Method for synthesizing vinyltributylacetonatoximosilane by catalysis using a membrane reactor

Abstract

The invention relates to the field of chemical production technology, and specifically to a method for catalytically synthesizing vinyltributylacetonatomylic silane using a membrane reactor; the invention provides a method for catalytically synthesizing vinyltributylacetonatomylic silane using a membrane reactor, wherein the hydroxyl groups of ethylene glycol-based styrene polymers react with allyl bromide under the catalytic action of tetrabutylammonium bromide to obtain an alkaline resin catalyst, and then vinyltrichlorosilane reacts with butanone oxime in an external membrane reactor, and the resin catalyst of the external membrane reactor catalyzes the reaction, and the catalyst membrane is retained in the reactor, thereby realizing a continuous reaction process.

Description

Technical Field

[0001] The invention relates to the field of chemical production technology, and in particular to a method for catalytically synthesizing vinyltributylacetonato silane using a membrane reactor. Background Art

[0002] The advent of membrane reactor technology has achieved the coupling of membrane separation technology and reaction process, solving the problems of long process, low efficiency and high energy consumption. Nanjing University of Technology and Nanjing Jiusi High-tech Co., Ltd. have successfully developed ceramic membrane products of various specifications and models through more than 20 years of scientific research on continuous ceramic membrane reactors, realizing the large-scale application and continuous production of membrane reactors in the petrochemical field. Ceramic membrane reactors can significantly shorten the chemical production process, improve product yield, reduce production costs, and reduce the emission of "three wastes", and are resource-saving and environmentally friendly.

[0003] CN1012436B relates to a method for preparing 6-methyl-3,4-dihydro-1,2,3-thiazin-4-one 2,2-dioxide. Acetoacetamide-N-sulfonic acid and its salts and sulfur trioxide in an equimolar amount are reacted in a recommended special device (membrane reactor) to form 6-methyl-3,4-dihydro-1,2,3-thiazin-4-one 2,2-dioxide in a short time. When sulfur trioxide is used in excess of an equimolar amount, the latter forms an adduct of sulfur trioxide. The adduct needs to be hydrolyzed. The hydrolysis can also be carried out in a short time, preferably in a device of the same type as the closed-loop reaction. The non-toxic salts, especially the potassium salts, of 6-methyl-3,4-dihydro-1,2,3-thiazin-4-one 2,2-dioxide are valuable synthetic sweeteners.

[0004] CN102924494A discloses an organic oxime silane and a preparation method thereof, wherein the organic oxime silane has a composition such as a molecular structure (A), wherein the molecular structure (A) contains two or more different types of oxime substituents. The silane can be obtained by oxime-modifying the corresponding chlorosilane, aminosilane, and alkoxysilane. The silane can be used as a curing crosslinking agent or chain extender in condensation-type room temperature curing silicone rubber, and can provide adjustable reaction activity and control of the types of organic removal substances (VOC).

[0005] However, the existing technologies are all intermittent reactions and cannot achieve continuous production. The catalyst is not easy to separate from the product, so the efficiency is low and the output is small. Summary of the invention

[0006] The invention discloses a method for catalytically synthesizing vinyltributylacetonatoximinesilane using a membrane reactor, and belongs to the technical field of chemical production.

[0007] A method for catalytically synthesizing vinyltributylonoxime silane using a membrane reactor, characterized in that it comprises the following steps:

[0008] Step 1: Mix butanone oxime and solvent oil in a mixing kettle, then heat up and dropwise add vinyl trichlorosilane, then introduce a resin catalyst into an external membrane reactor, and react in the external membrane reactor, the molar ratio of vinyl trichlorosilane to butanone oxime is 1:5-8, the reaction temperature is 50-65°C, the reaction space velocity of the mixed liquid is 0.5-3h-1, the reaction pressure is 0.05-0.8MPa, the reaction mixture is pumped from the bottom of the reactor to a ceramic membrane filter to separate the catalyst and the reaction product, the separated product seeps out from the membrane tube in the form of a clear liquid, and the flow rate of the membrane permeate is automatically controlled to be consistent with the total amount of reactants entering the reactor;

[0009] Step 2: The product is layered, the upper and lower layers are separated, a neutralizing agent is added to the upper layer to neutralize it to make it alkaline, and the filtrate is sent to a distillation kettle, and the solvent is evaporated at a certain temperature. The solvent can be recycled and used, and the product is in the kettle; the product obtained by distillation of the lower layer is then washed and filtered to obtain the finished product of vinyl trisbutyl ketoxime silane.

[0010] More preferably, the dropping conditions in step 1 are as follows: the temperature during the dropping is 20-30° C., and the dropping time is controlled at 30-60 min;

[0011] More preferably, the resin catalyst content in step 1 is 30-60% of the volume of the external membrane reactor;

[0012] More preferably, the external membrane reactor in step 1 can be a commercially available product, such as the external membrane reactor produced by Nanjing Jiusi High-tech Co., Ltd.;

[0013] More preferably, the preparation method of the resin catalyst in step 1 is:

[0014] Step a: adding 1000-1300 parts of deionized water and 1-4 parts of dispersant by weight into a reaction kettle, and stirring evenly; then adding 100-120 parts of styrene, 10-16 parts of ethylene glycol diacrylate, and 1-4 parts of peroxide initiator, and stirring evenly; after the reaction is completed, discharging the material, washing with water, and drying to obtain an ethylene glycol-based styrene polymer;

[0015] Step b: by weight, 50-70 parts of ethylene glycol-based styrene polymer, 20-30 parts of allyl bromide, 2-5 parts of tetrabutylammonium bromide, 220-240 parts of toluene, react at 50-60°C for 2-5 hours, filter to remove the liquid, then add 6-11 parts of 4-mercaptopyridine and 100-140 parts of triethylamine, react at 50-70°C for 10-20 hours, filter after the reaction, wash the solid with ethanol, and dry to obtain a resin catalyst.

[0016] More preferably, the dispersant in step a is polyvinyl alcohol, gelatin or hydroxymethyl cellulose;

[0017] More preferably, the peroxide initiator in step a is selected from diisopropylbenzene peroxide, 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane and bis(tert-butyldioxyisopropyl)benzene, benzoyl peroxide;

[0018] More preferably, the reaction conditions in step a are: the reaction temperature is controlled at 80-95° C., and the reaction time is controlled at 12-17 h;

[0019] More optimized, the reaction conditions of step 1 are: reaction temperature is 50-65°C, and the reaction space velocity of the mixed solution is 0.5-3h -1 , the reaction pressure is 0.05-0.8MPa;

[0020] More preferably, the neutralizing agent in step 2 is sodium hydroxide or potassium hydroxide;

[0021] More optimally, the reduced pressure distillation conditions in step 2 are: pressure of 0.01-0.1 MPa, temperature of 92° C.-110° C., and the reaction liquid is distilled.

[0022] The reaction mechanism is:

[0023] (1) Vinyltrichlorosilane and butanone oxime react in an external membrane reactor. The resin catalyst of the external membrane reactor catalyzes the reaction and the catalyst is retained in the reactor by the membrane, thus realizing a continuous reaction process.

[0024] (2) The hydroxyl group of the ethylene glycol-based styrene polymer reacts with allyl bromide under the catalytic action of tetrabutylammonium bromide to obtain an allyl styrene polymer, which then undergoes a mercapto addition reaction with 4-mercaptopyridine under the action of triethylamine to obtain a pyridyl styrene polymer, which is then loaded with triethylamine to obtain an alkaline resin catalyst.

[0025] The technical effects are:

[0026] (1) Compared with liquid alkaline catalysts, the resin catalyst for producing vinyltributylonoxime silane obtained by the present invention has a long service life, has acetic acid / sulfonic acid groups on the skeleton, and does not cause large amounts of waste acid pollution.

[0027] (2) The catalyst can be recycled, and the external membrane reactor process can increase the production scale and achieve continuous production. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 This is the 1H NMR spectrum of the vinyltributylonoximesilane prepared in Example 2. DETAILED DESCRIPTION

[0029] The invention will be further described below by means of specific embodiments:

[0030] Example 1

[0031] The preparation method of the resin catalyst is as follows: step a: adding 1000g of deionized water and 1g of dispersant polyvinyl alcohol into a reaction kettle, and stirring evenly; then adding 100g of styrene, 10g of ethylene glycol diacrylate, and 1g of diisopropylbenzene peroxide, and stirring evenly; then reacting at 80°C for 12h, discharging after the reaction, washing with water, and drying to obtain an ethylene glycol-based styrene polymer; step b: reacting 50g of ethylene glycol-based styrene polymer, 20g of allyl bromide, 2g of tetrabutylammonium bromide, and 220g of toluene at 50°C for 2h, filtering to remove the liquid, and then adding 6g of 4-mercaptopyridine and 100g of triethylamine, reacting at 50°C for 10h, filtering after the reaction, washing the solid with ethanol, and drying to obtain a resin catalyst.

[0032] Step 1: Mix butanone oxime and solvent oil in a mixing kettle, then heat up to 20°C, drop vinyl trichlorosilane for 30 minutes, and then pass into an external membrane reactor filled with a resin catalyst that accounts for 30% of the volume of the external membrane reactor. React in the external membrane reactor. The molar ratio of vinyl trichlorosilane to butanone oxime is 1:5, the reaction temperature is 50°C, and the reaction space velocity of the mixed liquid is 0.5h -1 , the reaction pressure is 0.05MPa, the reaction mixture is pumped from the bottom of the reactor to the ceramic membrane filter to separate the catalyst and the reaction product, the separated product seeps out of the membrane tube in the form of clear liquid, and the flow rate of the membrane permeate is automatically controlled to be consistent with the total amount of reactants entering the reactor;

[0033] Step 2: The product is layered, the upper and lower layers are separated, the upper layer is neutralized by adding a neutralizing agent, sodium hydroxide, to make it alkaline, filtered, and the filtrate enters a distillation kettle to evaporate the solvent, the solvent can be recycled, and the kettle is the product; the vacuum distillation conditions are: at a pressure of 0.01 MPa and a temperature of 92° C., the reaction liquid is distilled, and the product obtained by distillation is then washed and filtered to obtain the finished product of vinyl trisbutyl ketoxime silane.

[0034] Example 2

[0035] The preparation method of the resin catalyst is as follows: step a: adding 1000g of deionized water and 2g of dispersant polyvinyl alcohol into a reaction kettle, and stirring evenly; then adding 105g of styrene, 12g of ethylene glycol diacrylate, and 2g of diisopropylbenzene peroxide and stirring evenly; then reacting at 80°C for 12h, discharging after the reaction, washing with water, and drying to obtain an ethylene glycol-based styrene polymer; step b: reacting 55g of ethylene glycol-based styrene polymer, 22g of allyl bromide, 2g of tetrabutylammonium bromide, and 220g of toluene at 60°C for 2h, filtering to remove the liquid, and then adding 7g of 4-mercaptopyridine and 100g of triethylamine, reacting at 60°C for 10h, filtering after the reaction, washing the solid with ethanol, and drying to obtain a resin catalyst.

[0036] Step 1: Mix butanone oxime and solvent oil in a mixing kettle, then heat up to 20°C, dropwise add vinyl trichlorosilane for 40 minutes, and then pass into an external membrane reactor filled with a resin catalyst accounting for 40% of the volume of the external membrane reactor, and react in the external membrane reactor. The molar ratio of vinyl trichlorosilane to butanone oxime is 1:5, the reaction temperature is 55°C, and the reaction space velocity of the mixed liquid is 1.0h -1 , the reaction pressure is 0.2MPa, the reaction mixture is pumped from the bottom of the reactor to the ceramic membrane filter to separate the catalyst and the reaction product, the separated product seeps out of the membrane tube in the form of clear liquid, and the flow rate of the membrane permeate is automatically controlled to be consistent with the total amount of reactants entering the reactor;

[0037] Step 2: The product is layered, the upper and lower layers are separated, the upper layer is neutralized by adding a neutralizing agent, sodium hydroxide, to make it alkaline, filtered, and the filtrate enters a distillation kettle to evaporate the solvent, the solvent can be recycled, and the kettle is the product; the vacuum distillation conditions are: the reaction liquid is distilled at a pressure of 0.03 MPa and a temperature of 92° C., and the product obtained by distillation is then washed and filtered to obtain the finished product of vinyl trisbutyl ketoxime silane.

[0038] Example 3

[0039] The preparation method of the resin catalyst is as follows: step a: add 1100g of deionized water and 2g of dispersant gelatin into a reaction kettle and stir evenly; then add 110g of styrene, 12g of ethylene glycol diacrylate, 2g of 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane and bis(tert-butyldioxyisopropyl)benzene and stir evenly; then react at 85°C for 14h, discharge the material after the reaction is completed, wash with water, and dry to obtain an ethylene glycol-based styrene polymer; step b: react 60g of ethylene glycol-based styrene polymer, 24g of allyl bromide, 3g of tetrabutylammonium bromide, and 220g of toluene at 60°C for 3h, filter to remove the liquid, then add 8g of 4-mercaptopyridine and 110g of triethylamine, react at 60°C for 14h, filter after the reaction is completed, wash the solid with ethanol, and dry to obtain a resin catalyst.

[0040] Step 1: Mix butanone oxime and solvent oil in a mixing kettle, then heat to 24°C, dropwise add vinyl trichlorosilane for 40 minutes, and then pass into an external membrane reactor filled with a resin catalyst that accounts for 50% of the volume of the external membrane reactor. React in the external membrane reactor. The molar ratio of vinyl trichlorosilane to butanone oxime is 1:6, the reaction temperature is 55°C, and the reaction space velocity of the mixed liquid is 1.5h -1 , the reaction pressure is 0.4MPa, the reaction mixture is pumped from the bottom of the reactor to the ceramic membrane filter to separate the catalyst and the reaction product, the separated product seeps out of the membrane tube in the form of clear liquid, and the flow rate of the membrane permeate is automatically controlled to be consistent with the total amount of reactants entering the reactor;

[0041] Step 2: The product is layered, the upper and lower layers are separated, the upper layer is neutralized by adding a neutralizing agent, sodium hydroxide, to make it alkaline, filtered, and the filtrate enters a distillation kettle to evaporate the solvent, the solvent can be recycled, and the kettle is the product; the vacuum distillation conditions are: at a pressure of 0.05 MPa and a temperature of 98° C., the reaction liquid is distilled, and the product obtained by distillation is then washed and filtered to obtain the finished product of vinyl trisbutyl ketoxime silane.

[0042] Example 4

[0043] The preparation method of the resin catalyst is as follows: step a: adding 1200g of deionized water and 3g of dispersant hydroxymethyl cellulose into a reaction kettle and stirring evenly; then adding 115g of styrene, 14g of ethylene glycol diacrylate, 3g of 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane and bis(tert-butyldioxyisopropyl)benzene and stirring evenly; then reacting at 90°C for 15h, discharging after the reaction is completed, washing with water, and drying to obtain an ethylene glycol-based styrene polymer; step b: reacting 65g of ethylene glycol-based styrene polymer, 26g of allyl bromide, 4g of tetrabutylammonium bromide, and 230g of toluene at 60°C for 4h, filtering to remove the liquid, then adding 9g of 4-mercaptopyridine and 125g of triethylamine, reacting at 60°C for 18h, filtering after the reaction is completed, washing the solid with ethanol, and drying to obtain a resin catalyst.

[0044] Step 1: Mix butanone oxime and solvent oil in a mixing kettle, then heat to 28°C, dropwise add vinyl trichlorosilane for 50 minutes, and then pass into an external membrane reactor filled with a resin catalyst accounting for 60% of the volume of the external membrane reactor, and react in the external membrane reactor. The molar ratio of vinyl trichlorosilane to butanone oxime is 1:7, the reaction temperature is 60°C, and the reaction space velocity of the mixed liquid is 2.0h -1 , the reaction pressure is 0.6MPa, the reaction mixture is pumped from the bottom of the reactor to the ceramic membrane filter to separate the catalyst and the reaction product, the separated product seeps out of the membrane tube in the form of clear liquid, and the flow rate of the membrane permeate is automatically controlled to be consistent with the total amount of reactants entering the reactor;

[0045] Step 2: The product is layered, the upper and lower layers are separated, the upper layer is neutralized by adding a neutralizing agent, sodium hydroxide, to make it alkaline, filtered, and the filtrate enters a distillation kettle to evaporate the solvent, the solvent can be recycled, and the kettle is the product; the vacuum distillation conditions are: the reaction liquid is distilled at a pressure of 0.08 MPa and a temperature of 105° C., and the product obtained by distillation is then washed and filtered to obtain the finished product of vinyl trisbutyl ketoxime silane.

[0046] Example 5

[0047] The preparation method of the resin catalyst is as follows: step a: adding 1300g of deionized water and 4g of dispersant hydroxymethyl cellulose into a reaction kettle and stirring evenly; then adding 120g of styrene, 16g of ethylene glycol diacrylate and 4g of benzoyl peroxide and stirring evenly; then reacting at 95°C for 17h, discharging after the reaction is completed, washing with water, and drying to obtain an ethylene glycol-based styrene polymer; step b: reacting 70g of ethylene glycol-based styrene polymer, 30g of allyl bromide, 5g of tetrabutylammonium bromide and 240g of toluene at 60°C for 5h, filtering to remove the liquid, then adding 11g of 4-mercaptopyridine and 140g of triethylamine, reacting at 70°C for 20h, filtering after the reaction is completed, washing the solid with ethanol and drying to obtain a resin catalyst.

[0048] Step 1: Mix butanone oxime and solvent oil in a mixing kettle, then heat to 30°C, dropwise add vinyl trichlorosilane for 60 minutes, and then pass into an external membrane reactor filled with a resin catalyst accounting for 60% of the volume of the external membrane reactor, and react in the external membrane reactor. The molar ratio of vinyl trichlorosilane to butanone oxime is 1:8, the reaction temperature is 65°C, and the reaction space velocity of the mixed liquid is 3.0h -1 , the reaction pressure is 0.8MPa, the reaction mixture is pumped from the bottom of the reactor to the ceramic membrane filter to separate the catalyst and the reaction product, the separated product seeps out of the membrane tube in the form of clear liquid, and the flow rate of the membrane permeate is automatically controlled to be consistent with the total amount of reactants entering the reactor;

[0049] Step 2: The product is layered, the upper and lower layers are separated, the upper layer is neutralized by adding a neutralizing agent, sodium hydroxide, to make it alkaline, filtered, and the filtrate enters a distillation kettle to evaporate the solvent, the solvent can be recycled, and the kettle is the product; the vacuum distillation conditions are: under a pressure of 0.1 MPa and a temperature of 110° C., the reaction liquid is distilled, and the product obtained by distillation is then washed and filtered to obtain the finished product of vinyl trisbutyl ketoxime silane.

[0050] Comparative Example 1

[0051] The preparation method of the resin catalyst is as follows: step a: adding 1000g of deionized water and 1g of dispersant polyvinyl alcohol into a reaction kettle, and stirring evenly; then adding 100g of styrene, 10g of ethylene glycol diacrylate, and 1g of diisopropylbenzene peroxide, and stirring evenly; then reacting at 80°C for 12h, discharging after the reaction, washing with water, and drying to obtain an ethylene glycol-based styrene polymer; step b: reacting 50g of the ethylene glycol-based styrene polymer, 2g of tetrabutylammonium bromide, and 220g of toluene at 50°C for 2h, filtering to remove the liquid, and then adding 6g of 4-mercaptopyridine and 100g of triethylamine, reacting at 50°C for 10h, filtering after the reaction, washing the solid with ethanol, and drying to obtain a resin catalyst.

[0052] Step 1: Mix butanone oxime and solvent oil in a mixing kettle, then heat up to 20°C, drop vinyl trichlorosilane for 30 minutes, and then pass into an external membrane reactor filled with a resin catalyst that accounts for 30% of the volume of the external membrane reactor. React in the external membrane reactor. The molar ratio of vinyl trichlorosilane to butanone oxime is 1:5, the reaction temperature is 50°C, and the reaction space velocity of the mixed liquid is 0.5h -1 , the reaction pressure is 0.05MPa, the reaction mixture is pumped from the bottom of the reactor to the ceramic membrane filter to separate the catalyst and the reaction product, the separated product seeps out of the membrane tube in the form of clear liquid, and the flow rate of the membrane permeate is automatically controlled to be consistent with the total amount of reactants entering the reactor;

[0053] Step 2: The product is layered, the upper and lower layers are separated, the upper layer is neutralized by adding a neutralizing agent, sodium hydroxide, to make it alkaline, filtered, and the filtrate enters a distillation kettle to evaporate the solvent, the solvent can be recycled, and the kettle is the product; the vacuum distillation conditions are: at a pressure of 0.01 MPa and a temperature of 92° C., the reaction liquid is distilled, and the product obtained by distillation is then washed and filtered to obtain the finished product of vinyl trisbutyl ketoxime silane.

[0054] Comparative Example 2

[0055] The preparation method of the resin catalyst is as follows: step a: adding 1000g of deionized water and 1g of dispersant polyvinyl alcohol into a reaction kettle, and stirring evenly; then adding 100g of styrene, 10g of ethylene glycol diacrylate, and 1g of diisopropylbenzene peroxide, and stirring evenly; then reacting at 80°C for 12h, discharging after the reaction, washing with water, and drying to obtain an ethylene glycol-based styrene polymer; step b: reacting 50g of ethylene glycol-based styrene polymer, 20g of allyl bromide, and 220g of toluene at 50°C for 2h, filtering to remove the liquid, and then adding 6g of 4-mercaptopyridine and 100g of triethylamine, reacting at 50°C for 10h, filtering after the reaction, washing the solid with ethanol, and drying to obtain the resin catalyst.

[0056] Step 1: Mix butanone oxime and solvent oil in a mixing kettle, then heat up to 20°C, drop vinyl trichlorosilane for 30 minutes, and then pass into an external membrane reactor filled with a resin catalyst that accounts for 30% of the volume of the external membrane reactor. React in the external membrane reactor. The molar ratio of vinyl trichlorosilane to butanone oxime is 1:5, the reaction temperature is 50°C, and the reaction space velocity of the mixed liquid is 0.5h -1 , the reaction pressure is 0.05MPa, the reaction mixture is pumped from the bottom of the reactor to the ceramic membrane filter to separate the catalyst and the reaction product, the separated product seeps out of the membrane tube in the form of clear liquid, and the flow rate of the membrane permeate is automatically controlled to be consistent with the total amount of reactants entering the reactor;

[0057] Step 2: The product is layered, the upper and lower layers are separated, the upper layer is neutralized by adding a neutralizing agent, sodium hydroxide, to make it alkaline, filtered, and the filtrate enters a distillation kettle to evaporate the solvent, the solvent can be recycled, and the kettle is the product; the vacuum distillation conditions are: at a pressure of 0.01 MPa and a temperature of 92° C., the reaction liquid is distilled, and the product obtained by distillation is then washed and filtered to obtain the finished product of vinyl trisbutyl ketoxime silane.

[0058] Comparative Example 3

[0059] The preparation method of the resin catalyst is as follows: step a: adding 1000g of deionized water and 1g of dispersant polyvinyl alcohol into a reaction kettle, and stirring evenly; then adding 100g of styrene, 10g of ethylene glycol diacrylate, and 1g of diisopropylbenzene peroxide and stirring evenly; then reacting at 80°C for 12h, discharging the material after the reaction is completed, washing with water, and drying to obtain an ethylene glycol-based styrene polymer; step b: reacting 50g of ethylene glycol-based styrene polymer, 20g of allyl bromide, 2g of tetrabutylammonium bromide, and 220g of toluene at 50°C for 2h, filtering to remove the liquid, and then adding 100g of triethylamine, reacting at 50°C for 10h, filtering after the reaction is completed, washing the solid with ethanol, and drying to obtain a resin catalyst.

[0060] Step 1: Mix butanone oxime and solvent oil in a mixing kettle, then heat up to 20°C, drop vinyl trichlorosilane for 30 minutes, and then pass into an external membrane reactor filled with a resin catalyst that accounts for 30% of the volume of the external membrane reactor. React in the external membrane reactor. The molar ratio of vinyl trichlorosilane to butanone oxime is 1:5, the reaction temperature is 50°C, and the reaction space velocity of the mixed liquid is 0.5h -1 , the reaction pressure is 0.05MPa, the reaction mixture is pumped from the bottom of the reactor to the ceramic membrane filter to separate the catalyst and the reaction product, the separated product seeps out of the membrane tube in the form of clear liquid, and the flow rate of the membrane permeate is automatically controlled to be consistent with the total amount of reactants entering the reactor;

[0061] Step 2: The product is layered, the upper and lower layers are separated, the upper layer is neutralized by adding a neutralizing agent, sodium hydroxide, to make it alkaline, filtered, and the filtrate enters a distillation kettle to evaporate the solvent, the solvent can be recycled, and the kettle is the product; the vacuum distillation conditions are: at a pressure of 0.01 MPa and a temperature of 92° C., the reaction liquid is distilled, and the product obtained by distillation is then washed and filtered to obtain the finished product of vinyl trisbutyl ketoxime silane.

[0062] Comparative Example 4

[0063] Step 1: Mix butanone oxime and solvent oil in a mixing kettle, then heat it to 20°C, drop vinyl trichlorosilane for 30 minutes, and then pass it into an external membrane reactor to react in the external membrane reactor. The molar ratio of vinyl trichlorosilane to butanone oxime is 1:5, the reaction temperature is 50°C, and the reaction space velocity of the mixed liquid is 0.5h -1 , the reaction pressure is 0.05MPa, the reaction mixture is pumped from the bottom of the reactor to the ceramic membrane filter to separate the catalyst and the reaction product, the separated product seeps out of the membrane tube in the form of clear liquid, and the flow rate of the membrane permeate is automatically controlled to be consistent with the total amount of reactants entering the reactor;

[0064] Step 2: The product is layered, the upper and lower layers are separated, the upper layer is neutralized by adding a neutralizing agent, sodium hydroxide, to make it alkaline, filtered, and the filtrate enters a distillation kettle to evaporate the solvent, the solvent can be recycled, and the kettle is the product; the vacuum distillation conditions are: at a pressure of 0.01 MPa and a temperature of 92° C., the reaction liquid is distilled, and the product obtained by distillation is then washed and filtered to obtain the finished product of vinyl trisbutyl ketoxime silane.

[0065] Test results of the embodiments and comparative examples: The content of the product vinyltributylonoximesilane was analyzed by gas chromatography, and the product yield was calculated based on the feeding amount of vinyltrichlorosilane.

[0066]

[0067] Wherein, M1: the feeding amount of vinyl trichlorosilane; M2: the product yield of vinyl tributylidene silane.

[0068] project purity% Yield % Example 1 97.2 86.5 Example 2 97.6 87.7 Example 3 98.0 88.4 Example 4 98.1 88.6 Example 5 98.8 89.1 Comparative Example 1 93.8 67.3 Comparative Example 2 93.1 65.2 Comparative Example 3 93.4 66.7 Comparative Example 4 92.5 58.4 .

Claims

1. A method for catalytically synthesizing vinyltributylidene oxime silane using a membrane reactor, the operating steps of which are: Step 1: Mix butanone oxime and solvent oil in a mixing kettle, then add vinyl trichlorosilane dropwise at elevated temperature, and then introduce The resin catalyst enters the external membrane reactor and reacts in the external membrane reactor. The molar ratio of vinyl trichlorosilane to butanone oxime is 1:5-8, the reaction temperature is 50-65°C, and the reaction space velocity of the mixed liquid is 0.5-3h -1 , the reaction pressure is 0.05-0.8MPa, the reaction mixture is pumped from the bottom of the reactor to the ceramic membrane filter to separate the catalyst and the reaction product, the separated product seeps out of the membrane tube in the form of clear liquid, and the flow rate of the membrane permeate is automatically controlled to be consistent with the total amount of reactants entering the reactor; Step 2: The product is separated into layers, and the upper and lower layers are separated. A neutralizing agent is added to the upper layer to neutralize it and make it alkaline. The filtrate is then filtered and distilled. In the distillation kettle, the solvent is evaporated at a certain temperature and can be recycled. The product is in the kettle; the lower layer is butanone oxime hydrochloride; The product obtained by distillation is then washed and filtered to obtain the finished product of vinyl trisbutyl ketoxime silane; The distillation conditions in step 2 are: pressure of 0.01-0.1 MPa, temperature of 92° C.-110° C., and distillation of the reaction liquid; The preparation method of the resin catalyst in step 1 is: Step a: Add 1000-1300 parts by weight of deionized water and 1-4 parts of dispersant into a reaction kettle and stir evenly; Then add 100-120 parts of styrene, 10-16 parts of ethylene glycol diacrylate, and 1-4 parts of peroxide initiator and stir evenly; After the reaction is completed, the material is discharged, washed with water, and dried to obtain an ethylene glycol-based styrene polymer; Step b: by weight, add 50-70 parts of ethylene glycol-based styrene polymer, 20-30 parts of allyl bromide, 2-5 parts of tetrabutylammonium bromide, and 220-240 parts of toluene, react at 50-60° C. for 2-5 hours, filter to remove the liquid, then add 6-11 parts of 4-mercaptopyridine and 100-140 parts of triethylamine, react at 50-70° C. for 10-20 hours, filter after the reaction, wash the solid with ethanol, and dry to obtain a resin catalyst.

2. The method for catalytically synthesizing vinyltributylidene oxime silane using a membrane reactor according to claim 1, characterized in that: The dropping conditions of step 1 are as follows: the temperature during the dropping is 20-30° C., and the dropping time is controlled at 30-60 min.

3. The method for catalytically synthesizing vinyltributylonoximesilane using a membrane reactor according to claim 1, characterized in that: The resin catalyst content in step 1 is 30-60% of the volume of the external membrane reactor.

4. The method for catalytically synthesizing vinyltributylidene oxime silane using a membrane reactor according to claim 1, characterized in that: The dispersant in step a is polyvinyl alcohol, gelatin or hydroxymethyl cellulose.

5. The method for catalytically synthesizing vinyltributylonoximesilane using a membrane reactor according to claim 1, characterized in that: The peroxide initiator in step a is selected from dicumyl peroxide, 2,5-bis(tert-butylperoxy)-2,5-dimethyl Hexane and bis(tert-butyldioxyisopropyl)benzene, benzoyl peroxide.

6. The method for catalytically synthesizing vinyltributylonoxime silane using a membrane reactor according to claim 1, characterized in that: The reaction conditions in step a are: the reaction temperature is controlled at 80-95° C., and the reaction time is controlled at 12-17 h.

7. The method for catalytically synthesizing vinyltributylonoxime silane using a membrane reactor according to claim 1, characterized in that: The neutralizing agent in step 2 is sodium hydroxide or potassium hydroxide.

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