CN116082387A - Method for preparing 3-chloropropyl triethoxysilane - Google Patents
Method for preparing 3-chloropropyl triethoxysilane Download PDFInfo
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- CN116082387A CN116082387A CN202211673419.4A CN202211673419A CN116082387A CN 116082387 A CN116082387 A CN 116082387A CN 202211673419 A CN202211673419 A CN 202211673419A CN 116082387 A CN116082387 A CN 116082387A
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- cobalt
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- triethoxysilane
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- chloropropyl triethoxysilane
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- KSCAZPYHLGGNPZ-UHFFFAOYSA-N 3-chloropropyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)CCCCl KSCAZPYHLGGNPZ-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 36
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 36
- 239000010941 cobalt Substances 0.000 claims abstract description 36
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000006459 hydrosilylation reaction Methods 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 239000012074 organic phase Substances 0.000 claims abstract description 10
- 238000005292 vacuum distillation Methods 0.000 claims abstract description 10
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims abstract description 3
- 230000002194 synthesizing effect Effects 0.000 claims abstract 2
- 238000005406 washing Methods 0.000 claims abstract 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 67
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 claims description 30
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 19
- 239000008346 aqueous phase Substances 0.000 claims description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- 238000005070 sampling Methods 0.000 claims description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 150000001868 cobalt Chemical class 0.000 claims description 2
- 238000004064 recycling Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 8
- 239000000243 solution Substances 0.000 claims 5
- 239000007864 aqueous solution Substances 0.000 claims 1
- 238000011534 incubation Methods 0.000 claims 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 9
- 229910000510 noble metal Inorganic materials 0.000 abstract description 8
- 229910052741 iridium Inorganic materials 0.000 abstract description 6
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- 229910052697 platinum Inorganic materials 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 239000012071 phase Substances 0.000 abstract description 2
- 239000012967 coordination catalyst Substances 0.000 abstract 1
- 239000012043 crude product Substances 0.000 description 14
- 238000004817 gas chromatography Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 239000012263 liquid product Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 238000000746 purification Methods 0.000 description 7
- 239000011541 reaction mixture Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 239000012141 concentrate Substances 0.000 description 5
- 229910052707 ruthenium Inorganic materials 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 125000000746 allylic group Chemical group 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 125000001309 chloro group Chemical group Cl* 0.000 description 3
- BKFAZDGHFACXKY-UHFFFAOYSA-N cobalt(II) bis(acetylacetonate) Chemical compound [Co+2].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O BKFAZDGHFACXKY-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- -1 iridium metal complex Chemical class 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229910001510 metal chloride Inorganic materials 0.000 description 2
- 230000008520 organization Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 description 1
- XDQWJFXZTAWJST-UHFFFAOYSA-N 3-triethoxysilylpropyl prop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C=C XDQWJFXZTAWJST-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000004754 hydrosilicons Chemical class 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2213—At least two complexing oxygen atoms present in an at least bidentate or bridging ligand
-
- 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
- C07F7/1876—Preparation; Treatments not provided for in C07F7/20 by reactions involving the formation of Si-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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
- B01J2231/323—Hydrometalation, e.g. bor-, alumin-, silyl-, zirconation or analoguous reactions like carbometalation, hydrocarbation
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/845—Cobalt
-
- 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
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
Abstract
The invention provides a method for preparing 3-chloropropyl triethoxysilane, and belongs to the technical field of organic synthesis. Firstly, synthesizing a metal cobalt catalyst, namely a cobalt-beta-diketone complex, preparing the cobalt catalyst into an organic solution, synchronously dripping triethoxy hydrosilane and allyl chloride into the organic solution containing the cobalt catalyst, and performing hydrosilylation; cooling after the reaction is finished, washing a product mixture solution, separating a water phase, distilling an organic phase to remove an organic solvent, transferring the organic solvent into vacuum distillation equipment, and collecting fractions at 100-102 ℃ per 10mmHg to obtain the 3-chloropropyl triethoxysilane product. The method uses the cobalt-beta-diketone complex as a metal coordination catalyst for the first time, is applied to the hydrosilylation reaction between triethoxy hydrosilane and allyl chloride, and obtains experimental results with industrial value. The price of the metal cobalt is far lower than that of noble metals such as platinum, iridium and the like, so the invention has great industrial practical value.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a method for preparing 3-chloropropyl triethoxysilane.
Background
3-Chloropropyltriethoxysilane, also known asγThe chloropropyl triethoxysilane is a YSiX3 type silane coupling agent with wide application, and is also an important raw material for preparing sol-gel. Since 3-chloropropyl triethoxy silane has a terminal chlorine atom far away from a central silicon atom and has certain chemical activity, the 3-chloropropyl triethoxy silane can be used for preparing silane coupling agents with other functional groups, such as 3-aminopropyl triethoxy silane, 3-mercaptopropyl triethoxy silane, 3-acryloxypropyl triethoxy silane and the like. 3-chloropropyl triethoxysilane is mainly used industrially as an affinity coupling agent and a tackifier.
The synthesis method of 3-chloropropyl triethoxysilane (KH 230) reported in domestic and foreign literature mainly uses triethoxy hydrosilane (TEOS) and allyl chloride as starting materials, and adopts the action of noble metal catalyst to produce hydrosilylation reaction.
Patent European Patent Organization, EP 709392A 1 1996 reports the use of iridium metal chloride (IrCl) 3 ) The product yield is up to 86% by the hydrosilylation reaction of catalytic triethoxy hydrosilane and allyl chloride. Patent World Intellectual Property Organization, WO2017154846 A1 2017 reports the published methods of one of the japanese research institutions using iridium metal complex with a complex structure: two-μThe chlorotetra-tetra (triethylsilyl) diidium-catalyzed hydrosilylation of triethoxysilane with allyl chloride gives a product yield of 84%. The method of the patent is limited in practical use because iridium and platinum are expensive together with noble metals belonging to main group VIII of the sixth cycle.
Journal Russian Journal of General Chemistry (2010), 80 (4), 728-733 disclose methods employed by russian chemists: the hydrosilylation reaction of triethoxysilane and allyl chloride was catalyzed using a Speier catalyst (complex of chloroplatinic acid and vinyl monopin), with a 3-chloropropyl triethoxysilane product yield of 89%. Patent United STates, US 20040092759A 1 2004 discloses the use of ruthenium metal chloride RuCl by American scientists 3 As a catalyst, the 3-chloropropyl triethoxysilane product yield was 71%. Ruthenium belongs to the fifth group VIII transition metal. Platinum and ruthenium belong to noble metals, are expensive, and are difficult to popularize and use in industry.
Therefore, the search for non-noble metals to perform catalytic hydrosilylation reactions between triethoxysilane and allyl chloride, replacing the noble metals iridium, platinum, ruthenium, etc., has been the goal of the organosilicon workers' efforts.
Disclosure of Invention
In order to solve the problems, the invention discloses a method for preparing 3-chloropropyl triethoxysilane.
The use of non-noble cobalt as a catalyst in organic synthesis has been reported in many years. The complexing effect of cobalt metal catalysts has been reported, for example, in the latest research article of the International journal of the catalytic field (Applied Catalysis B: environmental, vol. 317,15November 2022, 121766). However, to date, no cobalt catalyst, particularly a "cobalt-beta-diketone complex", has been reported for use in catalyzing hydrosilylation reactions.
The present invention investigates the catalytic properties of several "cobalt-beta-diketone complexes", for example: "cobalt-1, 3-diphenyl-beta-diketone complex" (abbreviated Co (dbm)) 2 ) "Co-1, 3-dimethyl-beta-diketone complex" (abbreviated Co (acac)) 2 ) "cobalt-1, 3-di-tert-butyl-beta-diketone complex" (abbreviated Co (dtbm)) 2 ). Their synthesis can be prepared as provided in literature (Journal of Molecular Catalysis (1990), 58 (2), 171-183).
The hydrosilylation reaction of triethoxy hydrosilane and allyl chloride is different from other hydrosilylation reactions, because allyl chloride contains active chlorine at the allylic position in the molecule, and under certain conditions, the active chlorine reacts with cobalt ions in the coordination center to deactivate the cobalt catalyst, thus catalyzingOn the one hand, the preparation is to allow one end of an olefinic bond to participate in hydrosilylation near a coordination center and to prevent an active chlorine atom at an allylic position from interfering with the reaction. "Co-1, 3-di-tert-butyl-beta-diketone complex" (Co (dtbm) 2 ) The four tertiary butyl groups with molecular structures have quite stable coordination structures due to the strong electron pushing effect, and meanwhile, the four tertiary butyl groups have huge steric hindrance effects, so that the active chlorine atoms of the allylic positions are prevented from approaching the reaction center from all directions. Co (dtbm) 2 And Co (dbm) 2 And Co (acac) 2 The former should exhibit better catalytic activity than the former. Subsequent experimental work confirmed our speculation.
The technical scheme of the invention is as follows:
the synthesis method of the 3-chloropropyl triethoxysilane comprises the following steps: (1) First, a metallic cobalt catalyst, i.e. "cobalt-beta-diketone complex", is synthesized. (2) Then preparing a certain amount of cobalt catalyst into an organic solution with a certain concentration, and synchronously dripping triethoxy hydrosilane and allyl chloride into the solution containing the cobalt catalyst at a certain temperature to perform hydrosilylation reaction. After the dripping is finished, the reaction is kept for a certain time, sampling GC is carried out to detect, and the reaction is stopped after triethoxy hydrosilane is converted into a product. (3) After cooling, the product mixture solution was washed rapidly with a small amount of dilute aqueous hydrochloric acid. And (3) separating the water phase to remove cobalt salt, distilling the organic phase to obtain an organic solvent for recycling, and finally transferring the organic solvent into vacuum distillation equipment, and collecting fractions of 100-102 ℃ per 10mmHg to obtain the 3-chloropropyl triethoxysilane product.
In the step (1), the catalyst "cobalt-beta-diketone complex" may be "cobalt-1, 3-diphenyl-beta-diketone complex" (Co (dbm) 2 ) "Co-1, 3-dimethyl-beta-diketone complex" (Co (acac) 2 ) "Co-1, 3-di-tert-butyl-beta-diketone complex" (Co (dtbm) 2 ). Preferably "cobalt-1, 3-di-tert-butyl-beta-diketone complex" (Co (dtbm) 2 ）。
In the step (2), the amount of the cobalt catalyst is 0.1-0.5% of the total mole number of the reaction substrates (namely the sum of the mole numbers of triethoxy hydrosilane and allyl chloride); preferably 0.3%.
In the step (2), the organic solution may be one of toluene and tetrahydrofuran. Toluene is preferred.
In the step (2), the concentration of the organic solution may be 0.5 to 2.0m. Preferably 1.0M.
In the step (2), the reaction temperature may be 50 ℃.
In the step (2), the reaction time of heat preservation after the completion of the dripping can be 0.5-2 hours. Preferably 1 hour.
The diluted hydrochloric acid in the step (3) has a mass concentration of 1.4% and is used in an amount of 60mL per mol of triethoxysilane.
The beneficial effects of the invention are as follows: the invention successfully applies the cobalt-beta-diketone complex catalyst to the hydrosilylation reaction between triethoxy hydrosilane and allyl chloride for the first time, and obtains experimental results with industrial value. Because the metal cobalt belongs to non-noble metals, the price of the cobalt is far lower than that of noble metals such as platinum, iridium, ruthenium and the like, the cobalt has great industrial practical value.
Detailed Description
The invention will be further illustrated by the following examples.
Example 1.
In a 1L four-necked flask thoroughly dried, a polytetrafluoroethylene magnetic stirrer and two constant-pressure dropping funnels are arranged in the flask
An argon protection device is arranged at the top ends of the built-in thermometer, the reflux condenser and the reflux condenser. All solvents need to be strictly anhydrous.
Cobalt catalysts were prepared according to the method provided in literature (Journal of Molecular Catalysis (1990), 58 (2), 171-183). Wherein "cobalt-1, 3-diphenyl-beta-diketone complex" (Co (dbm) 2 ) "Co-1, 3-dimethyl-beta-diketone complex" (Co (acac) 2 ) And "cobalt-1, 3-di-tert-butyl-beta-diketone complex" (Co (dtbm) 2 ) The molecular structure of (2) is as follows:
in a previously dried constant pressure dropping funnel, 164.3g (1.00 mol) of triethoxy hydrosilicon was introduced
Alkane was added and diluted with about 22mL of anhydrous toluene to give a total volume of 210mL.
In a further previously dried constant pressure dropping funnel, 78.1g (1.02 mol) of allyl are introduced
Chlorine was added and diluted with about 127mL of anhydrous toluene to give a total volume of 210mL.
Into a four-necked flask, 2.553g (0.006 mol) "cobalt-1, 3-di-tert-butyl- β -dione complex" (Co (dtbm) 2 ) And 80mL of anhydrous toluene (allowing the subsequent hydrosilylation reaction to proceed in a 1.0M solution concentration) was transferred, the magnetic stirrer was started, and stirred until the cobalt catalyst was completely dissolved.
Heating is started, so that the temperature of the solution in the reaction bottle reaches 50 ℃.
At this temperature, a toluene solution of triethoxysilane and allyl chloride was simultaneously added dropwise to the system via the above two constant pressure dropping funnels. The dropping speed is controlled so that the dropping speeds of the two constant pressure dropping funnels are equal.
After the dripping, the mixture was stirred at this temperature for 1 hour. Sampling GC analysis found that the triethoxysilane conversion was already greater than 95%.
The chemical equation of the hydrosilylation reaction catalyzed by the cobalt-1, 3-di-tert-butyl-beta-diketone complex is as follows:
the reaction system was cooled to room temperature and transferred to a separatory funnel, and the reaction mixture was washed with 60mL of a 1.4% dilute aqueous hydrochloric acid solution, the cobalt catalyst was decomposed, and the aqueous phase was separated. The organic phase was washed once again with 60mL of deionized water. The aqueous phase was again separated off.
The chemical equation for cobalt catalyst hydrolysis is as follows:
transfer to a rotary evaporator and concentrate off toluene solvent under negative pressure to recover 223g of crude product.
The crude product was transferred to a vacuum distillation apparatus and purification was started. And (5) collecting a fraction of 100-102 ℃ per 10mmHg to obtain 201.8g of colorless liquid product. The yield was 83.8% based on the amount of triethoxysilane charged, and the content was 99.2% by GC detection.
Example 2.
The experimental setup and raw material preparation were the same as in example 1.
Into a four-necked flask, 0.851g (0.002 mol) of Co (dtbm) was introduced 2 And 80mL of anhydrous toluene was transferred, and the magnetic stirrer was started, stirring was performed until the cobalt catalyst was completely dissolved.
Heating is started, so that the temperature of the solution in the reaction bottle reaches 50 ℃.
At this temperature, a toluene solution of triethoxysilane and allyl chloride was simultaneously added dropwise to the system via the above two constant pressure dropping funnels. The dropping speed is controlled so that the dropping speeds of the two constant pressure dropping funnels are equal.
After the dripping, the mixture was stirred at this temperature for 1 hour. Sampling GC analysis found that the triethoxysilane conversion was already greater than 90%.
The reaction system was cooled to room temperature and transferred to a separatory funnel, and the reaction mixture was washed with 60mL of a 1.4% dilute aqueous hydrochloric acid solution, the cobalt catalyst was decomposed, and the aqueous phase was separated. The organic phase was washed once again with 60mL of deionized water. The aqueous phase was again separated off.
Transfer to a rotary evaporator and concentrate off toluene solvent under negative pressure to recover 197g of crude product.
The crude product was transferred to a vacuum distillation apparatus and purification was started. And (5) collecting a fraction of 100-102 ℃ per 10mmHg to obtain 174.3g of colorless liquid product. The yield was 72.4% based on the amount of triethoxysilane charged, and the GC content was 98.5%.
Example 3.
The experimental setup and raw material preparation were the same as in example 1.
Into a four-necked flask, 1.702g (0.004 mol) of Co (dtbm) was introduced 2 And 80mL of anhydrous toluene was transferred, and the magnetic stirrer was started, stirring was performed until the cobalt catalyst was completely dissolved.
Heating is started, so that the temperature of the solution in the reaction bottle reaches 50 ℃.
At this temperature, a toluene solution of triethoxysilane and allyl chloride was simultaneously added dropwise to the system via the above two constant pressure dropping funnels. The dropping speed is controlled so that the dropping speeds of the two constant pressure dropping funnels are equal.
After the dripping, the mixture was stirred at this temperature for 1 hour. Sampling GC analysis found that the triethoxysilane conversion was already greater than 90%.
The reaction system was cooled to room temperature and transferred to a separatory funnel, and the reaction mixture was washed with 60mL of a 1.4% dilute aqueous hydrochloric acid solution, the cobalt catalyst was decomposed, and the aqueous phase was separated. The organic phase was washed once again with 60mL of deionized water. The aqueous phase was again separated off.
Transfer to a rotary evaporator, concentrate toluene solvent recovery under negative pressure to give 201g of crude product.
The crude product was transferred to a vacuum distillation apparatus and purification was started. And (5) collecting a fraction of 100-102 ℃ per 10mmHg to obtain 183.2g of colorless liquid product. The yield was 76.1% based on the amount of triethoxysilane charged, and the GC content was 99.1%.
Example 4.
The experimental setup and raw material preparation were the same as in example 1.
Into a four-necked flask, 3.404g (0.008 mol) of Co (dtbm) was charged 2 And 80mL of anhydrous toluene was transferred, and the magnetic stirrer was started, stirring was performed until the cobalt catalyst was completely dissolved.
Heating is started, so that the temperature of the solution in the reaction bottle reaches 50 ℃.
At this temperature, a toluene solution of triethoxysilane and allyl chloride was simultaneously added dropwise to the system via the above two constant pressure dropping funnels. The dropping speed is controlled so that the dropping speeds of the two constant pressure dropping funnels are equal.
After the dripping, the mixture was stirred at this temperature for 1 hour. Sampling GC analysis found that the triethoxysilane conversion was already greater than 95%.
The reaction system was cooled to room temperature and transferred to a separatory funnel, and the reaction mixture was washed with 60mL of a 1.4% dilute aqueous hydrochloric acid solution, the cobalt catalyst was decomposed, and the aqueous phase was separated. The organic phase was washed once again with 60mL of deionized water. The aqueous phase was again separated off.
Transferred to a rotary evaporator, and the toluene solvent was concentrated under negative pressure to recover 219g of a crude product.
The crude product was transferred to a vacuum distillation apparatus and purification was started. And (5) collecting a fraction of 100-102 ℃ per 10mmHg to obtain 198.4g of colorless liquid product. The yield was 82.4% based on the amount of triethoxysilane charged, and the GC-detected content was 98.8%.
Example 5.
The experimental setup and raw material preparation were the same as in example 1.
Into a four-necked flask, 4.255g (0.010 mol) of Co (dtbm) was introduced 2 And 80mL of anhydrous toluene was transferred, and the magnetic stirrer was started, stirring was performed until the cobalt catalyst was completely dissolved.
Heating is started, so that the temperature of the solution in the reaction bottle reaches 50 ℃.
At this temperature, a toluene solution of triethoxysilane and allyl chloride was simultaneously added dropwise to the system via the above two constant pressure dropping funnels. The dropping speed is controlled so that the dropping speeds of the two constant pressure dropping funnels are equal.
After the dripping, the mixture was stirred at this temperature for 1 hour. Sampling GC analysis found that the triethoxysilane conversion was already greater than 95%.
The reaction system was cooled to room temperature and transferred to a separatory funnel, and the reaction mixture was washed with 60mL of a 1.4% dilute aqueous hydrochloric acid solution, the cobalt catalyst was decomposed, and the aqueous phase was separated. The organic phase was washed once again with 60mL of deionized water. The aqueous phase was again separated off.
Transfer to a rotary evaporator, concentrate toluene solvent recovery under negative pressure to give 214g of crude product.
The crude product was transferred to a vacuum distillation apparatus and purification was started. And (5) collecting a fraction of 100-102 ℃ per 10mmHg to obtain 195.5g of colorless liquid product. The yield was 81.2% based on the amount of triethoxysilane charged, and the GC content was 98.7%.
Example 6.
The experimental setup and raw material preparation were the same as in example 1.
Into a four-necked flask, 1.543g (0.006 mol) of Co (acac) was charged 2 And 80mL of anhydrous toluene was transferred, and the magnetic stirrer was started, stirring was performed until the cobalt catalyst was completely dissolved.
Heating is started, so that the temperature of the solution in the reaction bottle reaches 50 ℃.
At this temperature, a toluene solution of triethoxysilane and allyl chloride was simultaneously added dropwise to the system via the above two constant pressure dropping funnels. The dropping speed is controlled so that the dropping speeds of the two constant pressure dropping funnels are equal.
After the dripping, the mixture was stirred at this temperature for 1 hour. Sampling GC analysis found that the triethoxysilane conversion was already greater than 90%.
The reaction system was cooled to room temperature and transferred to a separatory funnel, and the reaction mixture was washed with 60mL of a 1.4% dilute aqueous hydrochloric acid solution, the cobalt catalyst was decomposed, and the aqueous phase was separated. The organic phase was washed once again with 60mL of deionized water. The aqueous phase was again separated off.
Transferred to a rotary evaporator, and concentrated under negative pressure to recover toluene solvent to give 189g of a crude product.
The crude product was transferred to a vacuum distillation apparatus and purification was started. And (5) collecting fractions at 100-102 ℃ per 10mmHg to obtain 167.8g of colorless liquid product. The yield was 69.7% based on the amount of triethoxysilane charged, and the GC content was 98.2%.
Example 7.
The experimental setup and raw material preparation were the same as in example 1.
Into a four-necked flask, 3.033g (0.006 mol) Co (dbm) was introduced 2 And 80mL of anhydrous toluene was transferred, and the magnetic stirrer was started, stirring was performed until the cobalt catalyst was completely dissolved.
Heating is started, so that the temperature of the solution in the reaction bottle reaches 50 ℃.
At this temperature, a toluene solution of triethoxysilane and allyl chloride was simultaneously added dropwise to the system via the above two constant pressure dropping funnels. The dropping speed is controlled so that the dropping speeds of the two constant pressure dropping funnels are equal.
After the dripping, the mixture was stirred at this temperature for 1 hour. Sampling GC analysis found that the triethoxysilane conversion was already greater than 90%.
The reaction system was cooled to room temperature and transferred to a separatory funnel, and the reaction mixture was washed with 60mL of a 1.4% dilute aqueous hydrochloric acid solution, the cobalt catalyst was decomposed, and the aqueous phase was separated. The organic phase was washed once again with 60mL of deionized water. The aqueous phase was again separated off.
Transfer to a rotary evaporator and concentrate off toluene solvent recovery under negative pressure to give 171g of crude product.
The crude product was transferred to a vacuum distillation apparatus and purification was started. And (5) collecting a fraction of 100-102 ℃ per 10mmHg to obtain 147.4g of colorless liquid product. The yield was 61.2% based on the amount of triethoxysilane charged, and the GC content was 98.7%.
Comparative example 1.
The experimental setup and raw material preparation were the same as in example 1.
Into a four-necked flask, 0.778g (0.006 mol) of CoCl was introduced 2 And transferring into 80mL anhydrous tetrahydrofuran, starting a magnetic stirrer, and fully stirring and uniformly mixing as much as possible.
Heating is started, so that the temperature of the solution in the reaction bottle reaches 50 ℃.
At this temperature, a tetrahydrofuran solution of triethoxysilane (164.3 g of triethoxysilane was diluted with about 22mL of anhydrous tetrahydrofuran) and allyl chloride (78.1 g of allyl chloride was diluted with about 127mL of anhydrous tetrahydrofuran) was simultaneously added dropwise to the system via the above two constant pressure dropping funnels. The dropping speed is controlled so that the dropping speeds of the two constant pressure dropping funnels are equal.
After the dripping, the mixture was stirred at this temperature for 1 hour. Sampling GC analysis found only about 8% conversion of triethoxysilane. Is in a substantially non-reactive state. It appears that metallic cobalt is only catalytically active for hydrosilylation reactions when it is in a complex state with the beta-diketone compound.
It should be noted that the foregoing merely illustrates the technical idea of the present invention and is not intended to limit the scope of the present invention, and that a person skilled in the art may make several improvements and modifications without departing from the principles of the present invention, which fall within the scope of the claims of the present invention.
Claims (8)
1. A process for preparing 3-chloropropyl triethoxysilane comprising the steps of:
(1) Synthesizing a metallic cobalt catalyst, namely a cobalt-beta-diketone complex;
(2) Preparing an organic solution from the cobalt catalyst synthesized in the step (1), synchronously dripping triethoxy hydrosilane and allyl chloride into the organic solution containing the cobalt catalyst, performing hydrosilylation, after the hydrosilylation is finished and the reaction is kept warm for a certain time, sampling and detecting by GC, and stopping the reaction after the triethoxy hydrosilane is converted into a product;
(3) After cooling, a small amount of dilute hydrochloric acid aqueous solution is used for rapidly washing the product mixture solution, and after cobalt salt is removed by separating the aqueous phase, the organic phase is distilled out of the organic solvent for recycling; and finally, transferring to vacuum distillation equipment, and collecting fractions at 100-102 ℃ per 10mmHg to obtain the 3-chloropropyl triethoxysilane product.
2. A process for preparing 3-chloropropyl triethoxysilane as claimed in claim 1, wherein: the cobalt-beta-diketone complex in the step (1) is any one of cobalt-1, 3-diphenyl-beta-diketone complex, cobalt-1, 3-dimethyl-beta-diketone complex and cobalt-1, 3-di-tert-butyl-beta-diketone complex; cobalt-1, 3-di-tert-butyl-beta-dione complex is preferred.
3. A process for preparing 3-chloropropyl triethoxysilane as claimed in claim 1, wherein: the cobalt catalyst in step (2) is used in an amount of between 0.1% and 0.5%, preferably 0.3%, of the sum of the moles of triethoxysilane and allyl chloride.
4. A process for preparing 3-chloropropyl triethoxysilane as claimed in claim 1, wherein: the organic solution in the step (2) is one of toluene and tetrahydrofuran; toluene is preferred.
5. A process for preparing 3-chloropropyl triethoxysilane as claimed in claim 1, wherein: the concentration of the organic solution in the step (2) is 0.5-2.0M; preferably 1.0M.
6. A process for preparing 3-chloropropyl triethoxysilane as claimed in claim 1, wherein: the hydrosilylation reaction temperature in the step (2) is 50 ℃.
7. A process for preparing 3-chloropropyl triethoxysilane as claimed in claim 1, wherein: the incubation time in step (2) was 1 hour.
8. A process for preparing 3-chloropropyl triethoxysilane as claimed in claim 1, wherein: the diluted hydrochloric acid in the step (3) has a mass concentration of 1.4% and is used in an amount of 60mL per mol of triethoxysilane.
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