CN117186142A - Process for preparing 3-octanoyl thiopropyl triethoxysilane - Google Patents
Process for preparing 3-octanoyl thiopropyl triethoxysilane Download PDFInfo
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- CN117186142A CN117186142A CN202310698464.3A CN202310698464A CN117186142A CN 117186142 A CN117186142 A CN 117186142A CN 202310698464 A CN202310698464 A CN 202310698464A CN 117186142 A CN117186142 A CN 117186142A
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 68
- 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 abstract description 52
- 239000011734 sodium Substances 0.000 claims abstract description 52
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 52
- 238000000034 method Methods 0.000 claims abstract description 50
- AGBQKNBQESQNJD-UHFFFAOYSA-N alpha-Lipoic acid Natural products OC(=O)CCCCC1CCSS1 AGBQKNBQESQNJD-UHFFFAOYSA-N 0.000 claims abstract description 48
- 235000019136 lipoic acid Nutrition 0.000 claims abstract description 48
- 229960002663 thioctic acid Drugs 0.000 claims abstract description 48
- KSCAZPYHLGGNPZ-UHFFFAOYSA-N 3-chloropropyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)CCCCl KSCAZPYHLGGNPZ-UHFFFAOYSA-N 0.000 claims abstract description 45
- AGBQKNBQESQNJD-SSDOTTSWSA-N (R)-lipoic acid Chemical compound OC(=O)CCCC[C@@H]1CCSS1 AGBQKNBQESQNJD-SSDOTTSWSA-N 0.000 claims abstract description 39
- 239000002994 raw material Substances 0.000 claims abstract description 39
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 claims abstract description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 66
- 239000007864 aqueous solution Substances 0.000 claims description 43
- 239000000243 solution Substances 0.000 claims description 41
- -1 3-chloropropyl triethoxy silane toluene Chemical compound 0.000 claims description 21
- 239000003444 phase transfer catalyst Substances 0.000 claims description 21
- JPPLPDOXWBVPCW-UHFFFAOYSA-N s-(3-triethoxysilylpropyl) octanethioate Chemical compound CCCCCCCC(=O)SCCC[Si](OCC)(OCC)OCC JPPLPDOXWBVPCW-UHFFFAOYSA-N 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 12
- REEZZSHJLXOIHL-UHFFFAOYSA-N octanoyl chloride Chemical compound CCCCCCCC(Cl)=O REEZZSHJLXOIHL-UHFFFAOYSA-N 0.000 claims description 10
- 238000004821 distillation Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 8
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical group [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 claims description 7
- 238000011068 loading method Methods 0.000 claims description 6
- 238000005086 pumping Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 claims description 6
- LIGNULLGXFDSOL-UHFFFAOYSA-M sodium;octanethioate Chemical compound [Na+].CCCCCCCC([O-])=S LIGNULLGXFDSOL-UHFFFAOYSA-M 0.000 claims description 5
- UHZZMRAGKVHANO-UHFFFAOYSA-M chlormequat chloride Chemical compound [Cl-].C[N+](C)(C)CCCl UHZZMRAGKVHANO-UHFFFAOYSA-M 0.000 claims description 3
- ZNKXTIAQRUWLRL-UHFFFAOYSA-M sodium;sulfane;hydroxide Chemical compound O.[Na+].[SH-] ZNKXTIAQRUWLRL-UHFFFAOYSA-M 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052717 sulfur Inorganic materials 0.000 abstract description 5
- 239000011593 sulfur Substances 0.000 abstract description 5
- 239000006087 Silane Coupling Agent Substances 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 17
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 16
- 230000008569 process Effects 0.000 description 12
- 239000000463 material Substances 0.000 description 9
- 238000003860 storage Methods 0.000 description 9
- 230000006872 improvement Effects 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 238000010924 continuous production Methods 0.000 description 5
- 230000001276 controlling effect Effects 0.000 description 5
- 239000012074 organic phase Substances 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 239000002904 solvent Substances 0.000 description 4
- VQNVZLDDLJBKNS-UHFFFAOYSA-N carbamimidoylazanium;bromide Chemical compound Br.NC(N)=N VQNVZLDDLJBKNS-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000003408 phase transfer catalysis Methods 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 150000001266 acyl halides Chemical class 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical group C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 150000003983 crown ethers Chemical class 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000002357 guanidines Chemical class 0.000 description 2
- PJJJBBJSCAKJQF-UHFFFAOYSA-N guanidinium chloride Chemical compound [Cl-].NC(N)=[NH2+] PJJJBBJSCAKJQF-UHFFFAOYSA-N 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-M hydrosulfide Chemical compound [SH-] RWSOTUBLDIXVET-UHFFFAOYSA-M 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 239000003223 protective agent Substances 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical group 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- VFTFKUDGYRBSAL-UHFFFAOYSA-N 15-crown-5 Chemical compound C1COCCOCCOCCOCCO1 VFTFKUDGYRBSAL-UHFFFAOYSA-N 0.000 description 1
- 150000003990 18-crown-6 derivatives Chemical group 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000001983 dialkylethers Chemical class 0.000 description 1
- MHDVGSVTJDSBDK-UHFFFAOYSA-N dibenzyl ether Chemical compound C=1C=CC=CC=1COCC1=CC=CC=C1 MHDVGSVTJDSBDK-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- MSRJTTSHWYDFIU-UHFFFAOYSA-N octyltriethoxysilane Chemical compound CCCCCCCC[Si](OCC)(OCC)OCC MSRJTTSHWYDFIU-UHFFFAOYSA-N 0.000 description 1
- 229960003493 octyltriethoxysilane Drugs 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- ANOBYBYXJXCGBS-UHFFFAOYSA-L stannous fluoride Chemical compound F[Sn]F ANOBYBYXJXCGBS-UHFFFAOYSA-L 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- ALVYUZIFSCKIFP-UHFFFAOYSA-N triethoxy(2-methylpropyl)silane Chemical compound CCO[Si](CC(C)C)(OCC)OCC ALVYUZIFSCKIFP-UHFFFAOYSA-N 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
- JBWKIWSBJXDJDT-UHFFFAOYSA-N triphenylmethyl chloride Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)(Cl)C1=CC=CC=C1 JBWKIWSBJXDJDT-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention relates to the technical field of chemical synthesis, in particular to a method for preparing a sulfur-containing silane coupling agent by adopting a tubular reactor/a microchannel reactor. The invention discloses a method for preparing 3-octanoyl thiopropyl triethoxysilane, which comprises the following steps: the solution containing sodium thioctic acid prepared by sodium hydrosulfide is used as a first raw material, the 3-chloropropyl triethoxysilane solution is used as a second raw material, and any one of the following methods is adopted: the first method comprises the steps of reacting by using a tubular reactor; and secondly, carrying out reaction by utilizing a micro-channel reactor. The method can realize continuous and stable production of the 3-octanoyl thiopropyl triethoxysilane and increase production efficiency.
Description
Technical Field
The invention relates to the technical field of chemical synthesis, in particular to a method for preparing a sulfur-containing silane coupling agent by adopting a tubular reactor/a microchannel reactor.
Background
The 3-octanoyl thiopropyl triethoxy silane is an important sulfur-containing silane coupling agent, and has a structural formula of 1 as shown in the specification, and is widely used for rubber modification, coating and fireproof material modification.
The existing process route can be summarized as follows: firstly, 3-mercaptopropyl triethoxysilane reacts with octanoyl chloride to obtain the target product 3-octanoyl thiopropyl triethoxysilane. And secondly, using a phase transfer catalysis method, reacting sodium hydrosulfide or sodium sulfide as a sulfur source with octanoyl chloride to generate sodium thiocaprylate, and then reacting with 3-chloropropyl triethoxysilane to obtain the 3-octanoyl thiopropyl triethoxysilane.
For example, patent CN201310647241.0 reports a method for producing 3-octanoylthiopropyl triethoxysilane by using 3-mercaptopropyl triethoxysilane and octanoyl chloride as reaction raw materials, which does not use water as a solvent, thereby inhibiting the hydrolysis of organosilane, but the hydrogen chloride gas generated by the reaction cannot be discharged out of the system in time, the residual hydrogen chloride gas can adversely affect the product quality, and the method has quite high requirements on the purity of the reaction substrate and the material quality of the reaction equipment, and is not suitable for industrial production.
U.S. patent No. 2005027781A1 discloses a process for preparing 3-octanoylthiopropyl triethoxysilane by reacting a haloalkylsilane with an aqueous solution of a thiocarboxylate ester silane, and also discloses a process for preparing an aqueous solution of a thiocarboxylate from a sulfide or a hydrosulfide and an acid chloride. However, the method has the problems of low product yield, long reaction time, low production efficiency and the like. Patent CN201310127670.5 discloses a method for producing 3-octanoyl thiopropyl triethoxysilane using 3-chloropropyl triethoxysilane, octanoyl chloride, sodium sulfide or sodium hydrosulfide as a substrate, adding a phase transfer catalyst and a silicon hydroxyl protecting agent to prevent hydrogen sulfide from being produced and inhibiting alkoxy hydrolysis. The phase transfer catalyst is quaternary ammonium salt, crown ether, guanidine salt or polyether; the quaternary ammonium salt is tetrabutylammonium bromide, tetrabutylammonium chloride or methyltrioctylammonium chloride; the crown ether is 18-crown-6 or 15-crown-5; the polyether is polyethylene glycol dialkyl ether; the guanidine salt is hexabutyl guanidine chloride, hexabutyl guanidine bromide, hexaethyl guanidine bromide, tripiperidinyl guanidine chloride or tripiperidinyl guanidine bromide; the addition amount of the phase transfer catalyst is 0.01% -5% of the amount of acyl halide or anhydride substances; the silicon hydroxyl protecting agent is trimethyl chlorosilane, octyl triethoxy silane, isobutyl triethoxy silane, benzyl halide, benzyl ether, triphenylchloromethane, monomethoxy triphenyl or dimethoxy triphenyl. Reflux reaction is carried out for 6 to 15 hours at the temperature of 60 to 90 ℃; the molar ratio of the sulfide to the hydrosulfide to the acyl halide or anhydride is 1-4:2; the method has complicated steps and is unfavorable for the subsequent purification of the product due to the addition of a plurality of reagents in the process.
Patent CN105601661B reports a method in which sodium thioctic acid is prepared into an aqueous solution together with a phase transfer catalyst, and the aqueous solution is reacted with raw material 3-chloropropyl triethoxysilane in a tubular reactor to obtain 3-octanoyl thiopropyl triethoxysilane. The method solves the problems of long period, large odor, low selectivity and the like of producing the 3-octanoyl thiopropyl triethoxysilane by a kettle reactor to a certain extent, but the yield is still only 88.7%, and the raw material 3-chloropropyl triethoxysilane which is not completely converted still exists in a pipeline.
Based on the prior art, the reactor is mainly in the form of batch kettle reaction. Although the method has the advantages of simple operation, flexible production adjustment capability and the like, the method still has the following defects: (1) kettle type equipment has large size and large occupied area; (2) The reaction time is long, the material feeding amount is large, and the production efficiency of a single device cannot be maximized; (3) The automation degree is low, and the automatic continuous centralized control operation is difficult to realize.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a method for preparing 3-octanoyl thiopropyl triethoxysilane.
The invention provides a process for synthesizing 3-octanoyl thiopropyl triethoxysilane by a tubular reactor, which can realize continuous stable production and increase production efficiency; the invention also provides a process for synthesizing 3-octanoyl thiopropyl triethoxysilane by the micro-channel reactor, which greatly reduces the reaction time and increases the production efficiency.
In order to solve the technical problems, the invention provides a method for preparing 3-octanoyl thiopropyl triethoxysilane, which takes a solution containing sodium thiocaprylate prepared by sodium hydrosulfide as a raw material I, takes a 3-chloropropyl triethoxysilane solution as a raw material II, and adopts any one of the following methods:
the first method comprises the steps of reacting by using a tubular reactor;
and secondly, carrying out reaction by utilizing a micro-channel reactor.
As an improvement of the process for preparing 3-octanoylthiopropyl triethoxysilane of the present invention:
the method one comprises the following steps:
1.1 Dissolving 165+/-10 g sodium hydrosulfide hydrate and 10+/-0.5 g phase transfer catalyst in 400+/-40 g water, loading into a reaction kettle, adding 163+/-10 g octanoyl chloride into the reaction kettle at the temperature of not more than 10 ℃ (5-10 ℃) (dropwise adding, controlling the temperature of a system in the dropwise adding process to be not more than 10 ℃), and stirring for 1+/-0.1 hour at room temperature to obtain an aqueous solution containing sodium thiocaprylate as a raw material I for standby;
dissolving 192+/-10 g of 3-chloropropyl triethoxysilane in 300+/-30 g of toluene to obtain a toluene solution of 3-chloropropyl triethoxysilane, which is used as a raw material II for standby;
1.2 Pumping an aqueous solution (raw material I) containing sodium thioctic acid and a 3-chloropropyl triethoxysilane toluene solution (raw material II) into a premixer through respective feed pumps according to a set flow rate ratio to mix, allowing the mixture to enter a tubular reactor for reaction, and setting the pressure of a back pressure valve at the outlet of the tubular reactor to be 0.1-0.2 Mpa; the reaction temperature is 70-120 ℃, and the residence time of the mixture in the tubular reactor is 80-160 min;
the feeding flow rate ratio of the aqueous solution containing sodium thioctic acid (raw material I) to the 3-chloropropyl triethoxysilane toluene solution (raw material II) is 6.4-5.2:4.3-5.5, the flow rate of the aqueous solution of sodium thioctic acid can be set to be 6.4-5.2 g/min, and the flow rate of the 3-chloropropyl triethoxysilane toluene solution is 4.3-5.5 g/min; after the 3-chloropropyl triethoxysilane toluene solution (raw material II) is fed, the aqueous solution (raw material I) containing the sodium thioctic acid is stopped to be fed; that is, the feeding time of the two is consistent;
1.3 And (3) allowing the liquid obtained after the reaction to flow out from the outlet of the tubular reactor, collecting the effluent of the tubular reactor, and carrying out reduced pressure distillation on the effluent to obtain the 3-octanoyl thiopropyl triethoxysilane.
As a further improvement of the process for preparing 3-octanoylthiopropyl triethoxysilane of the present invention:
the phase transfer catalyst in step 1.1) of the method one is methyltrioctylammonium chloride, tetrabutylammonium bromide (preferred), tetrapropylammonium bromide.
As a further improvement of the process for preparing 3-octanoylthiopropyl triethoxysilane of the present invention:
the reaction temperature in step 1.2) of the first method is 100 ℃; the residence time is 120min; the feed flow rate ratio of the aqueous solution containing sodium thioctic acid (feed one) to the 3-chloropropyl triethoxysilane toluene solution (feed two) was 5.8:4.9.
as an improvement to the process of the present invention for preparing 3-octanoylthiopropyl triethoxysilane, said process two comprising the steps of:
2.1 Dissolving 206+ -10 g sodium hydrosulfide and 13+ -0.5 g phase transfer catalyst with 500 g+ -50 water, loading into a reaction kettle (kettle reactor), adding 204+ -10 g octanoyl chloride (dropwise adding, controlling the system temperature in the dropwise adding process to be not more than 10 ℃) into the reaction kettle at the temperature of not more than 10 ℃, stirring for 1+ -0.1 hour at room temperature to obtain an aqueous solution containing sodium thioctic acid as a raw material I for standby;
dissolving 240+/-10 g of 3-chloropropyl triethoxysilane in 380+/-30 g of toluene to obtain a toluene solution of the 3-chloropropyl triethoxysilane, which is used as a raw material II for standby;
2.2 Pumping an aqueous solution (raw material I) containing sodium thioctic acid and a 3-chloropropyl triethoxysilane toluene solution (raw material II) into a star-shaped mixer according to a set flow rate ratio respectively through respective feed pumps to pre-mix and preheat (controlling the retention time to be 2+/-0.5 min and the preheating temperature to be 70-120 ℃), and enabling the obtained mixture after preheating to enter a microchannel reactor for reaction, wherein the pressure of a back pressure valve at the outlet of the microchannel reactor is set to be 0.1-0.2 Mpa; the reaction temperature is 70-120 ℃, and the residence time of the mixture in the microchannel reactor after preheating is 120-300 s;
the ratio of the feeding flow rate of the aqueous solution containing sodium thioctic acid (raw material I) to the 3-chloropropyl triethoxysilane toluene solution (raw material II) is 14.9-8.1:10.8-14.6 (preferably 14.1-10.3:10.8-14.6), the flow rate of the aqueous solution containing sodium thioctic acid can be set to be 14.9-8.1 g/min, and the flow rate of the 3-chloropropyl triethoxysilane toluene solution is 10.8-14.6 g/min;
after the 3-chloropropyl triethoxysilane toluene solution (raw material II) is fed, the aqueous solution (raw material I) containing the sodium thioctic acid is stopped to be fed; that is, the feeding time of the two is consistent;
description: in the reaction, the excessive sodium thioctic acid aqueous solution does not need to be completely reacted; namely, the feeding time of the 3-chloropropyl triethoxysilane toluene solution and the water phase solution is kept consistent;
2.3 And (3) allowing the liquid obtained after the reaction to flow out from the outlet of the microchannel reactor, collecting effluent of the microchannel reactor, and carrying out reduced pressure distillation on the effluent to obtain the product 3-octanoyl thiopropyl triethoxysilane.
As a further improvement of the process for preparing 3-octanoylthiopropyl triethoxysilane of the present invention:
the phase transfer catalyst in step 2.1) of the second method is methyltrioctylammonium chloride, tetrabutylammonium bromide (preferred), tetrapropylammonium bromide and the like.
As a further improvement of the process for preparing 3-octanoylthiopropyl triethoxysilane of the present invention:
in the step 2.2) of the second method, the reaction temperature is 100 ℃, the residence time is 240s, and the back pressure valve is set to be 0.1Mpa;
the ratio of the feed flow rate of the aqueous solution containing sodium thioctic acid (feed one) to the 3-chloropropyl triethoxysilane toluene solution (feed two) was 13.5:11.4.
the method has the beneficial effects that:
1. the invention greatly shortens the reaction time and greatly improves the production efficiency.
2. The invention has convenient operation and less personnel operation.
3. The invention adopts the tubular reactor, has small occupied area and can realize continuous production.
4. The invention adopts the tubular reactor, and the product quality is stable.
5. The prior art (such as CN 201310127670.5) adopts single-phase reaction (aqueous solvent) and has poor reaction effect.
In the invention, the tubular reactor is used, sodium hydrosulfide and 3-chloropropyl triethoxy silane are used as raw materials, water and toluene are used as solvents, and the 3-octanoyl thiopropyl triethoxy silane is synthesized by a phase transfer catalysis method, so that the continuous production of the product is realized, and the production efficiency is improved.
The invention effectively solves the problem of easy gel of the tubular reactor, thereby ensuring that the tubular reactor is not blocked, and further achieving the effects of high efficiency, high speed and continuous production.
The second method has the beneficial effects that:
1. the invention enhances the mass transfer of the reaction, shortens the reaction and improves the production efficiency.
2. The invention realizes the continuous production of the 3-octanoyl thiopropyl triethoxy silane, has convenient operation and is convenient for realizing automatic control.
3. The invention adopts the micro-channel reactor, has stable product quality and no amplification effect, and can adjust the productivity according to actual needs.
The microchannel reactor is a special continuous reactor, has larger specific surface area compared with a common tubular reactor, can quickly transfer generated heat, and has high heat exchange efficiency. Little back mixing exists in the microchannel reactor, the material residence time distribution is narrow, and the microchannel reactor can be approximately regarded as a plug flow reactor. According to the invention, the micro-channel reactor is utilized, sodium thioctic acid and 3-chloropropyl triethoxysilane are used as reaction raw materials, and 3-octanoyl thiopropyl triethoxysilane is prepared by a phase transfer catalysis method, so that continuous production of products is realized, and the production efficiency is greatly improved.
Drawings
The following describes the embodiments of the present invention in further detail with reference to the accompanying drawings.
FIG. 1 is a schematic representation of a reactor apparatus used in the process of the present invention.
FIG. 2 is a schematic representation of a reactor apparatus used in the second process of the present invention.
Fig. 3 is a schematic diagram of the microchannel reactor 6 in fig. 2.
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 product obtained by the invention is proved to be really 3-octanoyl thiopropyl triethoxysilane by the detection modes of conventional standard sample comparison, nuclear magnetic hydrogen spectrum, nuclear magnetic carbon spectrum and the like.
The room temperature of the invention is 15-25 ℃.
Device example 1:
the device for preparing the 3-octanoyl thiopropyl triethoxysilane has the structure shown in figure 1, and comprises a preparation kettle 1, a first charging tank 2, a water phase metering pump 3, a second charging tank 4, an organic phase metering pump 5, a premixer 6, a tubular reactor 7, a constant temperature ultrasonic water bath 8 and a receiving tank 9; the tubular reactor 7 is positioned in a constant temperature ultrasonic water bath 8, and the reaction temperature in the tubular reactor 7 is controlled by the constant temperature ultrasonic water bath 8. The tube diameter of the tube reactor 7 is about phi 3mm.
The outlet of the preparation kettle 1 is provided with a ball valve V 1 And then is connected with the inlet of the first charging tank 2, and the outlet of the first charging tank 2 is connected with the outlet of the second charging tank through the ball valve V 2 And then is connected with the inlet of the water phase metering pump 3, and the outlet of the water phase metering pump 3 sequentially passes through the check valve V 4 Ball valve V 3 And then to the inlet of the premixer 6.
The outlet of the second charging tank 4 passes through a ball valve V 5 And then is connected with the inlet of the organic phase metering pump 5, and the outlet of the organic phase metering pump 5 sequentially passes through the check valve V 7 Ball valve V 6 And then to the inlet of the premixer 6.
The outlet of the pre-mixer 6 is connected with the inlet of the tubular reactor 7, and the outlet of the tubular reactor 7 sequentially passes through a back pressure valve V 8 Ball valve V 9 And then is connected with the top inlet of the receiving tank 9, and the bottom outlet of the receiving tank 9 is connected with the bottom inlet of the receiving tank through a ball valve V 10 The rear part is divided into two paths, one path is connected with the needle valve V 12 The other way is connected with the ball valve V 11 Are connected. The top of the receiving tank 9 is provided with a safety valve and a pressure gauge.
Sodium thioctic acid is prepared in a preparation kettle 1, and a ball valve V is opened after the preparation is finished 1 Leading into a charging tank I2 for storage; the charging tank 4 stores a mixed solution prepared by chloropropyl triethoxysilane and toluene, ball valves V2 and V3 and ball valves V5 and V6 are opened, so that the two raw materials enter a premixer 6, are mixed in the premixer 6 and then are conveyed into a tubular reactor 7 for reaction, the ball valve V9 is opened, the obtained reaction product flows into a receiving tank 9, and finally the 3-octanoyl thiopropyl triethoxysilane is obtained through reduced pressure distillation and purification.
Ball valve V 1 Ball valve V 3 Is used for controlling the content of thiooctylOpening and closing of sodium acid aqueous solution raw material pipeline and check valve V 4 The function of (2) is to prevent the backflow of the aqueous solution containing the sodium thioctic acid;
ball valve V 5 Ball valve V 6 The function of (1) is to control the opening and closing of the raw material pipeline of the 3-chloropropyl triethoxysilane toluene solution, and the check valve V 7 The function of the catalyst is to prevent the backflow of the toluene solution of the 3-chloropropyl triethoxysilane;
back pressure valve V 8 The function of (2) is to regulate the upstream pressure, thereby ensuring the stability of the output flow of the pump;
ball valve V 9 The function of the device is to control the opening and closing of the pipe from the pipe reactor 7 to the receiving tank 9;
ball valve V 10 Is used for controlling the opening and closing of the discharge pipeline upstream of the receiving tank 9, and the needle valve V 12 The function of (a) is to adjust the flow, the ball valve V 11 The function of which is to control the opening and closing of the discharge line downstream of the receiving tank 9.
Example 1-1, a process for preparing 3-octanoylthiopropyl triethoxysilane, comprising the steps of:
1) 165g (2.0 mol) of sodium hydrosulfide hydrate (68%) and 10g of tetrabutylammonium bromide are dissolved by 400g of water, the mixture is filled into a preparation kettle 1, 163g (1.0 mol) of octanoyl chloride is dripped into the preparation kettle 1 at 5-10 ℃, the temperature of the system is controlled to be not more than 10 ℃ in the dripping process, and after stirring is carried out for 1 hour at room temperature, the obtained product, namely the aqueous solution containing the sodium thioctic acid, is filled into a charging tank I2 for standby.
The reaction formula is:
192g of 3-chloropropyl triethoxysilane is dissolved by 300g of toluene to obtain a toluene solution of 3-chloropropyl triethoxysilane, and the toluene solution is filled into a second charging tank 4 for standby.
2) Setting the flow rate of the aqueous solution containing the sodium thioctic acid to be 5.8g/min, setting the flow rate of the 3-chloropropyl triethoxy silane toluene solution to be 4.9g/min, and pumping the aqueous phase metering pump 3 and the organic phase metering pump 5 into a premixing mode respectivelyMixing in a mixer 6, allowing the mixed materials to enter a tubular reactor 7 for reaction at 100 ℃ with a back pressure valve V 8 Setting 0.1MPa, and keeping the mixed materials in the tubular reactor 7 for 120min, namely, keeping the reaction time for 120min.
Description: the feed time of the toluene solution of 3-chloropropyl triethoxysilane was 100.4 minutes; the feeding time of the aqueous solution containing sodium lipoic acid was the same as that of the toluene solution of 3-chloropropyl triethoxysilane, and therefore the feeding amount of the aqueous solution containing sodium lipoic acid was 582.3g, i.e., the remaining aqueous solution containing sodium lipoic acid was still in the charging tank one 2.
The reaction formula is:
3) The liquid obtained after the reaction flows out from the outlet of the tubular reactor 7, enters the receiving tank 9, is finally discharged from the discharge port at the bottom of the receiving tank 9, is distilled under reduced pressure, and is collected into a fraction of 140-145 ℃ under the vacuum degree of 97kPa, thus obtaining 267.5g of 3-octanoyl thiopropyl triethoxysilane.
Examples 1-2 to 1-6
The 3-octanoyl thiopropyl triethoxysilane yield was measured by changing the temperature of the tube reactor 7 by changing the temperature of the thermostatic ultrasonic water bath 8 with respect to example 1-1, and the following data were obtained as shown in Table 1.
TABLE 1 influence of reaction temperature on yield
Yield = [ m (3-octanoylthiopropyltriethoxysilane obtained by distillation under reduced pressure)/364.6 ]/[ m (3-chloropropyltriethoxysilane starting material)/240 ].
That is, the yield was calculated by the present reaction based on the amount of 3-chloropropyl triethoxysilane used.
Examples 2-1 to 2-2
The type of phase transfer catalyst was changed relative to example 1-1, the weight remained unchanged, still 10g, and the rest was identical to example 1-1. The product yield was checked to give the following data (Table 2).
TABLE 2 influence of phase transfer catalyst on yield
| Group of | Phase transfer catalyst species | Yield (%) |
| Example 2-1 | Methyl trioctyl ammonium chloride | 84.2 |
| Example 2-2 | Tetrapropylammonium bromide | 89.5 |
Examples 3-1 to 3-3
The reaction residence time was changed by adjusting the tube length of the tube reactor 7 with respect to example 1-1, and the remainder was identical to example 1-1. The product yield was checked to give the following data (Table 3).
TABLE 3 influence of reaction residence time on yield
Examples 4-1 to 4-3
The total feed flow was maintained constant to control the reaction residence time relative to example 1-1, and the feed ratio was varied by varying the feed flow rate, the remainder being identical to example 1-1. The product yield was checked to give the following data (Table 4).
TABLE 4 influence of flow rate on yield
Comparative example 1
Comparative example 1 was directly conducted without adding a phase transfer catalyst with respect to example 1-1, and the rest of the conditions were identical to those of example 1-1, with a final yield of 73.3%.
Comparative example 2
Comparative example 2 was obtained by changing only the amount of tetrabutylammonium bromide relative to example 1-1, and the other conditions were the same as in example 1-1, to obtain the following data (Table 5)
TABLE 5 comparative example 2 final yield
Comparative examples 3-1 to 3-2
Comparative examples 3-1 to 3-2 with respect to example 1-1, the reaction residence time was changed by adjusting the tube length of the tube reactor 7, and the other conditions were the same as those of example 1-1, to obtain the following data (Table 6)
TABLE 6 final yields for comparative examples 4-1-4-2
Comparative example 4, reference CN201310127670.5 used only water as the reaction solvent, i.e., 300g of toluene was omitted and 192g of 3-chloropropyl triethoxysilane was used in tank two 4. The aqueous solution containing sodium lipoic acid in the first charging tank 2 is the same as in example 1-1.
The flow rate of the aqueous solution containing sodium lipoic acid was set to 8.0g/min, the flow rate of 3-chloropropyl triethoxysilane was set to 2.6g/min, and the remainder was identical to example 1-1.
The following drawbacks were found in this protocol: clogging is easily generated in the pipe, and thus the reaction cannot be effectively continued.
Device example 2:
the device for preparing the 3-octanoyl thiopropyl triethoxysilane is formed by connecting a micro-channel reactor 6 and other equipment, and the structure of the device is shown in figure 2, and comprises a sodium thiocaprylate storage tank 1; a sodium thioctic acid feed pump 2; a 3-chloropropyl triethoxysilane storage tank 3; 3-chloropropyl triethoxysilane feed pump 4; preheating the premixer 5; a microchannel reactor 6 (a microchannel reactor enhanced mass transfer type microchannel module 6); a receiving tank 7; a back pressure valve 8; check valves 9-13;
the receiving tank 7 is provided with a pressure gauge PG and a liquid level gauge LG.
The outlet of the sodium thiocctanoate storage tank 1 is connected with the inlet of the preheating premixing module 5 after passing through the one-way valve 9, the sodium thiocctanoate feed pump 2 and the one-way valve 10 in sequence;
the outlet of the 3-chloropropyl triethoxy silane storage tank 3 is connected with the inlet of the preheating pre-mixer 5 after passing through a one-way valve 11 and a one-way valve 12 of the 3-chloropropyl triethoxy silane feed pump 4 in sequence;
the outlet of the preheating pre-mixer 5 is connected with the inlet of the micro-channel reactor 6, and the outlet of the micro-channel reactor 6 is connected with the top inlet of the receiving tank 7 after passing through the back pressure valve 8 and the one-way valve 13 in sequence.
The microchannel reactor 6 is as described in fig. 3; the pre-heating premixer 5 and the microchannel reactor 6 are conventional and known in the art, and therefore the structure thereof is not described in detail in the present invention.
The sodium thioctic acid storage tank 1 is used for storing a mixed solution prepared by sodium thioctic acid, a phase transfer catalyst and a solvent, the 3-chloropropyl triethoxysilane storage tank 3 is used for storing a mixed solution prepared by 3-chloropropyl triethoxysilane and the solvent, the two raw materials are respectively conveyed into the preheating premixer 5 through the sodium thioctic acid feed pump 2 and the 3-chloropropyl triethoxysilane feed pump 4, enter the microchannel reactor 6 after the preheating premixer is finished, react for a period of time at a certain temperature, flow into the collecting tank 7, and are subjected to reduced pressure distillation purification to obtain the 3-octanoyl thiopropyl triethoxysilane.
Example one-1, a method for preparing 3-octanoylthiopropyl triethoxysilane, comprises the steps of:
1) Preparing raw material sodium thioctic acid:
dissolving 206g of sodium hydrosulfide and 13g of tetrabutylammonium bromide in 500g of water, loading into a reaction kettle (kettle reactor), dropwise adding 204g of octanoyl chloride into the reaction kettle at 5-10 ℃ in the dropwise adding process (the temperature of the system is controlled not to exceed 10 ℃), stirring for 1 hour at room temperature to obtain an aqueous solution containing sodium thioctic acid, and loading the aqueous solution containing sodium thioctic acid into a sodium thioctic acid storage tank 1 as a raw material I for later use.
240g of 3-chloropropyl triethoxysilane is dissolved in 380g of toluene and is filled into a 3-chloropropyl triethoxysilane storage tank 3 to be used as a raw material II.
2) Setting the flow rate of the aqueous solution containing the sodium thioctic acid prepared in the step 1) to be 13.5g/min, setting the flow rate of the 3-chloropropyl triethoxysilane solution to be 11.4g/min, pumping the aqueous solution into a preheating pre-mixer 5 respectively through a sodium thioctic acid feeding pump 2 and a 3-chloropropyl triethoxysilane feeding pump 4 to pre-mix and pre-heat (the pre-heat temperature is 100 ℃ for about 2 min), entering a micro-channel reactor 6 after the pre-mixing and pre-heating is finished, setting a back pressure valve 8 to be 0.1MPa, and setting the reaction temperature to be 100 ℃ and the reaction residence time to be 240s.
Description: the feed time of the toluene solution of 3-chloropropyl triethoxysilane was 54.4 minutes; the feeding time of the aqueous solution containing sodium lipoic acid was the same as that of the toluene solution of 3-chloropropyl triethoxysilane, and thus the feeding amount of the aqueous solution containing sodium lipoic acid was 734.2g, i.e., the remaining aqueous solution containing sodium lipoic acid was still in the sodium lipoic acid tank 1.
By adjusting the liquid holdup of the microchannel reactor 6, the reaction residence time can be controlled accordingly.
3) And the reacted solution flows out from the outlet of the enhanced mass transfer type reaction module 6, enters the receiving tank 7, finally flows out from the receiving tank 7, is distilled under reduced pressure, and is collected into a fraction of 140-145 ℃ under the vacuum degree of 97kPa, so as to obtain the 3-octanoyl thiopropyl triethoxysilane.
Example one-2 to example one-6;
the product yield and selectivity were measured by varying the temperature in the pre-heating premixer 5 and the microchannel reactor 6, resulting in the following data (Table 7).
TABLE 7 influence of reaction temperature on yield
Yield = [ m (3-octanoylthiopropyltriethoxysilane obtained by distillation under reduced pressure)/364.6 ]/[ m (3-chloropropyltriethoxysilane starting material)/240 ].
Description: in this reaction, sodium thioctic acid is used as an excessive sulfur source, and the yield is calculated based on the amount of 3-chloropropyl triethoxysilane used.
Examples two-1 to two-2
The weight was kept unchanged relative to example one-1 by changing the type of phase transfer catalyst; the remainder was identical to example one-1. The product yield was checked to give the following data (Table 8).
TABLE 8 influence of phase transfer catalyst on yield
| Group of | Phase transfer catalyst species | Yield (%) |
| Example two-1 | Methyl trioctyl ammonium chloride | 92.5 |
| Example two-2 | Tetrapropylammonium bromide | 93.1 |
Examples three-1 to three-3
The reaction residence time of the mixture in the microchannel reactor 6 was controlled by changing the flow rates of the aqueous phase solution and the organic phase solution in the same ratio as in example 1, and the remainder was identical to example 1. The product yield was checked to give the following data (Table 9).
Description: the residence time of the microchannel reactor 6 is regulated by scaling up/down the flow of material by the same ratio, with the total liquid holdup unchanged (without changing the number of plates).
TABLE 9 influence of reaction residence time on yield
Examples four-1 to four-3
The total feed flow was maintained and the reaction residence time was controlled as compared to example one-1, and the feed ratio was varied by varying the feed flow rate, the remainder being identical to example one-1. The product yield was checked to give the following data (Table 10).
TABLE 10 influence of flow rate on yield
Comparative example one
Comparative example one was conducted without mixing and preheating the reaction raw materials by using a preheating mixer, and the reaction was directly conducted, with respect to example one-1, and the other conditions were the same as example one-1, with a final yield of 91.2%.
Comparative example two
Comparative example two did not use a phase transfer catalyst with respect to example one-1, the remaining conditions were identical to example one-1 with a final yield of 75.6%.
Comparative examples three-1 to three-2
In comparison with example one-1, comparative examples three-1 to three-2, in which the flow rate of the material was changed in the same ratio to change the reaction residence time on the premise of ensuring the total flow rate of the material, and the other conditions were the same as those of example one-1, the following data were obtained (Table 11)
TABLE 11 final yields of comparative examples three-1 to three-2
Comparative example four: in contrast to example one-1, the use of toluene was eliminated and only 3-chloropropyl triethoxysilane was charged in the 3-chloropropyl triethoxysilane tank 3, and in practice, the reaction could not continue because the microchannel reactor 6 was blocked by a single-phase reaction.
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 (7)
1. A process for preparing 3-octanoylthiopropyl triethoxysilane characterized in that: the solution containing sodium thioctic acid prepared by sodium hydrosulfide is used as a first raw material, the 3-chloropropyl triethoxysilane solution is used as a second raw material, and any one of the following methods is adopted:
the first method comprises the steps of reacting by using a tubular reactor;
and secondly, carrying out reaction by utilizing a micro-channel reactor.
2. The process for preparing 3-octanoylthiopropyl triethoxysilane as claimed in claim 1, wherein:
the method one comprises the following steps:
1.1 Dissolving 165+/-10 g of sodium hydrosulfide hydrate and 10+/-0.5 g of a phase transfer catalyst in 400+/-40 g of water, loading the mixture into a reaction kettle, adding 163+/-10 g of octanoyl chloride into the reaction kettle at the temperature of not more than 10 ℃, and stirring the mixture for 1+/-0.1 hour at room temperature to obtain an aqueous solution containing sodium thioctic acid as a raw material I;
dissolving 192+/-10 g of 3-chloropropyl triethoxysilane in 300+/-30 g of toluene to obtain a toluene solution of 3-chloropropyl triethoxysilane as a second raw material;
1.2 Pumping the aqueous solution containing sodium thioctic acid and the 3-chloropropyl triethoxy silane toluene solution into a premixer through respective feed pumps according to a set flow rate ratio to mix, allowing the mixture to enter a tubular reactor for reaction, and setting the pressure of a back pressure valve at the outlet of the tubular reactor to be 0.1-0.2 Mpa; the reaction temperature is 70-120 ℃, and the residence time of the mixture in the tubular reactor is 80-160 min;
the feed flow rate ratio of the aqueous solution containing the sodium thioctic acid to the 3-chloropropyl triethoxysilane toluene solution is 6.4-5.2:4.3-5.5; after the 3-chloropropyl triethoxysilane toluene solution is fed, stopping feeding the aqueous solution containing the sodium thioctic acid;
1.3 And (3) allowing the liquid obtained after the reaction to flow out from the outlet of the tubular reactor, collecting the effluent of the tubular reactor, and carrying out reduced pressure distillation on the effluent to obtain the 3-octanoyl thiopropyl triethoxysilane.
3. The process for preparing 3-octanoylthiopropyl triethoxysilane as claimed in claim 2, wherein:
the phase transfer catalyst in step 1.1) of the method one is methyltrioctylammonium chloride, tetrabutylammonium bromide and tetrapropylammonium bromide.
4. A process for preparing 3-octanoylthiopropyl triethoxysilane as claimed in claim 3, wherein:
the reaction temperature in step 1.2) of the first method is 100 ℃; the residence time is 120min; the feed flow rate ratio of the aqueous solution containing sodium thioctic acid to the toluene solution of 3-chloropropyl triethoxysilane was 5.8:4.9.
5. the process for preparing 3-octanoylthiopropyl triethoxysilane as claimed in claim 1, wherein:
the second method comprises the following steps:
2.1 Dissolving 206+ -10 g sodium hydrosulfide and 13+ -0.5 g phase transfer catalyst with 500 g+ -50 water, loading into a reaction kettle, adding 204+ -10 g octanoyl chloride into the reaction kettle at a temperature not exceeding 10deg.C, stirring at room temperature for 1+ -0.1 hr to obtain aqueous solution containing sodium thiocaprylate as raw material I;
using 380+/-30 g toluene to dissolve 240+/-10 g 3-chloropropyl triethoxysilane to obtain a toluene solution of the 3-chloropropyl triethoxysilane as a second raw material;
2.2 Pumping the aqueous solution containing sodium thiocctate and the 3-chloropropyl triethoxysilane toluene solution into a star-shaped mixer through respective feed pumps according to a set flow rate ratio to pre-mix and preheat, enabling the obtained preheated mixture to enter a microchannel reactor for reaction, and setting the pressure of a back pressure valve at the outlet of the microchannel reactor to be 0.1-0.2 Mpa; the reaction temperature is 70-120 ℃, and the residence time of the mixture in the microchannel reactor after preheating is 120-300 s;
the feed flow rate ratio of the aqueous solution containing the sodium thioctic acid to the 3-chloropropyl triethoxysilane toluene solution is 14.9-8.1:10.8-14.6;
after the 3-chloropropyl triethoxysilane toluene solution is fed, stopping feeding the aqueous solution containing the sodium thioctic acid;
2.3 And (3) allowing the liquid obtained after the reaction to flow out from the outlet of the microchannel reactor, collecting effluent of the microchannel reactor, and carrying out reduced pressure distillation on the effluent to obtain the 3-octanoyl thiopropyl triethoxysilane.
6. The method for preparing 3-octanoyl thiopropyl triethoxysilane according to claim 5, wherein:
the phase transfer catalyst in step 2.1) of the second method is methyltrioctylammonium chloride, tetrabutylammonium bromide and tetrapropylammonium bromide.
7. The method for preparing 3-octanoyl thiopropyl triethoxysilane according to claim 6, wherein:
in the step 2.2) of the second method, the reaction temperature is 100 ℃, the residence time is 240s, and the back pressure valve is set to be 0.1Mpa;
the ratio of the feed flow rate of the aqueous solution containing sodium thioctic acid to the 3-chloropropyl triethoxysilane toluene solution was 13.5:11.4.
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