CN118344511A - Mannich base and preparation method and application thereof - Google Patents
Mannich base and preparation method and application thereof Download PDFInfo
- Publication number
- CN118344511A CN118344511A CN202310066511.2A CN202310066511A CN118344511A CN 118344511 A CN118344511 A CN 118344511A CN 202310066511 A CN202310066511 A CN 202310066511A CN 118344511 A CN118344511 A CN 118344511A
- Authority
- CN
- China
- Prior art keywords
- formula
- group
- linear
- mannich base
- branched 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
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 29
- 239000003502 gasoline Substances 0.000 claims abstract description 20
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 19
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 15
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 15
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 5
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract 3
- 150000001875 compounds Chemical class 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 28
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical group O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 22
- 239000003599 detergent Substances 0.000 claims description 21
- 150000002192 fatty aldehydes Chemical class 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 9
- 239000003085 diluting agent Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 6
- 229920000570 polyether Polymers 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 150000002430 hydrocarbons Chemical class 0.000 claims description 5
- 239000010688 mineral lubricating oil Substances 0.000 claims description 5
- 229920000098 polyolefin Polymers 0.000 claims description 5
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- CJAOGUFAAWZWNI-UHFFFAOYSA-N 1-n,1-n,4-n,4-n-tetramethylbenzene-1,4-diamine Chemical compound CN(C)C1=CC=C(N(C)C)C=C1 CJAOGUFAAWZWNI-UHFFFAOYSA-N 0.000 claims description 2
- OBCSAIDCZQSFQH-UHFFFAOYSA-N 2-methyl-1,4-phenylenediamine Chemical compound CC1=CC(N)=CC=C1N OBCSAIDCZQSFQH-UHFFFAOYSA-N 0.000 claims description 2
- XBTWVJKPQPQTDW-UHFFFAOYSA-N 4-n,4-n-diethyl-2-methylbenzene-1,4-diamine Chemical compound CCN(CC)C1=CC=C(N)C(C)=C1 XBTWVJKPQPQTDW-UHFFFAOYSA-N 0.000 claims description 2
- SKIBELYSXFYZPS-UHFFFAOYSA-N 4-n-ethylbenzene-1,4-diamine Chemical compound CCNC1=CC=C(N)C=C1 SKIBELYSXFYZPS-UHFFFAOYSA-N 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 claims 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 abstract description 17
- 230000015572 biosynthetic process Effects 0.000 abstract description 9
- 238000004140 cleaning Methods 0.000 abstract description 6
- 230000005764 inhibitory process Effects 0.000 abstract description 3
- 230000002265 prevention Effects 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 29
- 239000000047 product Substances 0.000 description 29
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 24
- 239000001257 hydrogen Substances 0.000 description 17
- 239000000126 substance Substances 0.000 description 12
- 238000002329 infrared spectrum Methods 0.000 description 11
- 239000013049 sediment Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
- -1 amine compounds Chemical class 0.000 description 10
- 238000001228 spectrum Methods 0.000 description 10
- 238000005481 NMR spectroscopy Methods 0.000 description 8
- 229920002367 Polyisobutene Polymers 0.000 description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 6
- 238000004821 distillation Methods 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 239000000446 fuel Substances 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- BZORFPDSXLZWJF-UHFFFAOYSA-N N,N-dimethyl-1,4-phenylenediamine Chemical compound CN(C)C1=CC=C(N)C=C1 BZORFPDSXLZWJF-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000005804 alkylation reaction Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000005452 bending Methods 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 230000002401 inhibitory effect Effects 0.000 description 4
- 239000008096 xylene Substances 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical group C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- IUNMPGNGSSIWFP-UHFFFAOYSA-N dimethylaminopropylamine Chemical compound CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 3
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 239000004711 α-olefin Substances 0.000 description 3
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- RREANTFLPGEWEN-MBLPBCRHSA-N 7-[4-[[(3z)-3-[4-amino-5-[(3,4,5-trimethoxyphenyl)methyl]pyrimidin-2-yl]imino-5-fluoro-2-oxoindol-1-yl]methyl]piperazin-1-yl]-1-cyclopropyl-6-fluoro-4-oxoquinoline-3-carboxylic acid Chemical compound COC1=C(OC)C(OC)=CC(CC=2C(=NC(\N=C/3C4=CC(F)=CC=C4N(CN4CCN(CC4)C=4C(=CC=5C(=O)C(C(O)=O)=CN(C=5C=4)C4CC4)F)C\3=O)=NC=2)N)=C1 RREANTFLPGEWEN-MBLPBCRHSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- 238000006683 Mannich reaction Methods 0.000 description 2
- 229930040373 Paraformaldehyde Natural products 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 239000002872 contrast media Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012847 fine chemical Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N n-decene Natural products CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 150000002924 oxiranes Chemical class 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229920002866 paraformaldehyde Polymers 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 150000003335 secondary amines Chemical group 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OYWRDHBGMCXGFY-UHFFFAOYSA-N 1,2,3-triazinane Chemical compound C1CNNNC1 OYWRDHBGMCXGFY-UHFFFAOYSA-N 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical group NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000002199 base oil Substances 0.000 description 1
- CNQCIQAIIFAKGC-UHFFFAOYSA-N benzene;2-methylphenol Chemical group C1=CC=CC=C1.CC1=CC=CC=C1O CNQCIQAIIFAKGC-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000001236 detergent effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920013639 polyalphaolefin Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a Mannich base and a preparation method and application thereof. The structure of the Mannich base is shown as a formula (I): In formula (I), R 0 is selected from the group consisting of linear or branched alkylene of C 1～8; each R 1, equal to or different from each other, is independently selected from the group consisting of linear or branched alkyl groups of H, C 1～4; each R 1' is independently selected from the group consisting of linear or branched alkyl and phenyl of H, C 1～4; r 2 is selected from hydrocarbon groups with the number average molecular weight Mn of 300-3000; r 3 is selected from the group consisting of linear or branched alkyl of C 1～6. The Mannich base disclosed by the invention can be applied to gasoline, and has very excellent cleaning performance, deposit formation inhibition performance and rust prevention performance.
Description
Technical Field
The invention relates to a gasoline detergent, in particular to a Mannich base detergent with a phenylenediamine structure.
Background
The gasoline fuel contains polyunsaturated hydrocarbons and sulfur and nitrogen compounds, is easily contacted with air in the storage and use processes and is oxidized into colloid, carbon deposition and sediments are directly generated in an electric nozzle, an air inlet valve and a combustion chamber in the fuel combustion process, so that the problems of unsmooth oil supply, air-fuel ratio imbalance, incomplete combustion, fuel waste, reduction of engine efficiency and the like are caused, a large amount of harmful gases are discharged, and friction and abrasion among moving parts are increased.
In order to solve the problems of the gasoline in the combustion process, one or more multi-effect composite additives are generally added into the existing gasoline fuel, the performance among different additives is utilized to play a role in improving the performance of the gasoline, and meanwhile, the cleanliness and the oxidation resistance of the gasoline are improved. At present, most of the latest generation of detergent main agents use Mannich base, so that the deposit of an air inlet valve can be effectively removed.
A mixture of mannich base detergents is reported in US 20160289584A1 comprising a first mannich base detergent component derived from a diamine or polyamine and a second mannich base detergent component derived from a monoamine, but the manner of synthesis and detergency properties of the diamine-type amine compounds reported are not disclosed in the examples.
A Mannich base prepared from a polyamine containing a primary amino group, a hydroxyaromatic compound and an aldehyde is reported in U.S. Pat. No. 3, 8557003B2 to have a good effect on removal of intake valve deposits.
In US 7384434B 2a mannich base is reported which is prepared by reacting hexahydrotriazine with hydroxyaromatic compounds, the reaction product of which is similar to the structure synthesized using N, N-dimethyl-1, 3-propanediamine, with a large number of byproducts and the detergent effect being improved.
GB 19592-2019 puts higher demands on the detergency of gasoline, and there is still a need in the art for a Mannich base detergent with better detergency, deposit formation inhibition and rust prevention.
Disclosure of Invention
The invention provides a Mannich base and a preparation method and application thereof.
The present invention includes the following aspects.
In a first aspect, the present invention provides a mannich base.
The structure of the Mannich base is shown as a formula (I):
In formula (I), R 0 is selected from the group consisting of linear or branched alkylene of C 1～8; each R 1, equal to or different from each other, is independently selected from the group consisting of linear or branched alkyl groups of H, C 1～4; each R 1' is independently selected from the group consisting of linear or branched alkyl and phenyl of H, C 1～4; r 2 is selected from hydrocarbon groups with the number average molecular weight Mn of 300-3000; r 3 is selected from the group consisting of linear or branched alkyl of C 1～6.
According to the invention, preferably, R 0 is selected from the group consisting of linear or branched alkylene of C 1～4, each R 1 is independently selected from H or methyl, each R 1' is independently selected from H, methyl, R 2 is selected from polyisobutenyl having a number average molecular weight Mn of 500-2500; r 3 is selected from the group consisting of linear or branched alkyl of C 1～4.
In a second aspect, the invention provides a method for preparing a mannich base.
The preparation method of the Mannich base comprises the steps of reacting a compound shown in a formula (X), fatty aldehyde and a compound shown in a formula (Y), and collecting a product;
In the formula (X), R 2 is selected from hydrocarbon groups with a number average molecular weight Mn of 300-3000; r 3 is selected from the group consisting of linear or branched alkyl of C 1～6;
The carbon number of the fatty aldehyde is 1-8;
In formula (Y), each R 1, equal to or different from each other, is independently selected from the group consisting of linear or branched alkyl groups of H, C 1～4; each R 1' is independently selected from the group consisting of linear or branched alkyl and phenyl of H, C 1～4.
According to the invention, preferably, in formula (X), R 2 is selected from polyisobutenyl groups having a number average molecular weight Mn of 500 to 2500, R 3 is selected from linear or branched alkyl groups of C 1～4; the carbon number of the fatty aldehyde is 1-4; in formula (Y), each R 1 is independently selected from H or methyl, and each R 1' is independently selected from H, methyl.
According to the invention, the compounds of formula (X) can be prepared by alkylation of phenols and/or mono-ortho C 1～6 -alkylphenols with polyolefins. The alkylation reaction can be referred to as an alkylation reaction method as proposed in CN 103664655A.
According to the invention, the fatty aldehyde is preferably formaldehyde or acetaldehyde, more preferably formaldehyde, which may be aqueous formaldehyde, paraformaldehyde or paraformaldehyde.
According to the present invention, the compound represented by the formula (Y) may be selected from one or more of p-phenylenediamine, 2-methyl-p-phenylenediamine, tetramethyl-p-phenylenediamine, N-dimethyl-1, 4-phenylenediamine, N-ethyl-p-phenylenediamine, N-diethyl-p-phenylenediamine and N, N-diethyl-3-methyl-p-phenylenediamine.
According to the present invention, the molar ratio between the compound represented by the formula (X), the fatty aldehyde, and the compound represented by the formula (Y) is preferably 1:0.1 to 3.5:0.3 to 3.
According to the present invention, the reaction temperature between the compound represented by the formula (X), the fatty aldehyde and the compound represented by the formula (Y) is 50 to 200 ℃, preferably 80 to 180 ℃, and most preferably 90 to 160 ℃.
According to the present invention, the longer the reaction time between the compound represented by the formula (X), the fatty aldehyde and the compound represented by the formula (Y) is, the better, and the longer the reaction time is, the more preferably, 1 to 10 hours, more preferably, 2 to 8 hours, and most preferably, 3 to 6 hours.
According to the present invention, a solvent selected from hydrocarbons having a boiling point of 100 to 160 c, such as toluene, xylene, and solvent gasoline No. 150, may be added to the reaction of the compound represented by the formula (X), the fatty aldehyde, and the compound represented by the formula (Y), and the solvent may be added in an amount of 2 to 80%, preferably 10 to 70% by mass of the compound represented by the formula (X). The solvent may be removed after the end of the reaction by methods known in the art, such as a reduced pressure distillation method.
According to the present invention, a diluent may be added to the reaction of the compound represented by the formula (X), the fatty aldehyde, and the compound represented by the formula (Y), and the diluent may be one or more of mineral lubricating oil, polyolefin, and polyether. The mineral lubricating oil can be selected from API I, II and III mineral lubricating oil, preferably mineral lubricating oil with viscosity of 20-120 cSt at 40 ℃ and viscosity index of more than 50; the polyolefin is polyolefin obtained by polymerizing ethylene, propylene and alpha-olefin singly or jointly, wherein the alpha-olefin comprises one or more of n-butene, isobutene, n-pentene, n-hexene, n-octene and n-decene, and the polyalphaolefin with the viscosity of 2-25 cSt at 100 ℃ is preferred; the polyether is a polymer generated by reacting alcohol with epoxide, wherein the alcohol is ethylene glycol and/or 1, 3-propylene glycol, the epoxide is ethylene oxide and/or propylene oxide, and the number average molecular weight of the polyether is 500-3000, preferably 700-3000. After the reaction of the compound represented by the formula (X), the fatty aldehyde and the compound represented by the formula (Y) is completed, the diluent can be separated and removed, or the diluent can be remained in the reaction product, wherein the reaction product is a composition containing the Mannich base and the diluent, and the composition can be added into gasoline as a detergent concentrate for use. The detergent concentrate can also be obtained by mixing the prepared Mannich base product with a diluent at 20-60 ℃ for 1-6 h.
The Mannich base disclosed in the first aspect or the Mannich base prepared by the method disclosed in the second aspect can be applied to gasoline, and has very excellent detergency, deposit formation inhibition and rust prevention.
In a third aspect, the present invention provides the use of a mannich base as set forth in the first aspect and the use of a mannich base as produced according to the method of the second aspect.
The mannich base may be used as a gasoline detergent.
Drawings
FIG. 1 is a comparative infrared spectrum of a highly reactive polyisobutylene starting material and a polyisobutenyl ortho-methylphenol product of example 1, wherein the upper panel (1) is the infrared spectrum of a highly reactive polyisobutylene and the lower panel (2) is the infrared spectrum of a polyisobutenyl ortho-methylphenol product.
FIG. 2 is the high field portion of the nuclear magnetic resonance hydrogen spectrum (1H NMR) of the polyisobutenyl ortho-methylphenol product of example 1.
FIG. 3 is the nuclear magnetic resonance hydrogen spectrum (1H NMR) low field portion of the polyisobutenyl ortho-methylphenol product of example 1.
FIG. 4 is an infrared spectrum of the product of example 2.
FIG. 5 is a nuclear magnetic resonance hydrogen spectrum of the product of example 2.
FIG. 6 is an infrared spectrum of the product of comparative example 1.
FIG. 7 is a nuclear magnetic resonance hydrogen spectrum of the product of comparative example 1.
Detailed Description
The invention is further illustrated by the following examples, which are not to be construed as limiting the invention.
The comparative examples all adopt the main methods reported in the current patent literature for the synthesis of Mannich bases.
The main raw materials used are as follows: o-cresol, AR, shanghai aladine biochemistry technologies, inc; highly reactive polyisobutylene (HRPIB, mn ≡ 1000), product of yangzi petrochemicals-basf, inc; n-hexane, GC, product of beijing enokic technologies limited; toluene, AR, beijing enoki technologies limited; xylene, AR, a product of the company, rich and fine chemical engineering, tianjin; commercial gasoline detergent 6416, yafuton corporation; anhydrous methanol, AR, tianjin metallocene chemical plant products; aqueous formaldehyde solution, 37%, product of sameiser's technology (china) limited; boron trifluoride diethyl etherate, beijing enoki technology Co., ltd; p-phenylenediamine, N-dimethyl-1, 4-phenylenediamine, GC, shanghai aladine biochemical technologies, inc; ethylenediamine, AR, beijing enokic technologies limited; s150, aromatic hydrocarbon solvent, polyether and Beijing Xingpu fine chemical technology development limited company; n, N-dimethyl-1, 3-propanediamine, AR, beijing enokic technologies Co., ltd; 1,3, 5-tris (dimethylaminopropyl) -1,3, 5-hexahydrotriazine, AR, beijing enokawa technologies limited.
EXAMPLE 1 Synthesis of polyisobutenyl ortho-methylphenols
Into a 1L reaction vessel equipped with a stirrer, an N 2 -inlet tube, a thermocouple thermometer, a bulb condenser and a feed pump, 64.96g (0.601 mol) of o-cresol, 12.88g (0.091 mol) of boron trifluoride diethyl ether catalyst, 215.03g of N-hexane solvent and 300.91g (0.300 mol) of polyisobutylene (Mn=1000) were charged and reacted at 30℃for 6 hours. After the reaction is finished, 64ml of deionized water is added, the mixture is transferred to a 1L separating funnel, 160ml of methanol is added, the mixture is kept stand for 1h for layering after oscillation, the lower liquid is separated out and is repeated twice, and the upper liquid is distilled under reduced pressure to obtain a light yellow polyisobutenyl o-methylphenol product. F content in the product is less than 1ppm through elemental analysis, o-cresol content is less than 0.006% through GC-MS analysis, and polyisobutenyl o-methylphenol yield is 99% through oxygen content analysis.
FIG. 1 is a comparative infrared spectrum of a highly reactive polyisobutylene starting material and a polyisobutenyl ortho-methylphenol product of example 1, wherein the upper panel (1) is the infrared spectrum of a highly reactive polyisobutylene and the lower panel (2) is the infrared spectrum of a polyisobutenyl ortho-methylphenol product.
As can be seen from fig. 1, after the alkylation reaction is completed, the characteristic peaks of the Highly Reactive Polyisobutylene (HRPIB) disappear are: 3070cm -1 (asymmetric stretching vibration of terminal α -olefin C-H bond), 1640cm -1 (stretching vibration of terminal α -methylene c=c double bond). The characteristic absorption peaks of the synthetic polyisobutenyl o-methylphenol are: 3620cm -1 (no stretching vibration peak of the association agent free phenolic hydroxyl O-H, sharp peak shape), 3500-3200cm -1 (O-H stretching vibration of the phenolic hydroxyl after intermolecular hydrogen bond association is wide absorption peak), 1605cm -1 and 1505cm -1 (two absorption bands of skeleton vibration of single-core aromatic hydrocarbon C=C double bond), 1262cm -1 (stretching vibration absorption peak of Ar-O on benzene ring) and 818cm -1 (out-of-plane bending vibration of C-H on benzene ring when benzene ring generates 1,2,4 substitution).
FIG. 2 is the high field portion of the nuclear magnetic resonance hydrogen spectrum (1H NMR) of the polyisobutenyl ortho-methylphenol product of example 1. FIG. 3 is the nuclear magnetic resonance hydrogen spectrum (1 HNMR) low field portion of the polyisobutenyl ortho-methylphenol product of example 1.
As can be seen from fig. 2 and 3, at chemical shift 2.261, there is a characteristic peak of methyl hydrogen on the polyisobutenyl ortho-methylphenol benzene ring; at chemical shift 4.561, there is a characteristic peak of hydroxyl hydrogen on the polyisobutenyl o-methylphenol benzene ring; the integral of methyl hydrogen was defined as 3, resulting in an integral ratio of hydrogen, hydroxyl hydrogen and methyl hydrogen on the benzene ring of 0.98:0.99:0.98:0.97:3.00, approaching theoretical 1:1:1:1:3, so that the polyisobutenyl o-methylphenol as the target product is prepared by nuclear magnetic analysis.
An example reaction equation for example 1 is as follows.
EXAMPLE 2 Synthesis of Mannich bases
55.11G of polyisobutenyl o-methylphenol, 56.03g of dimethylbenzene and 6.14g of N, N-dimethyl-1, 4-phenylenediamine in example 1 are added into a four-neck flask provided with an N 2 inlet pipe, a thermocouple thermometer, a spherical condenser pipe and a feed pump, 4.89g of formaldehyde aqueous solution with the mass concentration of 37% is dropwise added, the temperature is raised to 150 ℃ for reaction for 3 hours, and after the reaction is finished, the mannich base is obtained through reduced pressure distillation.
FIG. 4 is an infrared spectrum of the product of example 2. As can be seen from fig. 4, the characteristic peaks generated after the synthesis of the mannich base are: 3500-3300cm -1 (N-H stretching vibration, and O-H stretching vibration overlap, peak shape further widens), 1749.35cm -1 (broad band of C-H out-of-plane bending vibration of benzene ring when 1,2,4,6 substitution occurs), 1162.11cm -1 and 1056.47cm -1 (fatty amine C-N stretching vibration), 871.49cm -1 (C-H out-of-plane bending vibration of benzene ring when 1,2,4,6 substitution occurs).
FIG. 5 is a nuclear magnetic resonance hydrogen spectrum of the product of example 2.
As can be seen from FIG. 5, in the nuclear magnetic spectrum of the Mannich product, the chemical shift is 5.23 of proton hydrogen on secondary amine group of N, N-dimethyl-1, 4-phenylenediamine for Mannich reaction, the shift peak of hydrogen proton on methylene generated by carbonyl conversion of formaldehyde is 4.47, the chemical shift is 2.84 of methyl proton peak of N, N-dimethyl-1, 4-phenylenediamine, and the area ratio of the three is 1:1.99: and 6.03, which accords with the theoretical area ratio. In addition, the lower field is more disordered because the peaks of the two benzene rings overlap each other, but the benzene ring peak of the higher field can still be seen as the benzene ring on the N, N-dimethyl-1, 4-phenylenediamine, and the area accords with the proportion. The chemical shift peak of the hydroxyl group on the benzene ring disappears because the content of the hydroxyl group in the whole chemical molecule is low, and part of the hydroxyl group participates in the reaction, so that the content of the hydroxyl group is further reduced, and the disappearance of the chemical shift peak of the hydroxyl proton is caused, and the by-products are less.
The yield obtained by analysis of the oxygen content was 84%.
An example reaction equation for example 2 is as follows.
Example 3
Into a four-necked flask equipped with an N 2 inlet pipe, a thermocouple thermometer, a spherical condenser pipe and a feed pump, 33.14g of polyisobutenyl o-methylphenol, 34.91g of toluene solvent and 3.34g of p-phenylenediamine in example 1 were added, 2.92g of 37% formaldehyde aqueous solution was added dropwise at a flow rate of 0.06ml/min, the temperature was raised to 90 ℃ for reaction for 3 hours, and after the reaction was completed, the Mannich base of the present invention was obtained by distillation under reduced pressure.
An example reaction equation for example 3 is as follows.
Comparative example 1
55.11G of polyisobutenyl o-methylphenol and 56.03g of xylene in example 1 are added into a four-necked flask equipped with an N 2 inlet pipe, a thermocouple thermometer, a spherical condenser and a feed pump, the temperature is raised to 45 ℃, 5.17g of 1,3, 5-tris (dimethylaminopropyl) -1,3, 5-hexahydrotriazine is added, the temperature is raised to 140 ℃ for reaction for 4 hours, and the comparative detergent product is obtained by reduced pressure distillation.
FIG. 6 is an infrared spectrum of the product of comparative example 1.
As can be seen from fig. 6, the characteristic peaks generated after the synthesis of the mannich base are: 3500-3300cm -1 (N-H stretching vibration, overlap O-H stretching vibration, peak shape further broadened), 1748.64cm -1 (N-H bending vibration peak of secondary amine), 1015.76cm -1 (C-N stretching vibration peak).
FIG. 7 is a nuclear magnetic resonance hydrogen spectrum of the product of comparative example 1.
As can be seen from FIG. 7, the chemical shift of the benzene ring moiety is complex, and there are various structures, chemical shifts 4.82 and 3.92 are hydrogen proton shift peaks of secondary amino-NH-in different structures, chemical shift 3.61 is a shift peak of hydrogen proton on methylene generated by carbonyl conversion of formaldehyde, and chemical shift 2.71 is a shift peak of methylene linked to amine group which undergoes Mannich reaction.
The presence of the bis-mannich and cyclomannich by-products in this comparative example is evident from the infrared spectrum and nmr hydrogen spectrum of comparative example 1, in accordance with the report in US7384434B 2.
An example reaction equation for comparative example 1 is as follows.
Comparative example 2
To a four-necked flask equipped with an N 2 inlet pipe, a thermocouple thermometer, a spherical condenser pipe and a feed pump, 38.14g of polyisobutylene o-cresol, 38.13g of xylene and 3.29g of N, N-dimethyl-1, 3-propanediamine in example 1 were added, 3.44g of formaldehyde aqueous solution with a mass concentration of 37% was added dropwise, the temperature was raised to 150 ℃ for reaction for 3 hours, and after the reaction was completed, a comparative detergent product was obtained by reduced pressure distillation.
An example reaction equation for comparative example 2 is as follows.
Comparative example 3
Into a four-neck flask equipped with an N 2 inlet pipe, a thermocouple thermometer, a spherical condenser pipe and a feed pump, 33.12g of polyisobutenyl o-methylphenol, 35.7g of toluene solvent and 1.64g of ethylenediamine in the example 1 are added, 2.89g of formaldehyde aqueous solution with the mass concentration of 37% is dropwise added at the flow rate of 0.06ml/min, the temperature is raised to 110 ℃ for reaction for 3 hours, and after the reaction is finished, the Mannich base of the invention is obtained by reduced pressure distillation.
An example reaction equation for comparative example 3 is as follows.
Example 4
To 300ml of 95 # gasoline meeting the national VI standard, 300ppm (about 0.0673 g) of the Mannich base or comparative detergent of the examples (including the comparative Mannich base of comparative examples 1-3 and 6416 commercial comparative) and 300ppm of a polyether base oil were added, and blended, respectively, to prepare a gasoline composition comprising the Mannich base detergent.
EXAMPLE 5 evaluation of cleaning Performance
740 Μl of dicyclopentadiene coke-producing agent was added to the gasoline composition of example 4 and blank gasoline, respectively, and the cleaning performance of the Mannich base of the present invention and the comparative detergent was evaluated by using an L-2 type intake valve deposit simulation tester manufactured by Velcro instruments, orchikungunya, according to GB/T37322-2019 "Petrol cleaning evaluation Petrol intake valve deposit simulation test method".
The specific operation method is as follows:
After the dry sediment collector and the reference plate are weighed and recorded and averaged twice, the sediment collector is put into test equipment and clamped, and a cleaning performance evaluation test is carried out, wherein the test time is 85min, the oil spraying time is 75min, the test temperature is 175 ℃, and the temperature control precision is +/-1 ℃. After the air source is connected, the air pressure is 80kPa plus or minus 1kPa, and the air flow rate is 700L/h plus or minus 20L/h. Taking out the sediment collector by using tweezers after the test is finished, cooling to room temperature, placing the sediment collector into a container containing n-heptane, standing and soaking for 6min, taking out the sediment collector, placing the sediment collector into a container containing petroleum ether (60-90 ℃) for 1min, taking out the sediment collector after standing and soaking, plugging the sediment collector into a temperature measuring hole of the collector by using a paper rod, sucking out the reagent in the hole, weighing the weight of the collector, and calculating the sediment mass. The deposit cleaning effect is shown in Table 1.
TABLE 1
| Detergent | Amount of sediment | Deposit rate of decline |
| Blank space | 9.0mg | - |
| Example 2 | 1.10mg | 87.78％ |
| Example 3 | 1.27mg | 85.88％ |
| Comparative example 1 | 2.02mg | 77.56％ |
| Comparative example 2 | 1.56mg | 82.67％ |
| Comparative example 3 | 1.78mg | 80.22％ |
| 6416 Commercial contrast agent | 1.43mg | 84.11％ |
EXAMPLE 6 evaluation of rust inhibitive performance
The rust inhibitive performance is evaluated by using a GB/T19230.1-2003 gasoline detergent rust inhibitive performance test method. The method is that under the temperature condition of (38+/-1) DEG C, a cylindrical test bar is completely immersed into a mixture of 30ml of test gasoline and 30ml of distilled water under the stirring condition, and a 4-hour rust test is carried out to observe the rust degree of the test bar.
The degree of corrosion was evaluated as follows:
mild rust: the number of rust points is not more than 6, and the diameter of each rust point is less than or equal to 1mm.
Moderate rust: rust points are more than 6, but less than 5% of the surface area of the test bar.
Severe rust: rust points exceeded 5% of the surface area of the test bar.
The Mannich base or comparative detergent of the examples and the blank were evaluated for rust inhibitive performance, and the results are shown in Table 2.
TABLE 2
| Detergent | Dosage/mg/kg | Degree of rust |
| Blank space | - | Severe severity of |
| Example 2 | 100 | Mild and mild |
| Example 3 | 100 | Mild and mild |
| Comparative example 1 | 100 | Moderate degree |
| Comparative example 2 | 100 | Moderate degree |
| Comparative example 3 | 100 | Moderate degree |
| 6416 Commercial contrast agent | 100 | Moderate degree |
Claims (10)
1. The structure of the Mannich base is shown as a formula (I):
In formula (I), R 0 is selected from the group consisting of linear or branched alkylene of C 1～8; each R 1, equal to or different from each other, is independently selected from the group consisting of linear or branched alkyl groups of H, C 1～4; each R 1' is independently selected from the group consisting of linear or branched alkyl and phenyl of H, C 1～4; r 2 is selected from hydrocarbon groups with the number average molecular weight Mn of 300-3000; r 3 is selected from the group consisting of linear or branched alkyl of C 1～6.
2. Mannich base according to claim 1, characterized in that R 0 is selected from the group consisting of linear or branched alkylene groups of C 1～4, each R 1 is independently selected from the group consisting of H or methyl, each R 1' is independently selected from the group consisting of H, methyl, R 2 is selected from the group consisting of polyisobutenyl groups having a number average molecular weight Mn of 500 to 2500; r 3 is selected from the group consisting of linear or branched alkyl of C 1～4.
3. The preparation method of the Mannich base comprises the steps of reacting a compound shown in a formula (X), fatty aldehyde and a compound shown in a formula (Y), and collecting a product;
In the formula (X), R 2 is selected from hydrocarbon groups with a number average molecular weight Mn of 300-3000; r 3 is selected from the group consisting of linear or branched alkyl of C 1～6;
The carbon number of the fatty aldehyde is 1-8;
In formula (Y), each R 1, equal to or different from each other, is independently selected from the group consisting of linear or branched alkyl groups of H, C 1～4; each R 1' is independently selected from the group consisting of linear or branched alkyl and phenyl of H, C 1～4.
4. A process according to claim 3, wherein in formula (X), R 2 is selected from polyisobutenyl groups having a number average molecular weight Mn of 500 to 2500 and R 3 is selected from linear or branched alkyl groups of C 1～4; the carbon number of the fatty aldehyde is 1-4; in formula (Y), each R 1 is independently selected from H or methyl, and each R 1' is independently selected from H, methyl.
5. A method according to claim 3, wherein the fatty aldehyde is formaldehyde or acetaldehyde; the compound shown in the formula (Y) is selected from one or more of p-phenylenediamine, 2-methyl-p-phenylenediamine, tetramethyl-p-phenylenediamine, N-dimethyl-1, 4-phenylenediamine, N-ethyl-p-phenylenediamine, N-diethyl-p-phenylenediamine and N, N-diethyl-3-methyl-p-phenylenediamine.
6. A method according to claim 3, wherein the molar ratio between the compound of formula (X), the fatty aldehyde, the compound of formula (Y) is 1:0.1 to 3.5:0.3 to 3.
7. The method according to claim 3, wherein the reaction temperature between the compound represented by the formula (X), the fatty aldehyde and the compound represented by the formula (Y) is 50 to 200 ℃.
8. A process according to claim 3, characterized in that a solvent is added to the reaction of the compound of formula (X), the fatty aldehyde, the compound of formula (Y), said solvent being selected from hydrocarbons having a boiling point between 100 ℃ and 160 ℃.
9. A method according to claim 3, wherein a diluent is added to the reaction of the compound of formula (X), the fatty aldehyde, and the compound of formula (Y), the diluent being one or more of a mineral lubricating oil, a polyolefin, and a polyether.
10. Use of a mannich base according to claim 1 or 2 or a mannich base obtainable by a process according to one of claims 3 to 9 as a gasoline detergent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310066511.2A CN118344511A (en) | 2023-01-13 | 2023-01-13 | Mannich base and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310066511.2A CN118344511A (en) | 2023-01-13 | 2023-01-13 | Mannich base and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN118344511A true CN118344511A (en) | 2024-07-16 |
Family
ID=91810902
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310066511.2A Pending CN118344511A (en) | 2023-01-13 | 2023-01-13 | Mannich base and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN118344511A (en) |
-
2023
- 2023-01-13 CN CN202310066511.2A patent/CN118344511A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US9587198B2 (en) | Mannich base, production and use thereof | |
| EP3504303B1 (en) | Substituted mannich base fuel additives, compositions, and methods | |
| EP0183478B1 (en) | Glycidol modified succinimides | |
| US5514190A (en) | Fuel compositions and additives therefor | |
| US6069281A (en) | Process for producing organic nitrogen compounds, special organic nitrogen compounds and mixtures of such compounds and their use as fuel and lubricant additives | |
| US20040077507A1 (en) | Alkoxylated alkyl phenols and the use thereof in fuels and lubricants | |
| US20060196111A1 (en) | Fuel additive composition | |
| SK56399A3 (en) | Polyolefins and their functionalized derivatives | |
| SK284372B6 (en) | Polyalkene amines, a process for preparation of them, the compositions which contain them and using of polyalkene amines | |
| MXPA04008985A (en) | Polyisobutenamines. | |
| KR0143779B1 (en) | Long chain aliphatic hydrocarbyl amine additive having an oxy-alkylene hydroxy linking group | |
| US4526587A (en) | Deposit control additives-methylol polyether amino ethanes | |
| US10899985B2 (en) | Amine alkenyl substituted succinimide reaction product fuel additives, compositions, and methods | |
| CN102796592A (en) | Organic molybdenum additive, preparation method thereof and lubricating oil composition containing additive | |
| CN118344511A (en) | Mannich base and preparation method and application thereof | |
| KR20140103978A (en) | Amine mixture | |
| CN103664655A (en) | Mannich base detergent, preparation method thereof as well as detergent concentrate and fuel oil composition | |
| US6117198A (en) | Detergents for hydrocarbon fuels | |
| CN106590833B (en) | Two-stroke engine lubricating oil composition and its manufacturing method | |
| CN118344512A (en) | Mannich base and preparation method and application thereof | |
| US20180223017A1 (en) | Isomerization of polyisobutylene | |
| CN104946350B (en) | Lubricant oil composite | |
| EP0147438B1 (en) | Methylol polyether amino ethanes in fuel and lubricant compositions | |
| KR100602448B1 (en) | Hydro polyoxyalkylen oxyalkyl amine compound for fuel oil purifier | |
| CN108728217B (en) | Two-cycle engine oil composition and method for producing same |
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 |