CN114989210B - Method for continuously preparing aminopropylalkoxysilane - Google Patents
Method for continuously preparing aminopropylalkoxysilane Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 29
- -1 aminopropyl Chemical group 0.000 claims abstract description 26
- 239000002608 ionic liquid Substances 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 17
- 230000002745 absorbent Effects 0.000 claims abstract description 17
- 239000002250 absorbent Substances 0.000 claims abstract description 17
- 239000011259 mixed solution Substances 0.000 claims abstract description 16
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims abstract description 11
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims abstract description 11
- 229940045803 cuprous chloride Drugs 0.000 claims abstract description 11
- 238000000926 separation method Methods 0.000 claims abstract description 11
- 238000004821 distillation Methods 0.000 claims abstract description 10
- 239000011787 zinc oxide Substances 0.000 claims abstract description 8
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims abstract description 6
- 238000010924 continuous production Methods 0.000 claims abstract description 6
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 claims abstract description 6
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 6
- KSCAZPYHLGGNPZ-UHFFFAOYSA-N 3-chloropropyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)CCCCl KSCAZPYHLGGNPZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 6
- OXYZDRAJMHGSMW-UHFFFAOYSA-N 3-chloropropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCCl OXYZDRAJMHGSMW-UHFFFAOYSA-N 0.000 claims description 5
- KNTKCYKJRSMRMZ-UHFFFAOYSA-N 3-chloropropyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)CCCCl KNTKCYKJRSMRMZ-UHFFFAOYSA-N 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- UBQLCZUQCFNAGM-UHFFFAOYSA-N cyanoiminomethylideneazanide;2-(3-methylimidazol-3-ium-1-yl)ethanol Chemical compound N#C[N-]C#N.CN1C=C[N+](CCO)=C1 UBQLCZUQCFNAGM-UHFFFAOYSA-N 0.000 claims 1
- WLTHPEHYBIKNHR-UHFFFAOYSA-M methyl sulfate;tris(2-hydroxyethyl)-methylazanium Chemical compound COS([O-])(=O)=O.OCC[N+](C)(CCO)CCO WLTHPEHYBIKNHR-UHFFFAOYSA-M 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 21
- 125000003545 alkoxy group Chemical group 0.000 abstract description 16
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 abstract description 15
- 229910000077 silane Inorganic materials 0.000 abstract description 15
- 229910021529 ammonia Inorganic materials 0.000 abstract description 9
- 239000006227 byproduct Substances 0.000 abstract description 9
- 239000002253 acid Substances 0.000 abstract description 3
- 239000012429 reaction media Substances 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 239000012847 fine chemical Substances 0.000 abstract description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 8
- 239000011701 zinc Substances 0.000 description 7
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 6
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 description 5
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 235000005074 zinc chloride Nutrition 0.000 description 4
- 239000011592 zinc chloride Substances 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 238000006459 hydrosilylation reaction Methods 0.000 description 3
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 238000005915 ammonolysis reaction Methods 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- HXLAEGYMDGUSBD-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propan-1-amine Chemical compound CCO[Si](C)(OCC)CCCN HXLAEGYMDGUSBD-UHFFFAOYSA-N 0.000 description 1
- ZYAASQNKCWTPKI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propan-1-amine Chemical compound CO[Si](C)(OC)CCCN ZYAASQNKCWTPKI-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0093—Microreactors, e.g. miniaturised or microfabricated reactors
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/08—Halides
- B01J27/122—Halides of copper
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/20—Purification, separation
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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Abstract
The invention belongs to the technical field of fine chemical synthesis, and particularly relates to a method for continuously preparing aminopropyl alkoxy silane. Dissolving ammonia gas in an ionic liquid to reach a saturated state, sequentially adding chloropropyl alkoxy silane, a catalyst and an absorbent to form a mixed solution, injecting the mixed solution into a microchannel reactor through a plunger pump for reaction, collecting a product at the tail end of the microchannel reactor, and carrying out reduced pressure distillation and separation to obtain aminopropyl alkoxy silane. The invention adds the ionic liquid as a reaction medium, cuprous chloride or cuprous bromide as a catalyst and zinc oxide as an acid absorbent, so that the reaction can be carried out at normal temperature and normal pressure, the ammonia demand is low, the utilization rate is high, and the generation of secondary and tertiary aminopropylalkoxysilane byproducts is reduced. The invention is a synthetic route of aminopropyl alkoxy silane, which is green, environment-friendly, safe and stable, has few byproducts and high continuous production capacity.
Description
Technical Field
The invention belongs to the technical field of fine chemical synthesis, and particularly relates to a method for continuously preparing aminopropyl alkoxy silane.
Background
Aminopropyl alkoxy silane is a reactive silane coupling agent, is easy to generate hydrolysis reaction and crosslinking reaction, amino and alkoxy functional groups in molecules are respectively used for coupling organic high molecules and inorganic fillers to enhance the cohesiveness of the organic high molecules and the inorganic fillers and improve the mechanical, electrical, water-resistant, ageing-resistant and other performances of products, and in addition, the aminopropyl alkoxy silane can also be used as a reinforcing agent, a crosslinking accelerator, a resin modifier and the like and is commonly used in the industries of glass fibers, casting, textile auxiliaries, insulating materials, adhesives and the like.
The synthesis method of aminopropyl alkoxy silane mainly comprises three methods: the first method is a hydrosilylation method disclosed in patent nos. CN105669739A and CN110506046A, which is to prepare aminopropylalkoxysilane by hydrosilylation reaction of hydrogen-containing alkoxysilane and allylamine in the presence of a catalyst such as platinum, rhodium or iridium under normal pressure and at a certain temperature, however, in this method, due to the high reactivity of allylamine, the hydrosilylation reaction generates γ -position and β -position isomer products, and the yield of the target product is low and it is difficult to separate and purify. The second method is a hydrogenation reduction method related to patent CN109517005A, cyanoethyl alkoxysilane and hydrogen gas are subjected to reduction reaction under the conditions of pressurization and catalyst to prepare aminopropyl alkoxysilane, but the raw material cyanoethyl alkoxysilane has high cost, and the hydrogenation reduction reaction has strict requirements on process and equipment, so that the method is difficult to realize industrial application. The third method is an ammonolysis method related to patents CN101768180A and CN113501839A, two raw materials of chloropropyl alkoxysilane and ammonia gas (liquid ammonia) are subjected to an ammonia nucleophilic substitution reaction to prepare aminopropyl alkoxysilane under the conditions of high temperature and high pressure, although the method is a main way in the current industrial production, the method also has the defects of harsh reaction conditions (high temperature and high pressure), large ammonia demand, low utilization rate (the molar ratio is more than 20 times excessive), more byproducts (ammonium chloride salt and secondary and tertiary aminopropyl alkoxysilane) and the like. In addition, a batch kettle type reactor is often adopted in the industrial preparation of aminopropyl alkoxy silane, the stability among batches is poor, and the continuous production capacity is insufficient.
Therefore, it is highly desirable to develop a method for continuously preparing aminopropylalkoxysilane.
Disclosure of Invention
The invention aims to provide a method for continuously preparing aminopropyl alkoxy silane, and provides an aminopropyl alkoxy silane synthesis path which is environment-friendly, safe and stable, less in by-product and high in continuous production capacity.
The technical scheme adopted by the invention for solving the technical problems is as follows:
the method for continuously preparing the aminopropyl alkoxysilane comprises the steps of dissolving ammonia gas in an ionic liquid to reach a saturated state, sequentially adding chloropropyl alkoxysilane, a catalyst and an absorbent to form a mixed solution, injecting the mixed solution into a microchannel reactor through a plunger pump for reaction, collecting a product at the tail end of the microchannel reactor, and carrying out reduced pressure distillation and separation to obtain the aminopropyl alkoxysilane.
Wherein:
the ionic liquid is [ MTEOA ]] + [MeOSO 3 ] - 、[EtOHmim] + [DCA] - Or [ Bmim ]] + [Zn 2 Cl 5 ] - Preferably, [ Bmim ]] + [Zn 2 Cl 5 ] - 。
The chloropropyl alkoxy silane is gamma-chloropropyl triethoxy silane, gamma-chloropropyl methyl diethoxy silane, gamma-chloropropyl trimethoxy silane or gamma-chloropropyl methyl dimethoxy silane, and preferably gamma-chloropropyl triethoxy silane.
The catalyst is cuprous bromide (CuBr) or cuprous chloride (CuCl), preferably cuprous chloride (CuCl).
The absorbent is zinc oxide (ZnO).
The mol ratio of the chloropropylalkoxysilane to the ammonia gas is 1.53 to 2, preferably 1.
The mass ratio of the chloropropylalkoxysilane to the ionic liquid to the catalyst to the absorbent is 1: 0.46-0.85, and 0.2-0.076: 0.04-0.076.
The reaction temperature is 30 to 60 ℃, and preferably 40 ℃; the reaction pressure was atmospheric pressure (0.1 MPa).
The flow rate in the reaction is 0.5 to 1.5mL/h, preferably 1mL/h.
The liquid holdup of the microchannel reactor is 60-70mL.
After the vacuum distillation separation, the ionic liquid and the catalyst in the residual fraction can be recycled.
The reaction principle of the invention is as follows (taking gamma-chloropropyltriethoxysilane as an example):
in the above reaction principle formula, IL represents an ionic liquid, and [ Bmim ] is preferably selected] + [Zn 2 Cl 5 ] - . Compared with the conventional ammonolysis method applied to industrial production, the method disclosed by the invention has the advantages that the ionic liquid is added as a reaction medium, so that the solubility of ammonia and chloropropylalkoxysilane can be improved, and the nucleophilic substitution reaction activity of ammonia is promoted due to the large molecular polarity, so that the reaction can be carried out at normal temperature and normal pressure, and the ammonia demand is low and the utilization rate is high. And a cuprous chloride catalyst is added to reduce the reaction activation energy and the generation of secondary and tertiary aminopropylalkoxysilane byproducts. Adding zinc oxide as acid absorbent, reacting with hydrochloric acid to obtain zinc chloride, reducing the generation of ammonium chloride by-product, promoting the reaction to proceed in forward direction, and supplementing the generated zinc chloride to the anion component [ Zn ] in the ionic liquid 2 Cl 5 ] - . In addition, after the reaction is finished and the product is separated, the ionic liquid and the catalyst can be repeatedly recycled.
The normal temperature of the invention is 30 to 60 ℃, and the normal temperature refers to the low reaction temperature of the invention.
The invention has the following beneficial effects:
(1) The method of the invention adds the ionic liquid as the reaction medium innovatively, can improve the solubility of the ammonia and the chloropropyl alkoxy silane, and further promotes the nucleophilic substitution reaction activity of the ammonia due to the large molecular polarity, so that the reaction can be carried out at normal temperature and normal pressure, and the ammonia demand is small, and the utilization rate is high.
(2) The method of the invention adds cuprous chloride or cuprous bromide as a catalyst, reduces the reaction activation energy, and reduces the generation of secondary and tertiary aminopropyl alkoxy silane byproducts.
(3) According to the method, zinc oxide is added as an acid absorbent to react with the product hydrochloric acid to generate zinc chloride, the generation of ammonia chloride by-products is reduced, the reaction forward is promoted, and meanwhile, the generated zinc chloride is supplemented to the anion component [ Zn ] in the ionic liquid 2 Cl 5 ] - 。
(4) The method adopts a continuous microchannel reactor to react at normal temperature and normal pressure, and the key reactants of ionic liquid and catalyst can be recycled, thereby providing a synthetic approach with environmental protection, safety and stability, less by-products and high continuous production capacity.
Drawings
FIG. 1 is a drawing of the product of example 1 of the invention 1 H NMR spectrum.
Detailed Description
The present invention is further described below with reference to examples.
Example 1
2mol (34 g) of ammonia gas are dissolved in 111g of ionic liquid [ Bmim ]] + [Zn 2 Cl 5 ] - And reaching a saturated state, sequentially adding 1mol (240.8 g) of gamma-chloropropyltriethoxysilane, 9.6g of catalyst CuCl and 50g of absorbent ZnO to form a mixed solution, injecting the mixed solution into a microchannel reactor with a liquid holdup of 60mL through a plunger pump, adjusting the plunger pump to ensure that the flow rate reaches 1mL/h, the reaction temperature is 40 ℃, the reaction pressure is normal pressure (0.1 MPa), and collecting a product (the product of which the tail end is connected with the microchannel reactor) 1 The H NMR spectrum is shown in figure 1), and the aminopropyltriethoxysilane is obtained by reduced pressure distillation separation, the yield reaches 90 percent, and the purity is 99.5 percent.
Example 2
1mol (17 g) of ammonia gas are dissolved in 78g of ionic liquid [ MTEOA ]] + [MeOSO 3 ] - And when the neutralization state is reached, sequentially adding 0.5mol (99.4 g) of gamma-chloropropyltrimethoxysilane, 5g of catalyst CuCl and 30g of absorbent ZnO to form a mixed solution, injecting the mixed solution into a microchannel reactor with the liquid holdup of 60mL through a plunger pump, adjusting the plunger pump to ensure that the flow rate of the mixed solution reaches 0.5mL/h, the reaction temperature is 50 ℃, the reaction pressure is normal pressure (0.1 MPa), collecting a product at the tail end of the microchannel reactor, and carrying out reduced pressure distillation and separation to obtain aminopropyltrimethoxysilane, wherein the yield is 86% and the purity is 99.3%.
Example 3
0.5mol (8.5 g) of ammonia gas was dissolved in 45g of ionic liquid [ EtOHMim] + [DCA] - Adding 0.25mol (52.7 g) of gamma-chloropropyl methyl diethoxy silane, 4g of catalyst CuBr and 10.5g of absorbent ZnO in sequence to form a mixed solution when the neutralization reaches a saturated state, and injecting the mixed solution into a microchannel with the liquid holdup of 60mL through a plunger pumpIn the reactor, a plunger pump is adjusted to ensure that the flow rate reaches 1.5mL/h, the reaction temperature is 30 ℃, the reaction pressure is normal pressure (0.1 MPa), a product is collected at the tail end of the microchannel reactor, and the product is subjected to reduced pressure distillation and separation to obtain the aminopropyl methyl diethoxysilane, wherein the yield reaches 82%, and the purity is 99.4%.
Example 4
0.4mol (6.8 g) of ammonia gas are dissolved in 22.2g of ionic liquid [ Bmim ]] + [Zn 2 Cl 5 ] - And when the reaction temperature reaches a saturated state, sequentially adding 0.26mol (48.2 g) of gamma-chloropropyl methyl dimethoxy silane, 3g of catalyst CuCl and 10g of absorbent ZnO to form a mixed solution, injecting the mixed solution into a microchannel reactor with the liquid holdup of 70mL through a plunger pump, adjusting the plunger pump to ensure that the flow rate of the mixed solution reaches 1.5mL/h, the reaction temperature is 60 ℃, the reaction pressure is normal pressure (0.1 MPa), collecting a product at the tail end of the microchannel reactor, and carrying out reduced pressure distillation and separation to obtain aminopropyl methyl dimethoxy silane, wherein the yield reaches 89% and the purity is 99.5%.
Example 5
The ionic liquid and the catalyst collected in the example 1 are reused, the rest steps and the reaction conditions are the same as those of the example 1, the product is collected at the tail end of the microchannel reactor, and the aminopropyl triethoxysilane is obtained by reduced pressure distillation and separation, wherein the yield reaches 89%, and the purity is 99.3%.
Comparative example 1
The steps and reaction conditions were the same as in example 1, except that no ionic liquid, catalyst, and absorbent were added. By passing 1 H NMR spectrum and gas chromatography, etc. find that aminopropyl triethoxysilane is not produced in the product collected at the end of the microchannel reactor.
Comparative example 2
The procedure and reaction conditions were the same as in example 1, except that no ionic liquid was added. By passing 1 And H NMR spectrogram, gas chromatography and other characterization means find that no aminopropyltriethoxysilane is generated in the product collected at the tail end of the microchannel reactor.
Comparative example 3
The procedure and reaction conditions were the same as in example 1, except that no catalyst was added. By passing 1 The target product is found by characterization means such as H NMR spectrum and gas chromatographyAnd collecting the product at the tail end of the microchannel reactor, and carrying out reduced pressure distillation and separation to obtain the aminopropyltriethoxysilane, wherein the yield reaches 63 percent, and the purity is 99.1 percent.
Comparative example 4
The procedure and reaction conditions were the same as in example 1 except that no absorbent was added. By passing 1 And (3) finding a target product by using characterization means such as an H NMR spectrum and a gas chromatography, collecting the product at the tail end of the microchannel reactor, and carrying out reduced pressure distillation and separation to obtain the aminopropyltriethoxysilane, wherein the yield reaches 70%, and the purity is 99.0%.
Claims (6)
1. A method for continuously preparing aminopropyl alkoxysilane, characterized in that: dissolving ammonia gas in an ionic liquid to reach a saturated state, sequentially adding gamma-chloropropyl triethoxysilane or gamma-chloropropyl methyldiethoxysilane or gamma-chloropropyl trimethoxysilane or gamma-chloropropyl methyldimethoxysilane, a catalyst and an absorbent to form a mixed solution, injecting the mixed solution into a microchannel reactor through a plunger pump for reaction, collecting a product at the tail end of the microchannel reactor, and carrying out reduced pressure distillation and separation to obtain aminopropyl alkoxysilane;
the ionic liquid is 2-hydroxy-N, N-di (2-hydroxyethyl) -N-methyl ethyl ammonium methyl sulfate, 1- (2-hydroxyethyl) -3-methylimidazolium dicyanamide or 1-butyl-3-methylimidazolium zinc chloride;
the catalyst is cuprous bromide or cuprous chloride; the absorbent is zinc oxide.
2. The continuous process for producing aminopropylalkoxysilane according to claim 1, wherein: the molar ratio of the gamma-chloropropyltriethoxysilane, the gamma-chloropropylmethyldiethoxysilane, the gamma-chloropropyltrimethoxysilane or the gamma-chloropropylmethyldimethoxysilane to ammonia gas is 1.53 to 2.
3. The process for continuously preparing aminopropylalkoxysilane according to claim 1, wherein: the mass ratio of the gamma-chloropropyltriethoxysilane or gamma-chloropropylmethyldiethoxysilane or gamma-chloropropyltrimethoxysilane to the ionic liquid, the catalyst and the absorbent is 1.46 to 0.85, and the mass ratio of the gamma-chloropropyltriethoxysilane to the ionic liquid to the catalyst to the absorbent is 0.04 to 0.076.
4. The process for continuously preparing aminopropylalkoxysilane according to claim 1, wherein: the reaction temperature is 30 to 60 ℃, and the reaction pressure is normal pressure.
5. The process for continuously preparing aminopropylalkoxysilane according to claim 1, wherein: the flow rate during the reaction was 0.5 to 1.5mL/h.
6. The continuous process for producing aminopropylalkoxysilane according to claim 1, wherein: the liquid holdup of the microchannel reactor is 60 to 70mL.
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