CN113234101A - Gas-liquid two-phase synthesis method and reaction device of gamma-chloropropyltrichlorosilane - Google Patents
Gas-liquid two-phase synthesis method and reaction device of gamma-chloropropyltrichlorosilane Download PDFInfo
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- CN113234101A CN113234101A CN202110698394.2A CN202110698394A CN113234101A CN 113234101 A CN113234101 A CN 113234101A CN 202110698394 A CN202110698394 A CN 202110698394A CN 113234101 A CN113234101 A CN 113234101A
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- chloropropyltrichlorosilane
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- OOXSLJBUMMHDKW-UHFFFAOYSA-N trichloro(3-chloropropyl)silane Chemical compound ClCCC[Si](Cl)(Cl)Cl OOXSLJBUMMHDKW-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 239000007788 liquid Substances 0.000 title claims abstract description 24
- 238000001308 synthesis method Methods 0.000 title claims abstract description 13
- 238000003786 synthesis reaction Methods 0.000 title abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 58
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000005052 trichlorosilane Substances 0.000 claims abstract description 24
- 239000007783 nanoporous material Substances 0.000 claims abstract description 23
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 12
- OWXJKYNZGFSVRC-NSCUHMNNSA-N (e)-1-chloroprop-1-ene Chemical compound C\C=C\Cl OWXJKYNZGFSVRC-NSCUHMNNSA-N 0.000 claims abstract description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical group CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 16
- FLCYFPXJIOADLU-UHFFFAOYSA-N platinum;triphenylphosphane;dihydrochloride Chemical compound Cl.Cl.[Pt].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 FLCYFPXJIOADLU-UHFFFAOYSA-N 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 11
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 claims description 8
- 230000002194 synthesizing effect Effects 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 4
- 238000005086 pumping Methods 0.000 claims description 4
- 238000005245 sintering Methods 0.000 claims description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims description 4
- 239000010935 stainless steel Substances 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 10
- NQNFKQOIDNMNBB-UHFFFAOYSA-L dichloroplatinum;triphenylphosphane Chemical compound Cl[Pt]Cl.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NQNFKQOIDNMNBB-UHFFFAOYSA-L 0.000 abstract description 6
- 238000007086 side reaction Methods 0.000 abstract description 5
- 239000012190 activator Substances 0.000 abstract description 4
- 238000009833 condensation Methods 0.000 abstract description 3
- 230000005494 condensation Effects 0.000 abstract description 3
- 239000002683 reaction inhibitor Substances 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 230000035484 reaction time Effects 0.000 abstract description 2
- 239000012071 phase Substances 0.000 description 26
- 239000007789 gas Substances 0.000 description 19
- 239000000047 product Substances 0.000 description 11
- 239000006087 Silane Coupling Agent Substances 0.000 description 8
- 239000003921 oil Substances 0.000 description 5
- 238000010812 external standard method Methods 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 239000011799 hole material Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- KSCAZPYHLGGNPZ-UHFFFAOYSA-N 3-chloropropyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)CCCCl KSCAZPYHLGGNPZ-UHFFFAOYSA-N 0.000 description 1
- OXYZDRAJMHGSMW-UHFFFAOYSA-N 3-chloropropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCCl OXYZDRAJMHGSMW-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 231100000481 chemical toxicant Toxicity 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000011350 dental composite resin Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 238000006459 hydrosilylation reaction Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000007791 liquid phase Substances 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
- 239000000178 monomer Substances 0.000 description 1
- 239000005304 optical glass Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- UIDUKLCLJMXFEO-UHFFFAOYSA-N propylsilane Chemical class CCC[SiH3] UIDUKLCLJMXFEO-UHFFFAOYSA-N 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000003466 welding Methods 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
- C07F7/12—Organo silicon halides
- C07F7/121—Preparation or treatment not provided for in C07F7/14, C07F7/16 or C07F7/20
- C07F7/122—Preparation or treatment not provided for in C07F7/14, C07F7/16 or C07F7/20 by reactions involving the formation of Si-C linkages
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D5/00—Condensation of vapours; Recovering volatile solvents by condensation
- B01D5/0003—Condensation of vapours; Recovering volatile solvents by condensation by using heat-exchange surfaces for indirect contact between gases or vapours and the cooling medium
- B01D5/0006—Coils or serpentines
-
- 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
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/08—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with moving particles
- B01J8/10—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with moving particles moved by stirrers or by rotary drums or rotary receptacles or endless belts
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
Abstract
The invention discloses a gas-liquid two-phase synthesis method and a reaction device of gamma-chloropropyltrichlorosilane, and relates to the technical field of synthesis of gamma-chloropropyltrichlorosilane. The synthesis method uses cis-bis (triphenylphosphine) platinum dichloride (II) as a catalyst, and trichlorosilane is fed into chloropropene simultaneously, so that the occurrence of side reactions is reduced. The reaction device adds the platinum catalyst into the reaction kettle, adsorbs the platinum catalyst to the nano-pore material, and is filled into the gas phase reactor, so that the raw materials can still react in the gas phase, the reaction time is shortened, and the condensation cost is reduced. The method does not need to add various cocatalysts, activators and side reaction inhibitors, is simple to operate, has mild reaction conditions, and can obtain the main product with the yield as high as 88-95%.
Description
Technical Field
The invention relates to the technical field of gamma-chloropropyltrichlorosilane production, in particular to a gas-liquid two-phase synthesis method and a reaction device of gamma-chloropropyltrichlorosilane.
Background
The silane coupling agent is a fourth major organosilicon product following three major organosilicon products, namely silicone oil, silicone rubber and silicone resin, the position of the silane coupling agent in the organosilicon industry is increasingly important, and the silane coupling agent becomes an indispensable matched chemical auxiliary agent in the modern organosilicon industry, the organic polymer industry, the composite material industry and related high and new technology fields.
The silane coupling agent is an important coupling agent, and can be used as a commonly used auxiliary agent in the composite material to improve the wettability of matrix resin on the filler and the glass fiber, so that the matrix resin is connected with the filler or the glass fiber through chemical bonds, and the bending strength, the impact strength, the water resistance, the electrical property and the like of the composite material are further improved. Further, silane coupling agents are also used as adhesives such as epoxy and nitrile rubber, and as tackifiers in sealants such as polyurethane and chloroprene rubber.
The gamma-chloropropyl trichlorosilane is one of gamma-substituted propyl silane coupling agents with the largest domestic yield and the widest application, is one of the most basic monomers in the silane coupling agents, is used as a main production raw material, and can be used for synthesizing dozens of high-grade silane coupling agent products, such as gamma-chloropropyl triethoxysilane, gamma-chloropropyl trimethoxysilane, gamma-aminopropyl triethoxysilane, rubber aids Si69 and Si75, dental composite resin, an organic silicon antibacterial finishing agent, an optical glass antifogging agent and the like.
At present, chloropropene and trichlorosilane are used as raw materials, and a platinum complex is used for catalyzing hydrosilylation to synthesize gamma-chloropropyltrichlorosilane. In the process of catalytically synthesizing gamma-chloropropyltrichlorosilane by using traditional chloroplatinic acid as a main catalyst, the following defects exist: (1) various cocatalysts, activators and side reaction inhibitors are required to be added; (2) the promoter n-butylamine belongs to highly toxic chemicals; (3) the reaction temperature is high, the pressure is high, and the time is long; (4) the product yield is low, and the by-product components are complex.
Disclosure of Invention
In order to solve the technical problems, the invention provides a gas-liquid two-phase synthesis method and a reaction device of gamma-chloropropyltrichlorosilane, which are not suitable for a cocatalyst and an activator and have mild reaction conditions.
In order to realize the technical purpose, the method adopts the following scheme: the gas-liquid two-phase synthesis method of gamma-chloropropyltrichlorosilane comprises the following steps:
firstly, loading a platinum catalyst in a nano-pore material of a gas phase reactor;
secondly, sequentially adding gamma-chloropropyltrichlorosilane, 3-chloropropene and a platinum catalyst into a reaction kettle, fully stirring, and heating the reaction kettle to 60-70 ℃;
thirdly, pumping trichlorosilane into the reaction kettle for 1-2 hours by using a feed pump, and adjusting the pumping flow rate in real time to control the temperature in the reaction kettle to be 80-100 ℃;
and fourthly, after trichlorosilane is added, adjusting the temperature in the reaction kettle to be 80-90 ℃ by utilizing the heat conducting oil of the reaction kettle, and preserving the temperature for 1-2 hours to obtain the product gamma-chloropropyltrichlorosilane.
Compared with the prior art, the method has the beneficial effects that: the invention provides a gas-liquid two-phase synthesis method of gamma-chloropropyltrichlorosilane, which uses cis-bis (triphenylphosphine) platinum dichloride (II) as a catalyst, and trichlorosilane is fed into 3-chloropropene simultaneously, so that the occurrence of side reactions is reduced; a small amount of gamma-chloropropyltrichlorosilane is added into the raw materials, so that the reaction temperature is increased; the method does not need to add various cocatalysts, activators and side reaction inhibitors, is simple to operate, has mild reaction conditions, and can obtain the main product with the yield as high as 88-95%.
The preferred scheme of the method of the invention is as follows:
the mol ratio of chloropropene to trichlorosilane is 1-1.2: 1; and in the second step, a small amount of gamma-chloropropyltrichlorosilane is added in order to increase the reaction temperature, wherein the addition amount of the gamma-chloropropyltrichlorosilane is 10-20% of the total mass of chloropropene and trichlorosilane.
The platinum catalyst in the first step and the platinum catalyst in the second step are the same reagent, the platinum catalyst is isopropanol solution of cis-bis (triphenylphosphine) platinum (II) dichloride, and the cis-bis (triphenylphosphine) platinum (II) dichloride accounts for 10-30% of the total mass of the solution. .
The nano-pore material is a sintering material with micropores, which is formed by sintering stainless steel powder and titanium powder, wherein the pore diameter of the micropores is 0.2-60 mu m, the porosity is 40-50%, the compressive strength is 3MPa, and the temperature resistance is 500 ℃; the nano-pore material loaded platinum catalyst is an isopropanol solution of cis-bis (triphenylphosphine) platinum (II) dichloride adsorbed on the nano-pore material, and the mass ratio of the isopropanol solution of the cis-bis (triphenylphosphine) platinum (II) dichloride loaded on the nano-pore material to the nano-pore material is 1: 10-100.
The dosage (calculated by Pt) of the platinum catalyst loaded on the nano-pore material is 20-40 ppm of the total mass of the 3-chloropropene and the trichlorosilane.
In the second step of reaction, the dosage (calculated by Pt) of the isopropanol solution of cis-bis (triphenylphosphine) platinum dichloride (II) is 20-40 ppm of the total mass of 3-chloropropene and trichlorosilane.
And in the third step, the pressure in the reaction kettle is-0.01 MPa-0.03 MPa, so that the byproduct hydrogen chloride can be conveniently pumped out.
In order to realize the technical purpose, the device adopts the following scheme: the reaction device used in the gas-liquid two-phase synthesis method of gamma-chloropropyltrichlorosilane comprises a gas phase reactor and a reaction kettle, wherein the gas phase reactor is of a pipe body structure, an upper baffle and a lower baffle are respectively fixed at the upper part and the lower part in the pipe body, and a nano-pore material is filled between the upper baffle and the lower baffle; the lower port of the gas phase reactor is connected with a reaction kettle, baffle plates are uniformly distributed on the inner wall of the reaction kettle, and the contact surface of the baffle plates and the material is an arc surface.
Compared with the prior art, the device has the beneficial effects that: the reaction device not only adds the platinum catalyst into the reaction kettle, but also adsorbs the platinum catalyst to the nanometer hole material and fills the nanometer hole material into the gas phase reactor, so that the raw materials still react in the gas phase, the reaction time is shortened, and the condensation cost is reduced.
Further, still include the condenser, the last port and the condenser one end of gas phase reactor are connected, prevent that the raw materials from volatilizing, reduce the race material.
Further, a stirring paddle is arranged in the reaction kettle, and the stirring paddle is a double-layer push type blade.
Drawings
Fig. 1 is a schematic structural diagram of a reaction apparatus for gas-liquid two-phase synthesis of gamma-chloropropyltrichlorosilane according to an embodiment of the present invention;
FIG. 2 is a schematic structural diagram of a gas phase reactor provided in an embodiment of the present invention;
labeled as: 1. a reaction kettle; 2. a striker plate; 3. a stirring paddle; 4. a gas phase reactor; 5. a condenser; 6. a heat conducting oil outlet; 7. a heat conducting oil inlet; 8. a discharge port; 9. a jacket; 10. a condensate inlet; 11. a condensate outlet; 12. a feed inlet; 13. an upper baffle plate; 14. a nanoporous material; 15. and a lower baffle plate.
Detailed Description
The present invention will be described in detail with reference to the following embodiments in order to fully understand the objects, features and effects of the invention, but the present invention is not limited thereto.
Referring to fig. 1, the gas-liquid two-phase synthesis reaction device for gamma-chloropropyltrichlorosilane provided by the invention comprises a gas phase reactor 4, a condenser 5 and a reaction kettle 1, wherein the gas phase reactor 4 is of a tube structure, an upper baffle 13 and a lower baffle 15 which are made of stainless steel materials are respectively fixed on the upper part and the lower part of the inner wall of the tube, the sections of the upper baffle 13 and the lower baffle 15 are both of W-shaped structures, through holes are formed in the surfaces of the upper baffle 13 and the lower baffle 15, and both the upper baffle 13 and the lower baffle 15 can support nano-pore materials 14 and allow gas to pass through. As shown in fig. 2, the nano-porous material 14 is a sintered material with micropores distributed therein, which is obtained by sintering stainless steel powder and titanium powder, and the sintered material is a purchased product, and has micropores with a pore diameter of 0.2-60 μm, a porosity of 40-50%, a compressive strength of 3MPa, and a temperature resistance of 500 ℃. The trichlorosilane has a boiling point of 33 ℃ and 3-chloropropene has a boiling point of 44 ℃, the two raw materials are volatile, and the gas phase reactor 4 is utilized to enable the two raw materials to react in a gas phase state and a liquid phase state, so that the reaction speed is increased, the condensation cost is saved, and the material leakage is reduced. The platinum catalyst in the gas phase reactor can be repeatedly used, and the nanometer porous material is sintered and recovered to be used after the catalyst is invalid.
The outer wall of reation kettle 1 is provided with and presss from both sides the cover 9, the upper end that presss from both sides cover 9 is provided with conduction oil export 6, the lower extreme that presss from both sides cover 9 is provided with conduction oil import 7, reation kettle 1's upper end sets up feed inlet 12 and connector respectively, the connector is connected with gas phase reactor 4's lower port, reation kettle 1's lower extreme is provided with discharge gate 8, 1 inner wall hoop equipartition of reation kettle is fixed with 6 striker plate 2, 2 vertical welding of striker plate are on the inner wall, 2 striker plates are the arcwall face with the material contact surface, promote the stirring, make the material stirring abundant, there is. The stirring paddle 3 is arranged in the reaction kettle 1, the stirring paddle 3 is a double-layer push type blade, the stirring paddle 3 is composed of a rotating shaft, an upper blade and a lower blade, the lower blade is fixed at the lower end of the rotating shaft, and the upper blade is parallel to the lower blade and fixed at the middle part or the lower part of the rotating shaft.
A spiral condenser pipe is arranged in the condenser 5, a condensate inlet 10 is arranged at the lower end of the spiral condenser pipe, a condensate outlet 11 is arranged at the upper end of the spiral condenser pipe, condensate is conveyed by a low-temperature cooling circulating pump, and the temperature of the condensate is-15 ℃. The condenser 5 is used for preventing the raw materials from volatilizing, so that the raw materials are wasted.
Example 1
Adding 0.8g of isopropanol solution of 10wt% cis-bis (triphenylphosphine) platinum (II) dichloride loaded by a nano porous material 14 into a gas phase reactor 4, adding 100g of gamma-chloropropyltrichlorosilane, 339g of chloropropene and 0.8g of isopropanol solution of 10wt% cis-bis (triphenylphosphine) platinum (II) dichloride into a reaction kettle 1, stirring and heating to 60 ℃, adding 602g of trichlorosilane in a flowing manner, controlling the reaction temperature at 80-100 ℃, and finishing the adding in 1 hour; after the trichlorosilane is added, the liquid is kept at the temperature of 80 ℃ for 1h in the reaction kettle 1. The product was sampled and the yield of gamma-chloropropyltrichlorosilane detected by TCD gas chromatography external standard method was 88.7%.
Example 2
Adding 0.7g of isopropanol solution of 20wt% cis-bis (triphenylphosphine) platinum (II) dichloride loaded by a nano porous material 14 into a gas phase reactor 4, adding 150g of gamma-chloropropyltrichlorosilane, 390g of chloropropene and 0.7g of isopropanol solution of 20wt% cis-bis (triphenylphosphine) platinum (II) dichloride into a reaction kettle 1, stirring and heating to 65 ℃, adding 602g of trichlorosilane in a flowing manner, controlling the reaction temperature at 80-100 ℃, and finishing the feeding within 1.5 h; after the trichlorosilane is added, the liquid is kept at the temperature of 90 ℃ for 1.5h in the reaction kettle 1. The product was sampled and the yield of gamma-chloropropyltrichlorosilane detected by TCD gas chromatography external standard method was 90.6%.
Example 3
Adding 0.6g of isopropanol solution of 25wt% cis-bis (triphenylphosphine) platinum (II) dichloride loaded by a nano porous material 14 into a gas phase reactor 4, adding 200g of gamma-chloropropyltrichlorosilane, 408g of chloropropene and 0.6g of isopropanol solution of 25wt% cis-bis (triphenylphosphine) platinum (II) dichloride into a reaction kettle 1, stirring and heating to 70 ℃, feeding 602g of trichlorosilane for 2h, controlling the reaction temperature at 80-100 ℃, and finishing the feeding within 1 h; after the trichlorosilane is added, the liquid is kept at the temperature of 100 ℃ in the reaction kettle 1 for 2 hours. The product was sampled and the yield of gamma-chloropropyltrichlorosilane was 92.8% by TCD gas chromatography external standard method.
Comparative example
Uniformly mixing 408g of chloropropene and 602g of trichlorosilane, adding 100g of gamma-chloropropyltrichlorosilane and 1.1g of 10wt% isopropanol solution of chloroplatinic acid into a reaction kettle, stirring and heating to 70 ℃, feeding the mixture of chloropropene and trichlorosilane for 1h, controlling the reaction temperature to be 100-140 ℃, and controlling the reaction pressure in the reaction kettle to be 3-5 MPa. After the mixture is added, the liquid is kept in the reaction kettle for 2 hours at the temperature of 140 ℃. The product was sampled and the yield of gamma-chloropropyltrichlorosilane was 72.5% as determined by TCD gas chromatography external standard method.
Finally, it is noted that: the above-mentioned list is only the preferred embodiment of the present invention, and naturally those skilled in the art can make modifications and variations to the present invention, which should be considered as the protection scope of the present invention provided they are within the scope of the claims of the present invention and their equivalents.
Claims (10)
1. A gas-liquid two-phase synthesis method of gamma-chloropropyltrichlorosilane is characterized by comprising the following steps:
firstly, loading a platinum catalyst in a nano-pore material of a gas phase reactor;
secondly, sequentially adding gamma-chloropropyltrichlorosilane, 3-chloropropene and a platinum catalyst into a reaction kettle, fully stirring, and heating the reaction kettle to 60-70 ℃;
thirdly, pumping trichlorosilane into the reaction kettle for 1-2 hours, and adjusting the pumping flow rate in real time to control the temperature in the reaction kettle to be 80-100 ℃;
and fourthly, after the trichlorosilane is added, adjusting the temperature in the reaction kettle to be 80-90 ℃, and preserving the temperature for 1-2 hours to obtain the gamma-chloropropyltrichlorosilane.
2. The method for synthesizing gamma-chloropropyltrichlorosilane in a gas-liquid two-phase manner according to claim 1, wherein the molar ratio of chloropropene to trichlorosilane is 1-1.2: 1; in the second step, the addition amount of the gamma-chloropropyltrichlorosilane is 10-20% of the total mass of the chloropropene and the trichlorosilane.
3. The method for synthesizing gamma-chloropropyltrichlorosilane in a gas-liquid two-phase manner according to claim 1, wherein the platinum catalyst in the first step and the platinum catalyst in the second step are the same agent, the platinum catalyst is an isopropanol solution of cis-bis (triphenylphosphine) platinum (II) dichloride, and the cis-bis (triphenylphosphine) platinum (II) dichloride accounts for 10-30% of the total mass of the solution.
4. The method for synthesizing gamma-chloropropyltrichlorosilane in a gas-liquid two-phase manner according to claim 3, wherein the nano-pore material is a sintered material with micropores, which is obtained by sintering stainless steel powder and titanium powder, and the micropores have a pore diameter of 0.2-60 μm, a porosity of 40-50%, a compressive strength of 3MPa and a temperature resistance of 500 ℃; the nano-pore material loaded platinum catalyst is an isopropanol solution of cis-bis (triphenylphosphine) platinum (II) dichloride adsorbed on the nano-pore material, and the mass ratio of the isopropanol solution of the cis-bis (triphenylphosphine) platinum (II) dichloride loaded on the nano-pore material to the nano-pore material is 1: 10-100.
5. The method for synthesizing gamma-chloropropyltrichlorosilane in a gas-liquid two-phase manner according to claim 4, wherein the amount of the platinum catalyst loaded on the nano-pore material (calculated by Pt) is 20-40 ppm of the total mass of 3-chloropropene and trichlorosilane.
6. The method for synthesizing gamma-chloropropyltrichlorosilane in a gas-liquid two-phase manner according to claim 1, wherein the amount of the platinum catalyst (calculated by Pt) in the second-step reaction is 20-40 ppm of the total mass of 3-chloropropene and trichlorosilane.
7. The method for synthesizing gamma-chloropropyltrichlorosilane in a gas-liquid two-phase manner according to claim 1, wherein the pressure in the reaction kettle is-0.01 MPa to 0.03 MPa.
8. A reaction device used in the gas-liquid two-phase synthesis method of gamma-chloropropyltrichlorosilane according to any one of claims 1 to 7, comprising a gas phase reactor and a reaction kettle, wherein the gas phase reactor is of a pipe body structure, an upper baffle plate and a lower baffle plate are respectively fixed at the upper part and the lower part in the pipe body, and a nano-pore material is filled between the upper baffle plate and the lower baffle plate; the lower port of the gas phase reactor is connected with a reaction kettle, baffle plates are uniformly distributed on the inner wall of the reaction kettle, and the contact surface of the baffle plates and the material is an arc surface.
9. The reaction apparatus used in the gas-liquid two-phase synthesis method of gamma-chloropropyltrichlorosilane according to claim 8, further comprising a condenser, wherein the upper port of the gas phase reactor is connected to one end of the condenser.
10. The reaction apparatus used in the vapor-liquid two-phase synthesis method of gamma-chloropropyltrichlorosilane according to claim 8, wherein a stirring paddle is provided in the reaction vessel, and the stirring paddle is a double-layer push-type blade.
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| CN115594706A (en) * | 2022-10-14 | 2023-01-13 | 山东阳谷华泰化工股份有限公司（Cn） | Method for synthesizing gamma-chloropropyltrichlorosilane through heterogeneous catalysis |
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