled with a supported catalyst.
9. The method of claim 8, wherein the supported catalyst is a NiCu supported catalyst.
10. Use of the polyetheramine of claim 1 as a main agent for a gasoline detergent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310055661.3A CN116284738A (en) | 2023-01-17 | 2023-01-17 | Polyether amine and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310055661.3A CN116284738A (en) | 2023-01-17 | 2023-01-17 | Polyether amine and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116284738A true CN116284738A (en) | 2023-06-23 |
Family
ID=86789638
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310055661.3A Pending CN116284738A (en) | 2023-01-17 | 2023-01-17 | Polyether amine and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116284738A (en) |
-
2023
- 2023-01-17 CN CN202310055661.3A patent/CN116284738A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103374085B (en) | A kind of Mannich base, its manufacture method and application thereof | |
| CN104761718B (en) | A kind of novel polyether amine and its synthetic method as gasoline cleaning agent | |
| CN113402705B (en) | Polyether amine and preparation method and application thereof | |
| CN101225332A (en) | Polyethenoxyamines used as main agent of gasoline detergent and preparation method thereof | |
| CN104151148B (en) | Prepared the method for polyoxymethylene dimethyl ethers by paraformaldehyde | |
| CN103739458B (en) | The preparation method of polyoxymethylene dimethyl ethers | |
| CN102247896A (en) | Alumina-zirconia composite carrier and preparation method thereof | |
| US20220315675A1 (en) | Preparation method of highly aromatic hydrocarbon hydrogenated resin | |
| CN109970553B (en) | Method for preparing 2,3, 5-trimethylhydroquinone diester | |
| CN116284738A (en) | Polyether amine and preparation method and application thereof | |
| CN114874431A (en) | Preparation method of tertiary amine-terminated polyether type nonionic surfactant | |
| CN111686746A (en) | Low-temperature methanation catalyst and preparation method thereof | |
| CN1219033C (en) | Fractional oil hydrogenation desulphurizing and deacromating process | |
| CN107915836B (en) | Polyether amine and preparation method thereof | |
| CN102471189A (en) | Method for producing low-odor n-butane | |
| CN113444237B (en) | Quaternized polyether reverse demulsifier and preparation method thereof | |
| CN103420812B (en) | Polymethoxy dimethyl ether preparation method | |
| CN105413694A (en) | Catalyst for catalyzing hydrogenation of petroleum resin as well as preparation method and application thereof | |
| CN113522182A (en) | Preparation method of used oil collecting agent for low-rank coal flotation | |
| CN103664546B (en) | Prepare the method for polymethoxy dimethyl ether | |
| CN115739102B (en) | Preparation method of hydroamination catalyst and method for amination reaction of polyether polyol | |
| CN105860053B (en) | A kind of continuous method and its special-purpose catalyst for preparing end secondary amino group polyethers | |
| CN111334349A (en) | High-cleanness methanol gasoline vehicle fuel | |
| CN1031409C (en) | Assistant for increasing octane value of gasoline and yield rate of propene and butene | |
| CN110484312B (en) | Gasoline detergent and preparation method thereof |
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 |