CN113234101B - Gas-liquid two-phase synthesis method and reaction device of gamma-chloropropyl trichlorosilane - Google Patents
Gas-liquid two-phase synthesis method and reaction device of gamma-chloropropyl trichlorosilane Download PDFInfo
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- CN113234101B CN113234101B CN202110698394.2A CN202110698394A CN113234101B CN 113234101 B CN113234101 B CN 113234101B CN 202110698394 A CN202110698394 A CN 202110698394A CN 113234101 B CN113234101 B CN 113234101B
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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 39
- 239000007788 liquid Substances 0.000 title claims abstract description 18
- 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 55
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000007783 nanoporous material Substances 0.000 claims abstract description 26
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000005052 trichlorosilane Substances 0.000 claims abstract description 23
- 239000003054 catalyst Substances 0.000 claims abstract description 21
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 18
- 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 abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 12
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 6
- 230000002194 synthesizing effect Effects 0.000 claims description 5
- 238000005086 pumping 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
- 239000011799 hole material Substances 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 238000005245 sintering Methods 0.000 claims description 3
- 239000003814 drug Substances 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 10
- OWXJKYNZGFSVRC-NSCUHMNNSA-N (e)-1-chloroprop-1-ene Chemical compound C\C=C\Cl OWXJKYNZGFSVRC-NSCUHMNNSA-N 0.000 abstract description 9
- 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
- 230000035484 reaction time Effects 0.000 abstract description 2
- -1 and simultaneously Substances 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 25
- 239000007789 gas Substances 0.000 description 18
- 239000000047 product Substances 0.000 description 11
- 239000006087 Silane Coupling Agent Substances 0.000 description 8
- 230000001276 controlling effect Effects 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 238000010812 external standard method Methods 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 239000002131 composite 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
- 239000003795 chemical substances by application 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
- 238000003825 pressing Methods 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
- 239000000654 additive Substances 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
- 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
- 239000007792 gaseous phase Substances 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
- 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
- 239000002699 waste material 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
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
- C07F7/12—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
Landscapes
- 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-chloropropyl trichlorosilane, and relates to the technical field of gamma-chloropropyl trichlorosilane synthesis. The synthesis method uses cis-bis (triphenylphosphine) platinum (II) dichloride as a catalyst, and simultaneously, trichlorosilane is fed into chloropropene, so that side reaction is reduced. The reaction device not only adds the platinum catalyst into the reaction kettle, but also adsorbs the platinum catalyst to the nano-pore material, and the nano-pore material 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 has the main product yield as high as 88% -95%.
Description
Technical Field
The invention relates to the technical field of gamma-chloropropyl trichlorosilane production, in particular to a gas-liquid two-phase synthesis method and a reaction device of gamma-chloropropyl trichlorosilane.
Background
The silane coupling agent is a fourth major organic silicon product after the organic silicon three major products, namely silicone oil, silicone rubber and silicone resin, the position of the silane coupling agent in the organic silicon industry is becoming important, and the silane coupling agent becomes an indispensable matched chemical auxiliary agent in the modern organic silicon industry, organic polymer industry, composite material industry and related high and new technical fields.
The silane coupling agent is an important coupling agent, is used as an auxiliary agent commonly used in composite materials, and can improve the wettability of matrix resin to filler and glass fiber, so that the matrix resin is connected with the filler or the glass fiber through chemical bonds, and further the bending strength, impact strength, water resistance, electrical property and the like of the composite materials are improved. Silane coupling agents are also used as adhesives such as epoxy and nitrile rubber, and 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 most wide application, is one of the most basic monomers in the silane coupling agents, and can be used as a main production raw material to synthesize dozens of high-grade silane coupling agent products, such as gamma-chloropropyl triethoxysilane, gamma-chloropropyl trimethoxysilane, gamma-aminopropyl triethoxysilane, rubber additives Si69 and Si75, dental composite resin, organosilicon antibacterial finishing agents, optical glass antifogging agents and the like.
At present, the common method is to use chloropropene and trichlorosilane as raw materials and utilize platinum complex to catalyze hydrosilylation reaction to synthesize gamma-chloropropyl trichlorosilane. In the process of catalyzing and synthesizing gamma-chloropropyl trichlorosilane by using traditional chloroplatinic acid as a main catalyst, the following defects exist: (1) Various cocatalysts, activators and side reaction inhibitors need to be added; (2) the cocatalyst n-butylamine belongs to a highly toxic chemical; (3) high reaction temperature, high pressure and long time; (4) low product yield and complex byproduct components.
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-chloropropyl trichlorosilane, which are not applicable to cocatalysts and activators and have mild reaction conditions.
In order to achieve the technical purpose, the method adopts the following scheme: the gas-liquid two-phase synthesis method of gamma-chloropropyl trichlorosilane comprises the following steps:
firstly, loading a platinum catalyst in a nano-pore material of a gas phase reactor;
sequentially adding gamma-chloropropyl trichlorosilane, 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 by using a feed pump for 1-2 hours, and adjusting the pumping flow rate in real time to control the temperature in the reaction kettle to be kept at 80-100 ℃;
and fourthly, after the trichlorosilane is added, regulating the temperature in the reaction kettle to be 80-90 ℃ by utilizing heat conduction oil of the reaction kettle, and preserving heat for 1-2 hours to obtain the gamma-chloropropyl trichlorosilane product.
Compared with the prior art, the method has the beneficial effects that: the invention provides a gas-liquid two-phase synthesis method of gamma-chloropropyl trichlorosilane, which uses cis-bis (triphenylphosphine) platinum (II) dichloride as a catalyst, and simultaneously adds trichlorosilane into 3-chloropropene in a flowing way, so that side reaction is reduced; a small amount of gamma-chloropropyl trichlorosilane 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 has the main product yield as high as 88% -95%.
The method of the invention has the preferable scheme that:
the mol ratio of chloropropene to trichlorosilane is 1-1.2:1; in the second step, a small amount of gamma-chloropropyl trichlorosilane is added for improving the reaction temperature, wherein the addition amount of the gamma-chloropropyl trichlorosilane is 10-20% of the total mass of chloropropene and trichlorosilane.
The platinum catalyst in the first step and the second step is the same medicament, 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 sintered material with micropores, wherein the sintered material is formed by sintering stainless steel powder and titanium powder, 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 characterized in that an isopropanol solution of cis-bis (triphenylphosphine) platinum (II) dichloride is adsorbed on the nano-pore material, and the mass ratio of the isopropanol solution of cis-bis (triphenylphosphine) platinum (II) dichloride loaded by the nano-pore material to the nano-pore material is 1:10-100.
The dosage (calculated by Pt) of the platinum catalyst loaded by the nano-pore material is 20-40 ppm of the total mass of 3-chloropropene and trichlorosilane.
In the second step of reaction, the dosage (calculated by Pt) of isopropanol solution of cis-bis (triphenylphosphine) platinum (II) dichloride is 20-40 ppm of the total mass of 3-chloropropene and trichlorosilane.
In the third step of reaction, the pressure in the reaction kettle is-0.01-0.03 MPa micro-positive pressure, so that byproduct hydrogen chloride can be conveniently extracted.
In order to achieve the technical purpose, the device adopts the following scheme: the reaction device used in the gas-liquid two-phase synthesis method of gamma-chloropropyl trichlorosilane comprises 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 nano hole materials are plugged between the upper baffle plate and the lower baffle plate; the lower port of the gas phase reactor is connected with a reaction kettle, the inner wall of the reaction kettle is uniformly provided with a baffle plate, and the contact surface of the baffle plate 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 nano-pore material and loads the nano-pore 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, the reactor also comprises a condenser, wherein the upper port of the gas phase reactor is connected with one end of the condenser, so that raw material volatilization is prevented, and material leakage is reduced.
Further, a stirring paddle is arranged in the reaction kettle, and the stirring paddle is a double-layer propelling blade.
Drawings
FIG. 1 is a schematic diagram of a gas-liquid two-phase synthesis reaction device for gamma-chloropropyl trichlorosilane provided by the embodiment of the invention;
FIG. 2 is a schematic diagram of a gas phase reactor according to an embodiment of the present invention;
marked in the figure as: 1. a reaction kettle; 2. a striker plate; 3. stirring paddles; 4. a gas phase reactor; 5. a condenser; 6. a heat transfer oil outlet; 7. a conduction 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; 14. a nano-pore material; 15. and a lower baffle.
Detailed Description
The present invention will be described in detail with reference to the following embodiments for a full understanding of the objects, features and effects of the present invention, but the present invention is not limited thereto.
Referring to fig. 1, the gas-liquid two-phase synthesis reaction device for gamma-chloropropyl trichlorosilane 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 pipe body structure, an upper baffle 13 and a lower baffle 15 which are made of stainless steel are respectively fixed on the upper part and the lower part of the inner wall of the pipe body, the sections of the upper baffle 13 and the lower baffle 15 are of a W-shaped structure, through holes are formed in the surfaces of the upper baffle 13 and the lower baffle 15, and nano-pore materials 14 can be supported by the upper baffle 13 and the lower baffle 15 and gas can be permeated. The nano-pore material 14 is plugged between the upper baffle 13 and the lower baffle 15, as shown in fig. 2, the nano-pore material 14 is a sintered material with distributed micropores formed by sintering stainless steel powder and titanium powder, the sintered material is a purchased product, the pore diameter of the micropores is 0.2-60 μm, the porosity is 40-50%, the compressive strength is 3MPa, and the temperature resistance is 500 ℃. Because the boiling point of trichlorosilane is 33 ℃, the boiling point of 3-chloropropene is 44 ℃, and the two raw materials are easy to volatilize, the two raw materials react in a gas phase state and also react in a liquid phase state by utilizing the gas phase reactor 4, the reaction speed is accelerated, the condensation cost is saved, and the material leakage is reduced. The platinum catalyst in the gas phase reactor can be repeatedly used for a plurality of times, and the nano-pore material is sintered and recovered for use after the catalyst is invalid.
The outer wall of reation kettle 1 is provided with and presss from both sides cover 9, and the upper end of pressing from both sides cover 9 is provided with conduction oil export 6, and the lower extreme of pressing from both sides cover 9 is provided with conduction oil import 7, and the upper end of reation kettle 1 sets up feed inlet 12 and connector respectively, and the connector is connected with the lower port of gaseous phase reactor 4, and the lower extreme of reation kettle 1 is provided with discharge gate 8, and the annular equipartition of reation kettle 1 inner wall is fixed with 6 striker plates 2, and striker plate 2 vertical welding is on the inner wall, and striker plate 2 is the arcwall face with the material contact surface, promotes the stirring, makes the material stir abundant, does not have the dead angle. The inside of reation kettle 1 is provided with stirring rake 3, and stirring rake 3 is double-deck propelled blade, and stirring rake 3 comprises pivot, upper blade and lower blade, and the lower blade is fixed in the lower extreme of pivot, and upper blade is parallel to the lower blade and is fixed in the middle part or the lower part of pivot.
A spiral condensing pipe is arranged in the condenser 5, the lower end of the spiral condensing pipe is a condensate inlet 10, the upper end of the spiral condensing pipe is a condensate outlet 11, 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 raw materials from volatilizing, and waste of the raw materials is caused.
Example 1
Adding 0.8g of isopropanol solution of 10wt% cis-bis (triphenylphosphine) platinum (II) dichloride loaded by a nano-pore material 14 into a gas phase reactor 4, adding 100g of gamma-chloropropyl trichlorosilane, 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 way, and controlling the reaction temperature to be 80-100 ℃ and finishing the adding in a flowing way for 1 hour; after the trichlorosilane is added, the liquid is kept at 80 ℃ for 1h in the reaction kettle 1. The product was sampled and the yield of gamma-chloropropyl trichlorosilane was 88.7% as measured by TCD gas chromatography external standard method.
Example 2
Adding 0.7g of isopropanol solution of 20wt% cis-bis (triphenylphosphine) platinum (II) dichloride loaded by a nano-pore material 14 into a gas phase reactor 4, adding 150g of gamma-chloropropyl trichlorosilane, 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, and controlling the reaction temperature to be 80-100 ℃ and finishing the feeding for 1.5 hours; after the addition of trichlorosilane is completed, the liquid is kept at 90 ℃ for 1.5 hours in the reaction kettle 1. The product was sampled and the yield of gamma-chloropropyl trichlorosilane was 90.6% as measured by TCD gas chromatography external standard method.
Example 3
Adding 0.6g of isopropanol solution of 25wt% cis-bis (triphenylphosphine) platinum (II) dichloride loaded by a nano-pore material 14 into a gas phase reactor 4, adding 200g of gamma-chloropropyl trichlorosilane, 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 ℃, adding 602g of trichlorosilane for 2h, and controlling the reaction temperature to be 80-100 ℃ and finishing the 1h feeding; after the trichlorosilane is added, the liquid is kept at 100 ℃ for 2 hours in the reaction kettle 1. The product was sampled and the yield of gamma-chloropropyl trichlorosilane was 92.8% as measured by TCD gas chromatography external standard method.
Comparative example
Mixing 408g of chloropropene and 602g of trichlorosilane uniformly, adding 100g of gamma-chloropropyl trichlorosilane and 1.1g of isopropanol solution of 10wt% chloroplatinic acid into a reaction kettle, stirring and heating to 70 ℃, adding 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 at 140 ℃ for 2 hours in the reaction kettle. The product was sampled and the yield of gamma-chloropropyl trichlorosilane was 72.5% as measured by TCD gas chromatography external standard method.
Finally, it should be noted that: the above list is only a preferred embodiment of the present invention, and it is understood that those skilled in the art can make modifications and variations thereto, and it is intended that the present invention be construed as the scope of the appended claims and their equivalents.
Claims (6)
1. The gas-liquid two-phase synthesis method of gamma-chloropropyl trichlorosilane is characterized by comprising the following steps of:
firstly, loading a platinum catalyst in a nano-pore material of a gas phase reactor;
the nano-pore material is a sintered material with micropores, wherein the sintered material is formed by sintering stainless steel powder and titanium powder, 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 characterized in that an isopropanol solution of cis-bis (triphenylphosphine) platinum (II) dichloride is adsorbed on the nano-pore material, and the mass ratio of the isopropanol solution of cis-bis (triphenylphosphine) platinum (II) dichloride loaded by the nano-pore material to the nano-pore material is 1:10-100;
sequentially adding gamma-chloropropyl trichlorosilane, 3-chloropropene and a platinum catalyst into a reaction kettle, fully stirring, and heating the reaction kettle to 60-70 ℃;
the platinum catalyst in the first step and the second step is the same medicament, 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;
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 kept at 80-100 ℃;
fourthly, after the trichlorosilane is added, regulating the temperature in the reaction kettle to be 80-90 ℃ and preserving heat for 1-2 hours to obtain the gamma-chloropropyl trichlorosilane;
the reaction device used in the gas-liquid two-phase synthesis method of gamma-chloropropyl trichlorosilane comprises 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 nano hole materials are plugged between the upper baffle plate and the lower baffle plate; the lower port of the gas phase reactor is connected with a reaction kettle, the inner wall of the reaction kettle is uniformly provided with a baffle plate, and the contact surface of the baffle plate and the material is an arc surface.
2. The gas-liquid two-phase synthesis method of gamma-chloropropyl trichlorosilane according to claim 1, wherein the molar ratio of 3-chloropropene to trichlorosilane is 1-1.2:1; in the second step, the addition amount of the gamma-chloropropyl trichlorosilane is 10-20% of the total mass of the 3-chloropropene and the trichlorosilane.
3. The gas-liquid two-phase synthesis method of gamma-chloropropyl trichlorosilane according to claim 1, wherein the amount of the platinum catalyst loaded by the nano-pore material is 20-40 ppm of the total mass of 3-chloropropene and trichlorosilane calculated by Pt.
4. The method for synthesizing gamma-chloropropyl trichlorosilane according to claim 1, wherein the pressure in the reaction kettle is-0.01-0.03 MPa.
5. The method for synthesizing gamma-chloropropyl trichlorosilane according to claim 1, wherein the reaction device used in the method for synthesizing gamma-chloropropyl trichlorosilane further comprises a condenser, and the upper port of the gas phase reactor is connected with one end of the condenser.
6. The method for synthesizing gamma-chloropropyl trichlorosilane according to claim 1, wherein stirring paddles are arranged in the reaction kettle, and the stirring paddles are double-layer propelling blades.
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| US4292433A (en) * | 1980-10-31 | 1981-09-29 | Chisso Corporation | Method for producing 3-chloropropyltrichlorosilane |
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| CN104974184A (en) * | 2014-04-03 | 2015-10-14 | 信越化学工业株式会社 | Preparation Of Silazane Compound |
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| CN101774872A (en) * | 2009-12-25 | 2010-07-14 | 盐城七善化工科技有限公司 | Preparation method of methyl chloride compounds and special device thereof |
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