CN111662319A - Preparation method of low-color 3-isocyanatopropyl trimethoxy silane - Google Patents
Preparation method of low-color 3-isocyanatopropyl trimethoxy silane Download PDFInfo
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- CN111662319A CN111662319A CN202010728271.4A CN202010728271A CN111662319A CN 111662319 A CN111662319 A CN 111662319A CN 202010728271 A CN202010728271 A CN 202010728271A CN 111662319 A CN111662319 A CN 111662319A
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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 System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/10—Magnesium; Oxides or hydroxides thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
-
- 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 System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Abstract
The invention provides a preparation method of 3-isocyanate propyl trimethoxy silane with low color, which comprises the following steps of enabling a raw material 3-trimethoxy silane methyl carbamate to enter from the middle part of a tower reactor with a catalyst at the bottom, and enabling the raw material to react with the catalyst; after the reaction is finished, the discharging material at the top of the reactor is an isocyanate silane product, and the discharging material at the bottom of the reactor is residual liquid which can be mixed with fresh raw materials and enter the reactor again for the re-cracking reaction. The bottom discharge of the reactor of the invention basically has no residue, and the conversion rate of the raw materials can reach 100 percent through the circulation reaction of the bed charge; the selected reaction raw materials are non-hazardous chemicals, the reaction is stable and controllable, no hazardous operation is caused, and particularly, the reaction can be continuously operated; the use of solvent is avoided, the steps of solvent separation and recovery are omitted, and the method conforms to the concept of environmental protection.
Description
Technical Field
The invention relates to the field of organic silicon chemicals, and particularly relates to a preparation method of 3-isocyanatopropyl trimethoxy silane.
Background
The 3-isocyanate propyl trimethoxy silane is a silane coupling agent containing NCO groups, is an excellent glass fiber treating agent, can improve the mechanical strength, the electrical property and the ageing resistance of a composite material, and is widely applied to the glass fiber surface treatment of glass fiber reinforced plastics such as polyethylene crosslinking, unsaturated resin, polyethylene, polypropylene resin and the like; can also be used as adhesive for surface moisture-proof treatment of electronic devices or surface treatment of inorganic silicon fillers.
The currently industrialized methods for preparing isocyanatosilanes are mainly the phosgene (triphosgene) method, the isocyanic acid method and the pyrolysis method.
In patent CN101307067, phosgene and amine are reacted in an inert solvent to generate an isocyanate group, in patent CN101492468, triphosgene is reacted with trialkoxysilanylamine at a low temperature to prepare trialkoxyisocyanate, the basic principles of the phosgene method and the triphosgene method are consistent, the triphosgene method improves the safety performance of the phosgene method to a great extent, but if the triphosgene is exposed to water or heated during operation, the phosgene still generates phosgene, so that safety hazards still exist, and the industrial equipment is easily corroded by a reaction byproduct, namely HCl.
In patent CN104262384, isocyanato silane is directly generated by using NaNCO and chlorosilane as raw materials, and the method has few reaction steps and is easy to operate. NaNCO is solid, a polar solvent needs to be added, but the NaNCO is poor in solubility, so that the reaction time is long, and the yield is low.
Patent CN101307067 uses carbamate silane as raw material, and generates isocyanate group by pyrolysis of carbamate group, and the byproduct is methanol. The process is a one-pot high-temperature cracking process, can greatly improve the safety problem of the preparation process, but the process disclosed by the patent does not use a catalyst, is easy to polymerize a raw material of carbamate silane by heating at high temperature for a long time, has serious coking phenomenon and causes low yield. Patent CN207259419 proposes to replace kettle heating part with tubular one to relieve the problem of raw material coking, but because no catalyst can only treat gas phase material, the processing capacity is low and the industrialization possibility is low.
In conclusion, the pyrolysis method has the advantages of high safety, short reaction time and no waste salt, and is well applied in industry, but the main bottleneck of the method is how to rapidly crack the raw material of the carbamate silane, so that the long-time high-temperature heating polymerization coking is avoided, the product yield is improved, and the generation of residues is reduced.
Disclosure of Invention
Aiming at the defects of the existing pyrolysis method for preparing the isocyanato silane, the invention provides a preparation method of 3-isocyanato propyl trimethoxy silane, which has the advantages of high cracking rate, less residue and low color.
The purpose of the invention is realized by the following technical scheme:
a preparation method of low-color 3-isocyanate propyl trimethoxy silane is disclosed, wherein the structural formula of the low-color 3-isocyanate propyl trimethoxy silane is as follows:
the preparation method comprises the following steps:
feeding a raw material 3-trimethoxy silane methyl carbamate from the middle part of a tower reactor with a catalyst at the bottom, wherein the raw material reacts with the catalyst;
after the reaction is finished, the discharging material at the top of the reactor is an isocyanate silane product, and the discharging material at the bottom of the reactor is residual liquid which can be mixed with fresh raw materials and enter the reactor again for the re-cracking reaction.
The catalyst is a metal-loaded catalyst and is prepared by loading an active component onto a carrier, wherein the active component is a metal oxide, and the carrier is selected from a molecular sieve and gamma-Al2O3Or activated carbon, the activity ofThe addition amount of the components is as follows: the mass ratio of the carrier to the carrier is 8-15%.
The active components are as follows: any one or combination of more of zinc oxide, magnesium oxide, titanium oxide or zirconium oxide.
The preferred support for the catalyst is a silica alumina molecular sieve.
In the method, the reaction temperature is controlled to be 220-260 ℃, and the space velocity of the raw materials is 0.05-1 g/h/g/cat.
Furthermore, the reaction temperature is preferably 220-240 ℃, and the space velocity of the raw material is preferably 0.15-0.25 g/h/g/cat.
The reactor in the above steps is divided into two sections: the upper section is used for placing rectification packing, the lower section is used for placing the catalyst, the raw materials enter from the middle part of the reactor and then are cracked through a catalyst bed layer, product steam upwards passes through a rectification layer to be refined to obtain a product and methanol, and the methanol can be removed by utilizing the boiling point difference to obtain a refined product.
The method is characterized in that a raw material 3-trimethoxy silane methyl carbamate enters from the middle part of a tower reactor filled with a catalyst, and specifically comprises the following steps: the raw materials pass through a raw material pump and enter from the middle part of a tower reactor filled with the catalyst by accurately controlling the flow rate through a mass flow controller. The range of flow rates is based on space velocity, 0.05-1g/h/g/cat, and once the catalyst weight is determined, the feed flow rate is determined.
The structural formula of the 3-trimethoxysilylcarbamate is as follows:
the preparation method of the catalyst comprises the following steps:
preparing a solution from the carrier serving as a matrix and a proper amount of deionized water, maintaining stirring until complete impregnation, standing and aging;
and then carrying out suction filtration, washing a filter cake by using deionized water, repeating the steps until no nitrate ions exist, drying the filter cake, crushing the filter cake, uniformly mixing the filter cake with a binder and a nitric acid aqueous solution, stirring the mixture into a mud shape, extruding the mud into a strip shape, drying the extruded strip shape, and roasting the dried strip shape in a muffle furnace to obtain the required catalyst.
Specifically, the carrier is a silicon-aluminum molecular sieve, the silicon-aluminum ratio of the molecular sieve is 25-40, and the specific surface area is 300-500 m2The pore volume is 0.2-0.4 ml/g.
The metal nitrate is one or more of zinc nitrate, magnesium nitrate, titanium nitrate and zirconium nitrate.
And drying the filter cake in an oven at 120-140 ℃, then crushing the filter cake, uniformly mixing the filter cake with a binder and a nitric acid aqueous solution, blending the mixture into a mud shape, extruding the mud into a cylindrical strip shape by using a strip extruding machine, drying the dried filter cake in the oven at 120-140 ℃, then placing the dried filter cake in a muffle furnace at 400-600 ℃ for roasting to obtain the catalyst, and finally shearing the catalyst into 2-5 mm for later use. The adhesive is gamma-Al2O3Powder, gamma-Al2O3The mass ratio of the powder to the carrier is 10-25%, and the nitric acid aqueous solution is a dilute nitric acid aqueous solution with the mass percentage of 5%.
The reaction equation of the present invention is as follows:
the invention has the following beneficial effects:
(1) the tower reactor is divided into two sections, the lower section of the tower reactor is used for reaction, the upper section of the tower reactor is used for separation and refining, the product can be obtained by discharging from the top of the tower reactor, the reaction conversion rate and the selectivity are high, and the color of the obtained product is light; the discharged material at the bottom of the reactor basically has no residue, and the conversion rate of the raw material can reach 100 percent through the circulation reaction of the bottom material;
(2) the reaction raw materials selected by the invention are non-hazardous chemicals, the reaction is stable and controllable, no hazardous operation is caused, and particularly, the reaction can be continuously operated;
(3) the method avoids the use of a solvent, omits the steps of solvent separation and recovery, and accords with the concept of environmental protection.
Detailed Description
Example 1: influence of different catalyst systems
Weighing 100g of gamma-Al2O3(5 parts) as a reference, viscosityMixture of gamma-Al2O315g (5 parts), weighing metal salts with different weights (shown in table 1) according to 4 different mass proportions, preparing the metal salts (in zinc nitrate, magnesium nitrate, titanium nitrate and zirconium nitrate) into solutions in proper amounts of deionized water, maintaining stirring until complete impregnation, standing and aging; then, carrying out suction filtration, washing a filter cake by using deionized water, repeating the steps until no nitrate ions exist, drying the filter cake in an oven at 120-140 ℃, crushing the filter cake and a binder gamma-Al2O3Uniformly mixing the powder and a 5% wtHNO3 aqueous solution, stirring into a mud shape, extruding into a cylindrical strip shape by using a strip extruding machine, drying in an oven at 120-140 ℃, then placing in a muffle furnace at 400-600 ℃ for roasting to obtain the required catalyst, and finally shearing into 2-5 mm to prepare the catalyst for later use.
The raw material 3-trimethoxy silane methyl carbamate enters from the middle part of the tower reactor at the flow speed controlled by a metering pump, the space velocity of the raw material is 0.4g/h/g/cat, the reaction temperature is 220 ℃, the discharge at the bottom of the reactor is residual liquid, the residual liquid can be mixed with fresh raw materials and then enters the reactor for re-cracking reaction, and the specific results are as follows:
table 1 effect of different catalysts on the reaction effect.
As can be seen from Table 1, the catalyst system of the present invention has a yield of more than 76% under the initial reaction conditions, which indicates that the prepared catalyst has better catalytic activity, wherein the catalyst activity of the active components of zinc oxide, titanium oxide and the combination thereof is better, and the catalyst activity of the active component of zirconium oxide is slightly worse. Meanwhile, it can also be seen that the reaction conditions are not optimal and need to be further optimized.
Example 2: influence of reaction temperature
The catalyst preparation process and the working principle of the embodiment are the same as those of the embodiment 1, and the differences are that: the results of the reactions at different reaction temperatures are shown in Table 2. Other conditions are as follows: the catalyst # of example 5 was used with a feed space velocity of 0.4 g/h/g/cat.
Table 2 effect of different reaction temperatures on the reaction effect.
The reaction temperature has obvious influence on the activity of reaction raw materials and the improvement of reaction rate, when the temperature is too low, the reaction can not be rapidly carried out, the temperature rise can cause the product to polymerize by itself to produce dimer and polymer, and by-products are greatly increased. When the temperature is between 220-260 deg.c, the conversion rate is raised in the temperature range, while the yield reaches the peak value at 230 deg.c, and the yield is raised continuously, so that the yield is reduced continuously, and in the comprehensive consideration of conversion rate and yield, 220-260 deg.c is proper reaction temperature and 230 deg.c is the most preferable reaction temperature.
Example 3: influence of the space velocity of the feed
The catalyst preparation process and the working principle of the embodiment are the same as those of the embodiment 1, and the differences are that: the results of the reactions at different space velocities are shown in Table 3. Other conditions are as follows: the catalyst of example 5# was used, the reaction temperature was 230 ℃.
Table 3 effect of different feed space velocities on reaction effect.
The space velocity can reflect the retention time of the material in the reactor, and different catalyst systems have matched material space velocities. As can be seen from Table 3, a suitable space velocity for the 5# catalyst of example 1 is 0.3 g/h/g/cat.
The tower reactor adopted by the embodiment of the invention comprises an upper section, a lower section and a middle part between the upper section and the lower section, wherein the upper section and the lower section are communicated, a rectification filler is placed in the upper section, a catalyst is placed in the lower section, a material inlet is arranged in the middle part, the middle part is communicated with the lower section, so that a raw material 3-trimethoxy silane methyl carbamate can enter the lower section from the middle part, the middle part is communicated with the upper section, and the tower reactor is specifically designed into a structure which can be used for gas circulation but can not pass through solids, such as: the baffle structure with a plurality of micropores can ensure that the product steam at the lower section can reach the rectification layer upwards, and the rectification packing in the upper section can not fall off. The method comprises the following steps that a raw material 3-trimethoxy silane methyl carbamate enters from the middle of a tower reactor and then reaches the lower section of the tower reactor, the top of the upper section of the tower reactor is used for discharging an isocyanate silane product and methanol, the product 3-isocyanate propyl trimethoxy silane is obtained through a primary condenser connected with the top of the upper section of the tower reactor, and the methanol is obtained through a secondary condenser connected with the primary condenser.
The operation pressure of the tower reactor is normal pressure or micro negative pressure: -0.05 to-0.03 MPa. The operation temperature of a catalyst layer at the lower section of the tower reactor is 220-260 ℃, and the operation temperature of a rectifying layer at the upper section of the tower reactor is 120-150 ℃.
The above description is provided for further details of the technical solutions according to the preferred embodiments of the present invention, and it should not be understood that the embodiments of the present invention are limited to the above description, and those skilled in the art of the technical field of the present invention should be considered as falling within the protection scope of the present invention by simple deduction and replacement without departing from the concept of the present invention.
Claims (10)
1. A preparation method of low-color 3-isocyanate propyl trimethoxy silane is disclosed, wherein the structural formula of the low-color 3-isocyanate propyl trimethoxy silane is as follows:
the preparation method comprises the following steps:
feeding a raw material 3-trimethoxy silane methyl carbamate from the middle part of a tower reactor with a catalyst at the bottom, wherein the raw material reacts with the catalyst;
after the reaction is finished, the discharging material at the top of the reactor is an isocyanate silane product, and the discharging material at the bottom of the reactor is residual liquid which can be mixed with fresh raw materials and enter the reactor again for the re-cracking reaction.
2. The method of claim 1, wherein: the catalyst is a metal-loaded catalyst and is prepared by loading an active component onto a carrier, wherein the active component is a metal oxide, and the carrier is selected from a molecular sieve and gamma-Al2O3Or one of the active carbon, the addition amount of the active components is as follows: the mass ratio of the carrier to the mass thereof is 8-15%.
3. The method of claim 2, wherein: the active components are as follows: any one or combination of more of zinc oxide, magnesium oxide, titanium oxide or zirconium oxide.
4. The method of claim 2, wherein: the carrier of the catalyst is a silicon-aluminum molecular sieve.
5. The method of claim 1, wherein: the reaction temperature is controlled to be 220-260 ℃, and the air speed of the raw material is 0.05-1 g/h/g/cat.
6. The method of claim 5, wherein: the reaction temperature is 220-240 ℃, and the space velocity of the raw materials is 0.15-0.25 g/h/g/cat.
7. The method of claim 1, wherein: the reactor is divided into two sections: the upper section is used for placing rectification packing, the lower section is used for placing the catalyst, the raw materials enter from the middle part of the reactor and then are cracked through a catalyst bed layer, product steam upwards passes through a rectification layer to be refined to obtain a product and methanol, and the methanol is removed by utilizing the boiling point difference to obtain a refined product.
8. The method of claim 1, wherein: the structural formula of the 3-trimethoxysilylcarbamate is as follows:
9. a method for preparing the catalyst of claim 2, comprising the steps of:
s1, preparing a solution from the carrier and deionized water, stirring until the solution is completely impregnated, standing and aging;
s2, performing suction filtration and washing a filter cake with deionized water;
and S3, repeating S2 until no nitrate ions exist, drying and crushing the filter cake, uniformly mixing the filter cake with the adhesive and the nitric acid aqueous solution, stirring the mixture into a mud shape, drying the mud, and roasting the mud in a muffle furnace to obtain the required catalyst.
10. The preparation method of claim 9, wherein the carrier is a silicon-aluminum molecular sieve, the silicon-aluminum molecular sieve has a silicon-aluminum ratio of 25-40 and a specific surface area of 300-500 m2The pore volume is 0.2-0.4 ml/g; the metal nitrate is one or more of zinc nitrate, magnesium nitrate, titanium nitrate and zirconium nitrate; drying the filter cake in an oven at 120-140 ℃ and then crushing, wherein the adhesive is gamma-Al2O3The mass ratio of the powder to the carrier is 10-25%, the nitric acid aqueous solution is a dilute nitric acid aqueous solution with the mass percentage of 5%, the temperature of the oven is 120-140 ℃, and the temperature of the muffle furnace is 400-600 ℃.
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| CN109534999A (en) * | 2018-11-30 | 2019-03-29 | 太原理工大学 | A kind of synthesis technology and device of dimethyl carbonate |
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