CN116253651B - Method for co-producing TMAEEEPA and BDMAEE - Google Patents
Method for co-producing TMAEEEPA and BDMAEE Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 26
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 34
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000012972 dimethylethanolamine Substances 0.000 claims abstract description 30
- 238000006266 etherification reaction Methods 0.000 claims abstract description 28
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 26
- -1 amine compounds Chemical class 0.000 claims abstract description 22
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 21
- 238000006722 reduction reaction Methods 0.000 claims abstract description 16
- 239000011259 mixed solution Substances 0.000 claims abstract description 15
- 238000006845 Michael addition reaction Methods 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 10
- GXVUZYLYWKWJIM-UHFFFAOYSA-N 2-(2-aminoethoxy)ethanamine Chemical compound NCCOCCN GXVUZYLYWKWJIM-UHFFFAOYSA-N 0.000 claims abstract description 7
- GTEXIOINCJRBIO-UHFFFAOYSA-N 2-[2-(dimethylamino)ethoxy]-n,n-dimethylethanamine Chemical compound CN(C)CCOCCN(C)C GTEXIOINCJRBIO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 36
- 239000007788 liquid Substances 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 24
- 238000006386 neutralization reaction Methods 0.000 claims description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 19
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical class [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 238000000926 separation method Methods 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- 238000007259 addition reaction Methods 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 239000012295 chemical reaction liquid Substances 0.000 claims description 8
- 230000009467 reduction Effects 0.000 claims description 8
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 239000011651 chromium Substances 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 3
- QOUPJMSRAZQXGO-UHFFFAOYSA-N 3-[2-[2-(dimethylamino)ethoxy]ethyl-methylamino]propanenitrile Chemical compound CN(C)CCOCCN(C)CCC#N QOUPJMSRAZQXGO-UHFFFAOYSA-N 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- 229960002887 deanol Drugs 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 2
- 239000001095 magnesium carbonate Substances 0.000 claims description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 2
- 239000000347 magnesium hydroxide Substances 0.000 claims description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 239000011572 manganese Substances 0.000 claims description 2
- 239000011736 potassium bicarbonate Substances 0.000 claims description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 235000011181 potassium carbonates Nutrition 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 239000011135 tin Substances 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 abstract description 5
- 239000004814 polyurethane Substances 0.000 abstract description 5
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 8
- 230000006872 improvement Effects 0.000 description 7
- 239000000706 filtrate Substances 0.000 description 6
- UOQYWMZLTNEIFI-UHFFFAOYSA-N 2-[3-aminopropyl(methyl)amino]ethanol Chemical compound OCCN(C)CCCN UOQYWMZLTNEIFI-UHFFFAOYSA-N 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 229920005830 Polyurethane Foam Polymers 0.000 description 2
- 229910000564 Raney nickel Inorganic materials 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- VXPJBVRYAHYMNY-UHFFFAOYSA-N n-methyl-2-[2-(methylamino)ethoxy]ethanamine Chemical group CNCCOCCNC VXPJBVRYAHYMNY-UHFFFAOYSA-N 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 239000011496 polyurethane foam Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- TZWPUBMUJFCAIO-UHFFFAOYSA-N 2-(2,2-diaminoethoxy)ethane-1,1-diamine Chemical compound NC(N)COCC(N)N TZWPUBMUJFCAIO-UHFFFAOYSA-N 0.000 description 1
- JHGANGDIYRLEJL-UHFFFAOYSA-N 3-[2-hydroxyethyl(methyl)amino]propanenitrile Chemical compound OCCN(C)CCC#N JHGANGDIYRLEJL-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 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
- 238000007796 conventional method Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000004619 high density foam Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- NCPHGZWGGANCAY-UHFFFAOYSA-N methane;ruthenium Chemical compound C.[Ru] NCPHGZWGGANCAY-UHFFFAOYSA-N 0.000 description 1
- 238000007069 methylation reaction Methods 0.000 description 1
- 239000013518 molded foam Substances 0.000 description 1
- DNRUQHYIUPKPOQ-UHFFFAOYSA-N n'-[2-[2-(dimethylamino)ethoxy]ethyl]-n'-methylpropane-1,3-diamine Chemical compound CN(C)CCOCCN(C)CCCN DNRUQHYIUPKPOQ-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/06—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton from hydroxy amines by reactions involving the etherification or esterification of hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/10—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention belongs to the field of polyurethane industry, and mainly relates to a method for co-producing two special amine compounds, namely a method for simultaneously synthesizing TMAEPA (N, N, N '-trimethyl-N' -aminopropyl bis (aminoethyl) ether) and BDMAEE (bis (dimethylaminoethyl) ether). The invention comprises the following steps: cross etherification reaction is carried out by taking MMEA and DMEA as main raw materials; carrying out Michael addition reaction on the obtained fraction mainly containing TMAEE and BDMAEE and acrylonitrile; and (3) carrying out hydrogenation reduction reaction on the obtained mixed solution of TMAEEEPN and BDMAEE, and then carrying out subsequent treatment to obtain TMAEPA and BDMAEE respectively.
Description
Technical Field
The invention belongs to the field of polyurethane industry, and mainly relates to a method for co-producing two special amine compounds, namely a method for simultaneously synthesizing TMAEPA (N, N, N '-trimethyl-N' -aminopropyl bis (aminoethyl) ether) and BDMAEE (bis (dimethylaminoethyl) ether).
Background
TMAEPA is a colorless or pale yellow transparent liquid, has active hydrogen functional groups, and thus can react with isocyanate during the reaction to bond with foam, and is a third generation low emission (No. Emissions) polyurethane blowing catalyst. The structural formula is shown in formula 1.
1 TMAEPA (N, N, N '-trimethyl-N' -aminopropyl bis (aminoethyl) ether) structural formula
The non-volatile catalyst is compatible with other conventional polyurethane catalysts and additives and is miscible with the polyol and the polyol/water mixture. Suitable for all molded foams and high density foams; the polyurethane foam can be used for any water-blown TDI or TDI/MDI High Resilience (HR) foam and TDI/MDI or MDI-based cold cure polyurethane foam system.
BDMAEE is one of important amine catalysts in the polyurethane industry, has extremely high catalytic activity and selectivity on foaming reaction, and has extremely high pure product activity, and is used after being diluted by common glycol. The structural formula is shown in formula 2.
BDMAEE (bis (dimethylaminoethyl) ether) formula
The TMAEPA synthesis method is as follows:
1) Patent CN105884629a discloses two methods:
the method comprises the following steps: TMAEE (N, N, N' -trimethylbis-aminoethyl ether) is prepared by first reacting sodium alkoxide (or its chloride) of DMEA with a chloride (or its sodium alkoxide) of MMEA. TMAEE is further reacted with acrylonitrile and then hydrogenated in the presence of catalysts such as framework nickel, palladium, carbon, ruthenium carbon, platinum carbon and the like to obtain N, N, N '-trimethyl-N' -aminopropyl bis (aminoethyl) ether. The equation for preparing TMAEE from the reaction of the chlorine of DMEA and sodium alkoxide of MMEA is as follows:
the second method is as follows: MMEA and acrylonitrile react first and then are subjected to hydrogenation reduction to obtain N-methyl-N-aminopropyl ethanolamine. And (3) dropwise adding N-methyl-N-aminopropyl ethanolamine into thionyl chloride and toluene to prepare a chloro compound. Dropping the chloride into sodium alkoxide of DMEA to obtain TMAEPA. The reaction process is as follows:
both of the methods mentioned in this patent use thionyl chloride and toluene, both chemicals are toxic substances, and thionyl chloride is corrosive to equipment and byproduct sulfur dioxide has an environmental impact.
2) There are two methods for preparing TMAEPA disclosed in patent CN 11153184A:
the first is prepared by Michael addition of bisaminoethyl ether to less than stoichiometric acrylonitrile, re-methylation, and final hydrogenation reduction.
A preferred second method is to methylate with slightly sub-stoichiometric amounts of formaldehyde and hydrogen using bis-aminoethyl ether to give TMAEE and other methylated products, then to react TMAEE with acrylonitrile, and then to hydrogenate and reduce.
The two methods adopt the diamine ethyl ether as the raw material, so that the sources are few, and the cost is high.
There are many preparation methods of BDMAEE, but the method for co-production with TMAEEEPA is not reported.
The invention of application number 202211213062.1, the co-production method of N, N, N '-trimethyl-N' - (3-aminopropyl) bis (aminoethyl) ether and bis (dimethylaminoethyl) ether, informs a synthetic method for co-production of NE300 and BDMAEE, and the reaction process mainly comprises the following steps: synthesis of sulphate ester starting from DMEA, synthesis of N- (3-aminopropyl) -N-methylethanolamine and NE300 synthesis:
disclosure of Invention
The invention aims to provide a method for co-producing TMAEEEPA and BDMAEE.
In order to solve the technical problems, the invention provides a method for co-producing TMAEPA (N, N, N '-trimethyl-N' -aminopropyl bis (aminoethyl) ether) and BDMAEE (bis (dimethylaminoethyl) ether), which comprises the following steps:
step one, cross etherification reaction:
cross etherification is carried out by taking MMEA and DMEA as main raw materials, and then subsequent treatment is carried out to obtain a fraction (third fraction) mainly containing BMAEE and a fraction (fourth fraction) mainly containing TMAEE and BDMAEE;
MMEA is N-methylethanolamine, DMEA is dimethylethanolamine, BMAEE is bis (methylaminoethyl) ether, TMAEE is N, N, N' -trimethylbis-aminoethyl ether, BDMAEE is bis (dimethylaminoethyl) ether;
step two, michael addition reaction:
carrying out Michael addition reaction on the fraction mainly containing TMAEE and BDMAEE obtained in the step one and acrylonitrile, and carrying out subsequent treatment to obtain a mixed solution of TMAEEEPN and BDMAEE;
TMAEPN is 3- [2- [2- (dimethylamino) ethoxy ] ethylmethylamino ] propionitrile;
step three, hydrogenation reduction reaction;
carrying out hydrogenation reduction reaction on the mixed solution of TMAEEEPN and BDMAEE obtained in the second step, and carrying out subsequent treatment to obtain TMAEPA and BDMAEE respectively;
TMAEPA is N, N, N '-trimethyl-N' -aminopropyl bis (aminoethyl) ether.
As an improvement of the method for co-producing TMAEEPA and BDMAEE of the present invention, the first step comprises the following steps:
1.1 Cross etherification):
adding MMEA, DMEA and sulfuric acid into a reactor, heating to 150-220 ℃ for etherification reaction, wherein the reaction time is 1-25 hours, and obtaining cross etherification solution after the reaction;
the molar ratio of DMEA to MMEA is: 0.5-3:1, the sum of dmea and MMEA being collectively referred to as an alcohol amine; the molar ratio of sulfuric acid to alcohol amine is 1-3:1;
1.2 Neutralization:
adding alkali liquor into the cross etherified liquid for neutralization until the pH value of the system is more than or equal to 12, thus obtaining a neutralization liquid;
the neutralization temperature is 0-100 ℃, and the neutralization time is 1-5 h;
1.3 Solid-liquid separation:
carrying out solid-liquid separation (for example, adopting a filtering mode) on the neutralization liquid obtained in the step 1.2), and drying the obtained solid to obtain sulfate solid;
1.4 Rectifying:
rectifying the liquid (filtrate) obtained by the solid-liquid separation in the step 1.3); obtaining a fraction (third fraction) mainly containing BMAEE and a fraction (fourth fraction) mainly containing TMAEE and BDMAEE;
description: rectifying in the step to obtain a first fraction, a second fraction, a third fraction and a fourth fraction respectively;
a first fraction: mainly comprises water (recycled to the neutralization step after the next round of cross etherification reaction); a second fraction: mainly comprises MMEA and/or DMEA (circularly applied to the next round of cross etherification reaction, and the conversion is carried out according to the content during feeding); third fraction: mainly contains BMAEE; fourth fraction: mainly contains TMAEE and BDMAEE.
As a further improvement of the method for co-producing TMAEEEPA and BDMAEE, the second step comprises the following steps:
2.1 Michael addition):
adding the fraction (fourth fraction) mainly containing TMAEE and BDMAEE obtained in the step one into a reaction kettle, adding water, starting stirring, dropwise adding (controlling the dropwise adding temperature to be not more than 60 ℃) acrylonitrile, and carrying out heat preservation reaction on a reaction system formed after the completion of the dropwise adding of the acrylonitrile for 1-5 hours at 50-100 ℃ to obtain an addition reaction liquid;
the molar ratio of acrylonitrile to TMAEE in the fraction (fourth fraction) is 1-2:1; water accounts for 1-10% of the total mass of the reaction system;
2.2 Distillation:
and (2) distilling the addition reaction liquid obtained in the step (2.1) under reduced pressure, so as to remove acrylonitrile in the addition reaction liquid (namely, removing the redundant acrylonitrile under the condition of reduced pressure), thereby obtaining the mixed liquid of TMAEPN and BDMAEE.
As a further improvement of the method for co-producing TMAEEPA and BDMAEE of the present invention, step three includes the steps of:
3.1 Hydrogenation reduction:
adding the mixed solution of TMAEEEPN and BDMAEE obtained in the second step and a modified Raney nickel catalyst into a hydrogenation reactor (high-pressure reaction kettle), introducing hydrogen, heating to 30-150 ℃ and hydrogenating under the pressure of 1-4 MPa until no hydrogen is absorbed (closing a hydrogen inlet valve, judging that no hydrogen is absorbed when the pressure of the high-pressure reaction kettle is no longer reduced), and preparing the mixed solution of TMAEPA and BDMAEE;
modified raney nickel catalyst: TMAEEPN and BDMAEE mixed liquor=5-20% mass ratio;
89-93% of nickel in the modified Raney nickel catalyst, 5-10% of aluminum and 0.1-2% of other metals; the other metal at least comprises more than three combinations of iron, chromium, molybdenum, sodium, copper, tin, tungsten, bismuth or manganese;
description: the conventional Raney nickel catalyst is a nickel-aluminum alloy catalyst with a porous structure, and the modification is to add other metals except nickel-aluminum, so that the activity of the catalyst can be obviously increased;
3.2 Rectifying:
rectifying the mixed liquid of TMAEPA and BDMAEE obtained in the step 3.1) to obtain TMAEPA and BDMAEE respectively.
As a further improvement of the co-production method of TMAEEEPA and BDMAEE of the invention:
in the step 1.1):
the etherification reaction temperature is 160-200 ℃; the etherification reaction time is 8-20 h; the molar ratio of DMEA to MMEA is: 0.5-2:1; the molar ratio of sulfuric acid to alcohol amine is: 1.2-2.5:1;
in the step 1.2):
the neutralization temperature is 60-80 ℃, and the neutralization time is 2-3 hours; the alkali liquor is prepared from an alkaline substance and water, wherein the alkaline substance is at least any one of the following components: ammonia, sodium hydroxide, potassium hydroxide, magnesium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, and magnesium carbonate;
in the step 1.4):
rectifying the liquid (filtrate) obtained in the solid-liquid separation of the step 1.3) at normal pressure to obtain a first fraction (100-102 ℃/760mmHg fraction), mainly water; and then carrying out vacuum distillation to obtain second fractions (30-100 ℃/10mHg fractions) respectively: mainly comprises MMEA and/or DMEA; third fraction (100-110 ℃/10mHg fraction): mainly contains BMAEE; fourth fraction (110-130 ℃ C./10 mHg fraction): mainly contains TMAEE and BDMAEE.
As a further improvement of the co-production method of TMAEEEPA and BDMAEE of the invention:
in the step 2.1):
the molar ratio of the acrylonitrile to TMAEE in the fourth fraction is 1-1.5:1; the water accounts for 3 to 10 percent of the total mass of the reaction system, the reaction temperature is 60 to 100 ℃, and the reaction time is 2 to 5 hours.
As a further improvement of the co-production method of TMAEEEPA and BDMAEE of the invention:
in the step 3.1): the hydrogenation reaction temperature is 80-120 ℃, and the reaction pressure is 1-3 MPa.
As a further improvement of the co-production method of TMAEEEPA and BDMAEE of the invention:
the water used for preparing the lye in step 1.2) may be the first fraction (mainly water) obtained in step 1.4).
The reaction equation of the present invention is as follows:
cross etherification reaction:
michael addition reaction:
hydrogenation reduction reaction:
the sulfuric acid refers to concentrated sulfuric acid with the mass concentration of more than or equal to 98 percent.
It should be noted that: the invention is different from 202211213062.1 in technical route: 202211213062.1 preparing BDMAEE and sulfate mixed solution by using DMEA; MMEA and acrylonitrile are subjected to addition reaction to obtain a (2-cyanoethyl) (2-hydroxyethyl) methylamine reaction solution, and then hydrogenation reduction is carried out to obtain an N- (3-aminopropyl) -N-methylethanolamine reaction solution; and the mixed solution of BDMAEE and sulfuric acid ester is reacted with the N- (3-aminopropyl) -N-methylethanolamine reaction solution to prepare TMAEPA and BDMAEE. The invention adopts the reaction of MMEA and DMEA to obtain BMAEE (1, 5-bis (methylamino) -3-oxapentane), TMAEE (N, N, N' -trimethyl bis-amino ethyl ether) and BDMAEE, and then the mixture of the TMAEE and BDMAEE is obtained by separation; adding the mixed solution and acrylonitrile, and then carrying out hydrogenation reduction to obtain TMAEPA and BDMAEE.
The invention takes MMEA, DMEA, sulfuric acid, acrylonitrile, hydrogen and the like as raw materials, and realizes TMAEPA and BDMAEE co-production mainly through cross etherification, michael addition and hydrogenation reduction, namely, two special amine products can be obtained simultaneously. Therefore, the invention has the technical advantages of low cost of raw materials, high product value and high economic benefit.
The invention introduces the cross etherification technology to replace the traditional chlorination technology, and has the technical advantages of environmental protection and suitability for industrial production.
The light components obtained by separation after cross etherification, namely the first fraction water, the second fraction MMEA and the DMEA, are used mechanically, so that the yield can be improved; therefore, the invention has the technical advantages of high raw material utilization rate and good economy.
In conclusion, the invention takes MMEA, DMEA, sulfuric acid, acrylonitrile and hydrogen as raw materials to realize the joint production of two special amine products, and has low raw material cost, high product value and high economic benefit; the whole process technology does not use thionyl chloride, toluene and metallic sodium, adopts the cross etherification technology to prepare TMAEE, replaces the traditional chlorination technology, and is environment-friendly. The Raney nickel catalyst can be recycled, and the production cost is reduced. The product has high selectivity, less byproducts and simple process, and is suitable for large-scale production.
Detailed Description
The invention will be further described with reference to the following specific examples, but the scope of the invention is not limited thereto:
the correctness of the product obtained by the invention is verified by a conventional method.
Example 1, cross etherification reaction, the following steps were performed in order:
1.1 Cross etherification):
142.4g (1.6 mol) of DMEA (methyl methacrylate) 240g (3.2 mol) and 771g (7.71 mol) of sulfuric acid are added into a reaction bottle, the temperature is raised to 180 ℃ under stirring, water is produced while the reaction is carried out, the reaction is carried out for 15 hours, heating is stopped, natural cooling is carried out, cross etherifying liquid is obtained, and about 26.7g of byproduct water is collected.
1.2 Neutralization of:
preparing alkali liquor by 924g of water and 616g of sodium hydroxide;
and (2) dripping alkali liquor into the cross etherified liquid obtained in the step (1.1) for neutralization, wherein the neutralization temperature is 60 ℃, the dripping time is about 3 hours, and the pH value of the system is more than 12 after the neutralization reaction is finished.
1.3 Solid-liquid separation:
the neutralization solution obtained in step 1.2) was filtered, and the obtained solid was dried by a conventional forced air drying oven (dried to constant weight at 70 to 100 ℃ C.) to obtain about 1094g of sodium sulfate solid.
1.4 Rectifying:
rectifying the filtrate obtained in the step 1.3), and collecting 910.46g of a first fraction (mainly containing water and being capable of being partially used for the neutralization of the next round etherification reaction liquid), 128.93g of a second fraction (mainly containing MMEA and being used for the raw material of the next round cross etherification reaction) of 30-100 ℃/10mmHg, 39.07g of a third fraction (mainly containing BMAEE) of 100-110 ℃/10mmHg and 170.2g of a fourth fraction (mainly containing TMAEE and BDMAEE) of 110-130 ℃/10mmHg, and 9.65g of still residue (being capable of being used for the rectification of the filtrate of the next round reaction).
Examples 1 to 1,
Changing "240 g of MMEA" from example 1, step 1.1) to "128.93 g of the second fraction from the upper run (example 1), supplementing the new MMEA to a total weight of still 240g";
the "924g water" from step 1.2) of example 1 was changed to 910.46g of the first fraction distilled off with the upper run (example 1) and fresh water was supplemented to a sodium hydroxide solution concentration of 40 wt.%;
the remainder was identical to example 1.
The results obtained are as follows:
step 1.3) gave sodium sulfate solids of about 1092g.
Rectifying the filtrate obtained in the step 1.4), and collecting 909.52g (mainly containing water) of a first fraction of 100-102 ℃/760mmHg, 127.49g (mainly containing MMEA) of a second fraction of 30-100 ℃/10mmHg, 41.03g (mainly containing BMAEE) of a third fraction of 100-110 ℃/10mmHg and 167.1g (mainly containing TMAEE and BDMAEE) of a fourth fraction of 110-130 ℃/10mmHg respectively, wherein the residue is 9.73g.
Examples 2 to 3, in which only the molar ratio of MMEA to DMEA was changed in example 1, the total molar amount of alcohol amine was kept unchanged; the other conditions were the same as in example 1.
Examples 4 to 6, in which only the molar ratio of sulfuric acid to alcohol amine in example 1 was changed, the amounts of MMEA and DMEA were kept unchanged; the other conditions were the same as in example 1.
Examples 7 to 9 were conducted under the same conditions as in example 1 except that the etherification temperature was changed only in example 1.
Examples 10 to 12 were conducted under the same conditions as in example 1 except that the etherification time was changed only in example 1.
The specific parameters and final results of examples 1-12 are shown in Table 1-1 and Table 1-2.
TABLE 1-1
Tables 1 to 2
Note that: in Table 1-1 and subsequent tables 1-2, the second fraction residual alcohol amine of example 2 was MMEA and DMEA in the following mass ratios: 43%,57%; the second fraction of residual alcohol amine of example 3 was DMEA; the second fraction residual alcohol amine of examples 1, 1-1 and 4 to 12 was MMEA.
Example 13, michael addition reaction, the following steps were carried out in order:
2.1 Michael addition):
using the fourth fraction collected as described in example 1- -TMAEE and BDMAEE mixed solution,
500g of a mixed solution of TMAEE and BDMAEE (the mass ratio of TMAEE is 70.8%) is added into a flask, 25g of water is added, stirring is started, 154g of acrylonitrile is dropwise added at room temperature, the dropwise heating temperature is controlled to be not more than 60 ℃, and after the dropwise addition is finished, the temperature is kept at 60 ℃ for 3 hours for reaction, so that an addition reaction solution is obtained.
Thus, the molar ratio of acrylonitrile to TMAEE in the fourth fraction was 1.2:1; water represents about 4% of the total mass of the reaction system.
2.2 Distillation:
distilling the addition reaction liquid obtained in the step 2.1) under reduced pressure (the pressure of 20mmHg and the temperature of 40-50 ℃) so as to remove acrylonitrile in the addition reaction liquid until the acrylonitrile is removed, obtaining 622g of a mixed liquid of TMAEPN and BDMAEE, and detecting according to a conventional gas chromatography, wherein the mass ratio of the two is as follows: 76.8 percent and 23.2 percent.
Example 14, hydrogenation reduction reaction, the following steps were performed in order:
3.1 And (c) hydrogenation reduction:
622g of the mixture of TMAEEPN and BDMAEE obtained in example 13 and 72g of the modified Raney nickel catalyst were added into a high-pressure reactor, the temperature was raised to 80 ℃ after three times of replacement by nitrogen, and hydrogen was introduced to a pressure of 2.0MPa for continuous hydrogenation until no more hydrogen was absorbed (i.e. the inlet valve was closed, and when the pressure of the reactor no more decreased, no more hydrogen was absorbed), and the reaction was carried out for about 3 hours. Cooling to room temperature, and filtering. The filter cake is catalyst for recycling, and the filtrate is about 628g of mixed liquor of TMAEEEPA and BDMAEE.
The preparation method of the modified Raney nickel catalyst comprises the following steps: adding 18.1g of nickel, 16.6g of aluminum, 0.03g of iron, 0.02g of copper, 0.11g of chromium and 0.10g of molybdenum into a smelting furnace for smelting to form uniform alloy, cooling by a high-speed rotary copper drum to obtain alloy thin strips, and grinding by a ball mill to obtain alloy powder; the alloy powder was added to 20% aqueous sodium hydroxide (about 100 ml) and stirred for 1.5h at 80 ℃; repeatedly washing with deionized water to neutrality, and storing in water for use. The detection shows that the modified Raney nickel catalyst contains 90.51% of nickel, 8.16% of aluminum and trace amounts of iron, copper, chromium and molybdenum.
3.2 And (3) rectifying:
rectifying the mixed solution of TMAEPA and BDMAEE obtained in the step 3.1), collecting fraction of 145-160 ℃/10mmHg as 478g of TMAEEEPA, and collecting fraction of 110-130 ℃/10mmHg as 141g of BDMAEE.
The fourth fraction obtained in examples 1 to 12 was subjected to Michael addition reaction under the reaction conditions of example 13, and the mass of the obtained mixture of TMAEPN and BDMAEE, and the mass ratio of the two were shown in Table 2. The above-obtained "mixture of TMAEEPN and BDMAEE" was further subjected to "example 14, hydrogenation reduction reaction", and the results are shown in Table 2.
TABLE 2
Finally, it should also be noted that the above list is merely a few specific embodiments of the present invention. Obviously, the invention is not limited to the above embodiments, but many variations are possible. All modifications directly derived or suggested to one skilled in the art from the present disclosure should be considered as being within the scope of the present invention.
Claims (5)
1. A method for co-producing TMAEEPA and BDMAEE, which is characterized by comprising the following steps:
step one, cross etherification reaction:
cross etherification is carried out by taking MMEA and DMEA as main raw materials, and then subsequent treatment is carried out to obtain fractions mainly containing TMAEE and BDMAEE;
MMEA is N-methylethanolamine, DMEA is dimethylethanolamine, TMAEE is N, N, N' -trimethylbis-aminoethyl ether, BDMAEE is bis (dimethylaminoethyl) ether;
the first step comprises the following steps:
1.1 Cross etherification):
adding MMEA, DMEA and sulfuric acid into a reactor, heating to 150-220 ℃ for etherification reaction, wherein the reaction time is 1-25 hours, and obtaining cross etherification solution after the reaction;
the molar ratio of DMEA to MMEA is: 0.5-3:1, the sum of dmea and MMEA being collectively referred to as an alcohol amine; the molar ratio of sulfuric acid to alcohol amine is 1-3:1;
1.2 Neutralization:
adding alkali liquor into the cross etherified liquid for neutralization until the pH value of the system is more than or equal to 12, thus obtaining a neutralization liquid;
the neutralization temperature is 0-100 ℃, and the neutralization time is 1-5 h;
1.3 Solid-liquid separation:
carrying out solid-liquid separation on the neutralization liquid obtained in the step 1.2);
1.4 Rectifying:
rectifying the liquid obtained by the solid-liquid separation in the step 1.3); obtaining fraction mainly containing TMAEE and BDMAEE;
step two, michael addition reaction:
carrying out Michael addition reaction on fraction mainly containing TMAEE and BDMAEE and acrylonitrile, and carrying out subsequent treatment to obtain a mixed solution of TMAEEEPN and BDMAEE;
TMAEPN is 3- [2- [2- (dimethylamino) ethoxy ] ethylmethylamino ] propionitrile;
the second step comprises the following steps:
2.1 Michael addition):
adding the fraction mainly containing TMAEE and BDMAEE obtained in the step one into a reaction kettle, adding water, starting stirring, dropwise adding acrylonitrile, and reacting at 50-100 ℃ for 1-5 h in a reaction system formed after the acrylonitrile is dropwise added, thereby obtaining an addition reaction solution;
the molar ratio of acrylonitrile to TMAEE in the fraction is 1-2:1; water accounts for 1-10% of the total mass of the reaction system;
2.2 Distillation:
distilling the addition reaction liquid obtained in the step 2.1) under reduced pressure, thereby removing acrylonitrile in the addition reaction liquid and obtaining a mixed liquid of TMAEEPN and BDMAEE;
step three, hydrogenation reduction reaction;
carrying out hydrogenation reduction reaction on the mixed solution of TMAEEEPN and BDMAEE, and then carrying out subsequent treatment to obtain TMAEPA and BDMAEE respectively;
TMAEPA is N, N, N '-trimethyl-N' -aminopropyl bis (aminoethyl) ether;
the third step comprises the following steps:
3.1 Hydrogenation reduction:
adding the mixed solution of TMAEEEPN and BDMAEE obtained in the second step and a modified Raney nickel catalyst into a hydrogenation reactor, introducing hydrogen, heating to 30-150 ℃ and hydrogenating under the pressure of 1-4 MPa until the hydrogen is not absorbed, so as to prepare the mixed solution of TMAEPA and BDMAEE;
modified raney nickel catalyst: TMAEEPN and BDMAEE mixed liquor=5-20% mass ratio;
89-93% of nickel in the modified Raney nickel catalyst, 5-10% of aluminum and 0.1-2% of other metals; the other metal at least comprises more than three combinations of iron, chromium, molybdenum, sodium, copper, tin, tungsten, bismuth or manganese;
3.2 Rectifying:
rectifying the mixed liquid of TMAEPA and BDMAEE obtained in the step 3.1) to obtain TMAEPA and BDMAEE respectively.
2. The method for co-producing TMAEEPA and BDMAEE according to claim 1, characterized in that:
in the step 1.1):
the etherification reaction temperature is 160-200 ℃; the etherification reaction time is 8-20 h; the molar ratio of DMEA to MMEA is: 0.5-2:1; the molar ratio of sulfuric acid to alcohol amine is: 1.2-2.5:1;
in the step 1.2):
the neutralization temperature is 60-80 ℃, and the neutralization time is 2-3 hours; the alkali liquor is prepared from an alkaline substance and water, wherein the alkaline substance is at least any one of the following components: ammonia, sodium hydroxide, potassium hydroxide, magnesium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, and magnesium carbonate;
in the step 1.4):
rectifying the liquid obtained in the step 1.3) through solid-liquid separation under normal pressure to obtain a first fraction containing water; then carrying out vacuum rectification to obtain second fractions mainly containing MMEA and/or DMEA respectively; a third fraction comprising mainly BMAEE; a fourth fraction mainly containing TMAEE and BDMAEE.
3. The method for co-producing TMAEEPA and BDMAEE according to claim 2, characterized in that:
in the step 2.1):
the molar ratio of the acrylonitrile to TMAEE in the fourth fraction is 1-1.5:1; the water accounts for 3 to 10 percent of the total mass of the reaction system, the reaction temperature is 60 to 100 ℃, and the reaction time is 2 to 5 hours.
4. A method for co-producing TMAEEPA and BDMAEE according to claim 3, characterized in that:
in the step 3.1): the hydrogenation reaction temperature is 80-120 ℃, and the reaction pressure is 1-3 MPa.
5. The method for co-producing TMAEEPA and BDMAEE according to claim 4, wherein:
the water for preparing the lye in the step 1.2) can be selected from the first fraction obtained in the step 1.4).
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