CN114570422B - Catalyst filler for producing ketoxime silane and preparation method thereof - Google Patents
Catalyst filler for producing ketoxime silane and preparation method thereof Download PDFInfo
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- CN114570422B CN114570422B CN202111188457.6A CN202111188457A CN114570422B CN 114570422 B CN114570422 B CN 114570422B CN 202111188457 A CN202111188457 A CN 202111188457A CN 114570422 B CN114570422 B CN 114570422B
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- silanol
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- 239000000945 filler Substances 0.000 title claims abstract description 88
- 239000003054 catalyst Substances 0.000 title claims abstract description 50
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229910000077 silane Inorganic materials 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- -1 transition metal salt Chemical class 0.000 claims abstract description 22
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 claims abstract description 11
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 claims abstract description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 20
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 17
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical group Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 17
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 14
- 238000007598 dipping method Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000013329 compounding Methods 0.000 claims description 9
- 239000000413 hydrolysate Substances 0.000 claims description 9
- 238000007493 shaping process Methods 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000005470 impregnation Methods 0.000 claims description 5
- 239000000919 ceramic Substances 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 229910021426 porous silicon Inorganic materials 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 229920002554 vinyl polymer Chemical group 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 11
- 239000000758 substrate Substances 0.000 abstract description 9
- 230000009286 beneficial effect Effects 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 238000010924 continuous production Methods 0.000 abstract description 4
- 239000003431 cross linking reagent Substances 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 3
- 230000001070 adhesive effect Effects 0.000 abstract description 2
- 239000011148 porous material Substances 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract description 2
- 125000004122 cyclic group Chemical group 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 16
- 238000006460 hydrolysis reaction Methods 0.000 description 15
- 239000002904 solvent Substances 0.000 description 15
- 230000007062 hydrolysis Effects 0.000 description 13
- KTQYJQFGNYHXMB-UHFFFAOYSA-N dichloro(methyl)silicon Chemical compound C[Si](Cl)Cl KTQYJQFGNYHXMB-UHFFFAOYSA-N 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 238000006356 dehydrogenation reaction Methods 0.000 description 9
- WHIVNJATOVLWBW-PLNGDYQASA-N (nz)-n-butan-2-ylidenehydroxylamine Chemical compound CC\C(C)=N/O WHIVNJATOVLWBW-PLNGDYQASA-N 0.000 description 8
- 238000006386 neutralization reaction Methods 0.000 description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 6
- 239000005048 methyldichlorosilane Substances 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000002033 PVDF binder Substances 0.000 description 4
- 108010009736 Protein Hydrolysates Proteins 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- AIPVRBGBHQDAPX-UHFFFAOYSA-N hydroxy(methyl)silane Chemical compound C[SiH2]O AIPVRBGBHQDAPX-UHFFFAOYSA-N 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 235000019270 ammonium chloride Nutrition 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 3
- 239000004005 microsphere Substances 0.000 description 3
- CDCMMFMDDMEKSC-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine;hydrochloride Chemical group Cl.CCC(C)=NO CDCMMFMDDMEKSC-UHFFFAOYSA-N 0.000 description 3
- 150000002923 oximes Chemical class 0.000 description 3
- 125000005372 silanol group Chemical group 0.000 description 3
- 229920002379 silicone rubber Polymers 0.000 description 3
- 239000004945 silicone rubber Substances 0.000 description 3
- VOYADQIFGGIKAT-UHFFFAOYSA-N 1,3-dibutyl-4-hydroxy-2,6-dioxopyrimidine-5-carboximidamide Chemical compound CCCCn1c(O)c(C(N)=N)c(=O)n(CCCC)c1=O VOYADQIFGGIKAT-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RSYNVVGMAGNQLP-UHFFFAOYSA-N CC[SiH2]O Chemical compound CC[SiH2]O RSYNVVGMAGNQLP-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000003386 deoximation reaction Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- XEJLGPLKNMJQFR-UHFFFAOYSA-N ethoxy(hydroxy)silane Chemical compound CCO[SiH2]O XEJLGPLKNMJQFR-UHFFFAOYSA-N 0.000 description 2
- YBRNUJSXEIBYFU-UHFFFAOYSA-N hydroxy(phenyl)silane Chemical compound O[SiH2]C1=CC=CC=C1 YBRNUJSXEIBYFU-UHFFFAOYSA-N 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 239000005055 methyl trichlorosilane Substances 0.000 description 2
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 2
- 239000011265 semifinished product Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 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
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- LPUQAYUQRXPFSQ-DFWYDOINSA-M monosodium L-glutamate Chemical compound [Na+].[O-]C(=O)[C@@H](N)CCC(O)=O LPUQAYUQRXPFSQ-DFWYDOINSA-M 0.000 description 1
- 235000013923 monosodium glutamate Nutrition 0.000 description 1
- 239000004223 monosodium glutamate Substances 0.000 description 1
- DFMZGZYTSBUWAH-UHFFFAOYSA-N n-nonan-5-ylidenehydroxylamine Chemical compound CCCCC(=NO)CCCC DFMZGZYTSBUWAH-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000013500 performance material Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
- B01J31/0274—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 containing silicon
-
- 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
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/30—Loose or shaped packing elements, e.g. Raschig rings or Berl saddles, for pouring into the apparatus for mass or heat transfer
-
- 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)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
Abstract
The invention relates to the field of organosilicon cross-linking agent production, and provides a catalyst filler for producing ketoxime silane and a preparation method thereof, aiming at overcoming the defects of low production efficiency, high energy consumption and poor catalyst recycling property in the prior art. The transition metal salt catalyst is fixed on the porous filler through silanol, and the catalyst is limited, so that continuous production can be performed, and the catalyst does not need to be separated and activated, so that the production efficiency is high, the cyclic utilization is facilitated, and the energy consumption is low; the silanol not only has an adhesive effect, but also has a similar structure with the silane and ketoxime of the reaction substrate in terms of structure, has higher affinity, and is beneficial to the reaction of the substrate on the active center in the porous filler; the porous filler has a large amount of pore structures, can contain more catalyst adhesion per unit volume, and improves the catalytic efficiency.
Description
Technical Field
The invention relates to the field of organosilicon cross-linking agent production, in particular to a catalyst filler for producing ketoxime silane and a preparation method thereof.
Background
Organosilicon is industrial monosodium glutamate, and belongs to a high-new-performance material. In recent years, the domestic organosilicon industry rapidly develops, and China becomes the largest organosilicon production country worldwide, and the domestic organosilicon monomer yield accounts for more than 70% of the global yield. Room temperature curing silicone rubber is a main product category in the organic silicon industry, and deoximation type silicone rubber has wide application in various industries due to simple preparation process, stable storage and good comprehensive performance, and has dominant market position.
The crosslinking agent of the deoximation type silicone rubber mainly comprises methyl tributyl ketoxime silane, methyl tripentyl ketoxime silane and the like. The preparation method has many reports, such as methyl trichlorosilane and ketoxime, and the ketoxime is used as an acid binding agent to prepare methyl trione oxime silane through reaction; methyl trichlorosilane is adopted to react with ketoxime, and simultaneously ammonia is introduced to neutralize hydrogen chloride generated by the reaction, so that methyl trione oxime silane is obtained. The reported process methods have batch reaction methods and continuous reaction methods. However, the preparation of methyltrionoxime silane by reacting organosilicon byproduct methyldichlorosilane with ketoxime is rarely reported. The inventor's prior Chinese patent application No. 201510559641.5 discloses a preparation method of methyltributylketon oxime-based silane, which comprises the following steps: (1) Adding butanone oxime, a solvent and a catalyst into a reaction kettle, heating to 50-60 ℃, dropwise adding methyldichlorosilane into the reaction kettle under the stirring condition, adjusting the dropping speed of the methyldichlorosilane, controlling the reaction temperature to 50-60 ℃, continuously introducing nitrogen for protection in the reaction process, and the molar ratio of the methyldichlorosilane to the butanone oxime is 1:5 to 5.25; the catalyst is anhydrous nickel chloride, and the dosage of the anhydrous nickel chloride is 200-2000ppm based on the weight of the methyldichlorosilane; (2) After the dripping is finished, keeping the reaction temperature at 50-60 ℃, continuing to react for 2-4 hours, standing and layering, wherein an upper product is a methyl tributyl ketoxime silane crude product, entering a first neutralization kettle, introducing ammonia gas for neutralization, filtering, separating ammonium chloride to obtain a semi-finished product of methyl tributyl ketoxime silane, entering the semi-finished product into a first thin film evaporator, and distilling out a solvent and excessive butanone oxime to obtain a methyl tributyl ketoxime silane product; the lower product is butanone oxime hydrochloride, the butanone oxime hydrochloride enters a second neutralization kettle, a solvent is added, stirred and mixed uniformly, ammonia gas is introduced for neutralization, then filtration is carried out, after ammonium chloride is separated out, filtrate enters a second thin film evaporator, the solvent is distilled out, butanone oxime is obtained, and the butanone oxime and the solvent are recycled. The method has the defects of low production efficiency and high energy consumption, and the catalyst is required to be separated to treat the product and can be recycled after further purification and activation treatment.
Disclosure of Invention
The invention aims to overcome the defects of low production efficiency, high energy consumption and poor catalyst recycling property in the prior art, and provides a catalyst filler for producing ketoxime silane, which has high efficiency, low energy consumption and capability of fixing and continuously producing the catalyst, and a preparation method thereof.
In order to achieve the above object, the present invention adopts the following technical scheme:
a catalyst filler for preparing ketoximino silane is composed of porous filler and transition metal salt catalyst fixed to porous filler by silanol.
In the prior art, anhydrous nickel chloride is used as a catalyst, and the catalyst needs to be separated from ammonium chloride after the reaction is finished and can be used in the production of the next batch after being activated again; the catalyst filler has better compatibility with a reaction substrate, and is more favorable for catalytic reaction compared with nickel chloride in the conventional method; the transition metal salt is attached to the porous filler, so that more catalyst is attached per unit volume, the contact area is increased, more catalytic centers can be formed, and the reaction rate is accelerated; the catalyst is fixed on the porous filler, and then the porous filler is fixed in the reaction kettle, so that the aim of continuous production can be fulfilled.
A method for preparing a catalyst filler for producing ketoximosilanes, comprising the steps of:
A. preparation of silanol: trialkoxysilaneHeating in a mixed solvent of water and alcohol for reaction, and separating to obtain a hydrolysate;
B. and (3) dipping and compounding: adding transition metal salt into the hydrolysate obtained in the step A, uniformly stirring, adding porous filler, dipping, and separating porous filler dipping;
C. drying and shaping: and (C) drying the porous filler impregnated material obtained in the step (B) to obtain the catalyst filler.
The hydrolysis product with the silanol structure is obtained through the hydrolysis of trialkoxysilane, then the hydrolysis product is mixed with the transition metal salt, the transition metal salt is fixed on the porous filler through the adhesiveness of the silanol structure, so that the obtained catalyst filler has the porous structure, is beneficial to catalysis, and on the other hand, the silanol structure has better compatibility with a substrate, the infiltration effect of the substrate on the catalyst filler is better, and the catalytic reaction is facilitated; the hydrolysis reaction is carried out in an aqueous solution of alcohol, so that the progress of the hydrolysis reaction can be controlled, the completely hydrolyzed product is easy to self-polymerize to form microspheres, and transition metal salt is packed into the microspheres, which is unfavorable for the catalytic reaction, so that the complete hydrolysis of trialkoxysilane needs to be inhibited, and the hydrolysis stays in a single hydrolysis stage or a double hydrolysis stage, thereby not only providing adhesive performance, but also not inhibiting catalytic activity.
Preferably, in step a, R is selected from methyl, vinyl or phenyl; r is R 1 、R 2 、R 3 Each of which is phenyl or alkyl having 1 to 5 carbon atoms.
Preferably, in the step A, the mass ratio of water, alcohol and trialkoxysilane in the reaction system is: alcohol: trialkoxysilane = 1: 5-20: 5-20; the heating temperature is 25-60 ℃; the reaction time is 1-24 hr.
Preferably, in step B, the transition metal salt is nickel chloride; the porous filler is at least one of porous alumina ceramic filler, porous silicon carbide ceramic filler and porous silicon nitride ceramic filler; the porosity of the porous filler is more than or equal to 60%; the mass ratio of the hydrolysate to the transition metal salt is 100:1-10.
Preferably, in step B, the soaking time is 1 to 24hr.
Preferably, in step C, the drying temperature is 50 to 200 ℃.
By adopting the technical scheme, the invention has the following beneficial effects: the transition metal salt catalyst is fixed on the porous filler through silanol, and the catalyst is limited, so that continuous production can be performed, and separation and activation of the catalyst are not needed; the silanol not only has the effect of adhesion, but also has a similar structure with the silane and ketoxime of the reaction substrate in terms of structure, has higher affinity, reduces repulsive force on a contact surface, is beneficial to infiltration of reactants to the catalyst filler and is beneficial to reaction of the substrate on the active center in the porous filler; the porous filler has a large amount of pore structures, can contain more catalyst adhesion per unit volume, and improves the catalytic efficiency.
Detailed Description
The invention is further described below in connection with the following detailed description.
A catalyst filler for preparing ketoximino silane is composed of porous filler and transition metal salt catalyst fixed to porous filler by silanol.
Example 1
A. Preparation of alkyl silanol: adding 100 parts of methanol and 20 parts of water into a hydrolysis kettle, dropwise adding 100 parts of methyltrimethoxysilane, keeping the dropwise adding temperature at 25 ℃, keeping the temperature at 25 ℃ for 24hr after the dropwise adding is finished, and evaporating the solvent to obtain a methyl silanol mixture; B. and (3) dipping and compounding: placing the methyl silanol mixture obtained in the step A into an impregnating tank, adding 1 part of nickel chloride, uniformly stirring, adding porous alumina ceramic filler with the porosity of 65% until the porous alumina ceramic filler is just completely immersed by the hydrolysate, and taking out porous filler impregnant after 1 hour of impregnation;
C. drying and shaping: and B, putting the porous filler impregnated material obtained in the step B into a dryer, and drying at 50 ℃ to obtain the filler loaded with the dehydrogenation catalyst.
Example 2
A. Preparation of aryl silanol: adding 100 parts of methanol and 5 parts of water into a hydrolysis kettle, dropwise adding 100 parts of phenyltriethoxysilane, keeping the dropwise adding temperature at 60 ℃, keeping the temperature at 60 ℃ after the dropwise adding is finished, reacting for 1hr, and evaporating the solvent to obtain a phenylsilanol mixture; B. and (3) dipping and compounding: placing the phenylsilanol mixture obtained in the step A into an impregnating tank, adding 10 parts of nickel chloride, uniformly stirring, adding porous alumina ceramic filler with the porosity of 70% until the porous alumina ceramic filler is just completely immersed by the hydrolysate, and taking out porous filler impregnant after 24 hours of impregnation;
C. drying and shaping: and B, putting the porous filler impregnated material obtained in the step B into a dryer, and drying at 200 ℃ to obtain the filler loaded with the dehydrogenation catalyst.
Example 3
A. Preparation of alkenyl silanol: adding 100 parts of methanol and 10 parts of water into a hydrolysis kettle, dropwise adding 80 parts of vinyl triethoxysilane, keeping the dropwise adding temperature at 40 ℃, keeping the temperature at 40 ℃ after the dropwise adding is finished, reacting for 11hr, and evaporating the solvent to obtain an ethyl silanol mixture; B. and (3) dipping and compounding: placing the ethyl silanol mixture obtained in the step A into an impregnating tank, adding 6 parts of nickel chloride, uniformly stirring, adding porous alumina ceramic filler with the porosity of 75% until the porous alumina ceramic filler is just completely immersed by the hydrolysate, and taking out porous filler impregnant after 8 hours of impregnation;
C. drying and shaping: and B, putting the porous filler impregnated material obtained in the step B into a dryer, and drying at 150 ℃ to obtain the filler loaded with the dehydrogenation catalyst.
Example 4
A. Preparation of alkoxy silanol: adding 100 parts of methanol and 10 parts of water into a hydrolysis kettle, dropwise adding 60 parts of tetraethoxysilane, keeping the dropwise adding temperature at 50 ℃, keeping the temperature at 50 ℃ after the dropwise adding is finished, reacting for 5hr, and evaporating the solvent to obtain an ethoxysilanol mixture; B. and (3) dipping and compounding: placing the ethoxysilanol mixture obtained in the step A into an impregnating tank, adding 5 parts of nickel chloride, uniformly stirring, adding porous alumina ceramic filler with the porosity of 70% until the porous alumina ceramic filler is just completely immersed by the hydrolysate, and taking out porous filler impregnant after the porous alumina ceramic filler is immersed for 6 hours;
C. drying and shaping: and B, putting the porous filler impregnated material obtained in the step B into a dryer, and drying at 100 ℃ to obtain the filler loaded with the dehydrogenation catalyst.
Comparative example 1
Comparative example 1 in comparison with example 1, polyvinylidene fluoride PVDF was used instead of silanol
A. And (3) dipping and compounding: adding 100 parts of N-methylpyrrolidone and 20 parts of water into an impregnating tank, adding 100 parts of PVDF, adding 1 part of nickel chloride, uniformly stirring to obtain impregnating solution, adding porous alumina ceramic filler with the porosity of 65% until the porous alumina ceramic filler is just completely immersed by the impregnating solution, and taking out porous filler impregnated matter after 1 hour of impregnation;
B. drying and shaping: and B, putting the porous filler impregnated material obtained in the step B into a dryer, and drying at 50 ℃ to obtain the filler loaded with the dehydrogenation catalyst.
Comparative example 2
Comparative example 2 in comparison with example 1, comparative example 2 preparation of alkylsilanol in a system without addition of methanol and having a pH of 5
A. Preparation of alkyl silanol: 120 parts of hydrochloric acid aqueous solution with the pH value of 5 is added into a hydrolysis kettle, 100 parts of methyltrimethoxysilane is slowly added dropwise, the dropwise adding temperature is kept at 25 ℃, the reaction is carried out for 24 hours at the temperature of 25 ℃ after the dropwise adding is finished, and the solvent is distilled off to obtain hydrolysate impregnating solution;
B. and (3) dipping and compounding: placing the hydrolysate impregnating solution obtained in the step A into an impregnating tank, adding 1 part of nickel chloride, uniformly stirring, adding porous alumina ceramic filler with the porosity of 65% until the porous alumina ceramic filler is just completely immersed by the hydrolysate impregnating solution, and taking out porous filler impregnating matter after impregnating for 1 hour;
C. drying and shaping: and B, putting the porous filler impregnated material obtained in the step B into a dryer, and drying at 50 ℃ to obtain the filler loaded with the dehydrogenation catalyst.
Comparative example 3
Comparative example 3 preparation of alkylsilanol in comparison with comparative example 1, comparative example 3 uses the same parts by mass of conventional alumina ceramic instead of porous alumina ceramic a: adding 100 parts of methanol and 20 parts of water into a hydrolysis kettle, dropwise adding 100 parts of methyltrimethoxysilane, keeping the dropwise adding temperature at 25 ℃, keeping the temperature at 25 ℃ for 24hr after the dropwise adding is finished, and evaporating the solvent to obtain a methyl silanol mixture; B. and (3) dipping and compounding: placing the methyl silanol mixture obtained in the step A into an impregnating tank, adding 1 part of nickel chloride, uniformly stirring, adding 10 parts of alumina ceramic filler, and taking out a porous filler impregnated material after impregnating for 1 hour;
C. drying and shaping: and B, putting the porous filler impregnated material obtained in the step B into a dryer, and drying at 50 ℃ to obtain the filler loaded with the dehydrogenation catalyst.
Filling the fillers of the examples 1-4 and the comparative examples 1-3, which are loaded with the dehydrogenation catalyst, into a 6000L reactor, adding 3000L solvent oil into the 6000L reactor, and starting a circulating pump to ensure that the materials in the reactor are 100m 3 The flow rate of/hr passes through the condenser (the temperature of the outlet material of the condenser is controlled to be 20-40 ℃ and the temperature in the reactor is kept at 60 ℃) and then enters the reactor, then methyl dichlorosilane with the feeding rate of 300kg/hr, butanone oxime with the feeding rate of 1190kg/hr and solvent oil with the feeding rate of 800kg/hr are continuously added into a feeder of the reactor, after preliminary reaction in the feeder, the solvent oil enters the reactor for further reaction, then flows out of the reactor from the outlet of the reactor, and hydrogen generated by the reaction escapes from the top of the reactor.
The material flowing out of the reactor outlet was stratified. The main components of the upper layer are methyl tributyl ketoxime silane and solvent oil, and the methyl tributyl ketoxime silane product is obtained after ammonia gas is introduced for neutralization, filtration and distillation. The lower layer is butanone oxime hydrochloride, after neutralization by ammonia water, the oil layer is separated and rectified to obtain butanone oxime, and the butanone oxime is returned to the reaction process for use.
After the reactor distillate materials which are continuously fed and discharged for 48 hours are layered, the upper product-containing oil layer is detected, and the purity of the methyltributyloxidoxysilane obtained after the subsequent neutralization and distillation and the content of the methyltributyloxidoxysilane and the content of the methyldiacetone oxime hydrosilicon in each reactor are shown in the following table.
| Example 1 | Example 2 | Example 3 | Example 4 | Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| Methyl tributylketoximino silane content (%) | 48.1 | 51.2 | 47.6 | 49.5 | 31.6 | 40.4 | 22.8 |
| Methyl diacetone oximino hydrosilicon content (%) | 0 | 0 | 0 | 0 | 18.2 | 11.2 | 28.1 |
| Purity of methyltributylketonoxime silane (%) | 98.2 | 98.1 | 97.9 | 98.6 | 73.4 | 83.3 | 55.6 |
From the above table, the reaction catalyzed by the supported dehydrogenation catalyst of examples 1 to 4 can also completely convert methyl dibutyl ketoxime silica and methyl dichloro silica into methyl tributylketoxime silane after 48hr of continuous feeding and discharging, and the purity of the final product system is still higher after post-treatment, which indicates that the catalyst filler of the invention has good catalytic efficiency and catalytic activity and can completely meet the requirement of continuous production. In comparative example 1, the presence of a portion of methyldiacetone oximino hydrosilicon was not dehydrogenated, and the lower catalytic efficiency was seen to be probably due to the limited compatibility of the substrate with PVDF, which is detrimental to the reaction of the substrate on the active center when entering the porous filler; the acidic system used in comparative example 2 prepares silanol, because silanol can be completely hydrolyzed under the acidic system, and methyl silicone triol is easy to self-polymerize to form microsphere structure, nickel chloride is difficult to play a catalytic role after partial nickel chloride is coated, resulting in reduced active center of catalyst filler and reduced catalytic efficiency; in comparative example 3, alumina ceramic having no porous structure has less nickel chloride supported, and no active center in the alumina ceramic has only a small amount of nickel chloride attached to the surface to perform the catalytic function, so that the catalytic efficiency is low, and a large amount of raw materials remain.
Claims (5)
1. A method for preparing a catalyst filler for producing ketoximosilanes, comprising the steps of:
A. preparation of silanol: trialkoxysilaneHeating in a mixed solvent of water and alcohol for reaction, and separating to obtain a hydrolysate; the mass ratio of water, alcohol and trialkoxysilane in the reaction system is as follows: alcohol: trialkoxysilane = 1: 5-20: 5-20; the heating temperature is 25-60 ℃; the reaction time is 1-24 hr;
B. and (3) dipping and compounding: adding transition metal salt into the hydrolysate obtained in the step A, and uniformly stirring, wherein the transition metal salt is nickel chloride; adding porous filler, dipping, and separating porous filler dipping matters;
C. drying and shaping: and (C) drying the porous filler impregnated material obtained in the step (B) to obtain the catalyst filler.
2. The method for preparing a catalyst filler for ketoximosilane production according to claim 1, wherein in step a, R is selected from methyl, vinyl or phenyl; r is R 1 、R 2 、R 3 Each of which is phenyl or alkyl having 1 to 5 carbon atoms.
3. The method for preparing a catalyst filler for producing ketoxime silane according to claim 1 wherein in step B, the porous filler is at least one of porous alumina ceramic filler, porous silicon carbide ceramic filler and porous silicon nitride ceramic filler; the porosity of the porous filler is more than or equal to 60%; the mass ratio of the hydrolysate to the transition metal salt is 100:1-10.
4. A method for preparing a catalyst filler for the production of ketoximosilane as defined in claim 1 or 3, wherein in said step B, the impregnation time is 1 to 24hr.
5. The method for preparing a catalyst filler for ketoximosilane production according to claim 1, wherein in step C, the drying temperature is 50 to 200 ℃.
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Citations (4)
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| CN102584887A (en) * | 2011-12-14 | 2012-07-18 | 上海交通大学 | Preparation method of novel epoxy group functionalized macrocyclic oligomeric silsesquioxane |
| JP2015052108A (en) * | 2013-08-07 | 2015-03-19 | 古河電気工業株式会社 | Heat-resistant silane crosslinked resin molded article and production method thereof, heat-resistant silane crosslinkable resin composition and production method thereof, heat-resistant product using heat-resistant silane crosslinked resin molded article and inorganic filler mixed with silane coupling agent |
| CN111514897A (en) * | 2020-05-11 | 2020-08-11 | 泰州禾益新材料科技有限公司 | Application of high-dispersion carbon-doped mesoporous silicon nanotube nickel-based catalyst in carbon dioxide methanation reaction |
| CN113004231A (en) * | 2021-03-01 | 2021-06-22 | 安徽金轩科技有限公司 | Preparation method for producing furan ammonium salt by using 2-acetylfuran |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102584887A (en) * | 2011-12-14 | 2012-07-18 | 上海交通大学 | Preparation method of novel epoxy group functionalized macrocyclic oligomeric silsesquioxane |
| JP2015052108A (en) * | 2013-08-07 | 2015-03-19 | 古河電気工業株式会社 | Heat-resistant silane crosslinked resin molded article and production method thereof, heat-resistant silane crosslinkable resin composition and production method thereof, heat-resistant product using heat-resistant silane crosslinked resin molded article and inorganic filler mixed with silane coupling agent |
| CN111514897A (en) * | 2020-05-11 | 2020-08-11 | 泰州禾益新材料科技有限公司 | Application of high-dispersion carbon-doped mesoporous silicon nanotube nickel-based catalyst in carbon dioxide methanation reaction |
| CN113004231A (en) * | 2021-03-01 | 2021-06-22 | 安徽金轩科技有限公司 | Preparation method for producing furan ammonium salt by using 2-acetylfuran |
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