CN103342715B - Preparation method of aminopropyl-containing organic oximido-silicon compound - Google Patents
Preparation method of aminopropyl-containing organic oximido-silicon compound Download PDFInfo
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- CN103342715B CN103342715B CN201310318551.8A CN201310318551A CN103342715B CN 103342715 B CN103342715 B CN 103342715B CN 201310318551 A CN201310318551 A CN 201310318551A CN 103342715 B CN103342715 B CN 103342715B
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Abstract
The invention relates to a preparation method of an aminopropyl-containing organic oximido-silicon compound, which comprises the following steps: mixing chloropropyl chlorosilane and organic amine, and reacting in a pressure reaction vessel to obtain aminopropyl-containing aminosilane; and reacting the aminopropyl-containing aminosilane used as a raw material with organic oxime to obtain the aminopropyl organic oximido-silane, wherein R is C1-C20 straight-chain, branch-chain or cyclic saturated or unsaturated alkane, aromatic hydrocarbon or any other organic hydrocarbon containing other substituent groups; R1 is C1-C6 alkane, comprising methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tertiary butyl groups; R2 and R3 are identical or different C0-C10 alkanes; and n and a are respectively a whole number ranging from 0 to 2. The method for preparing poly-oximido aminosilane prevents the product obtained by substituent group displacement of alkoxy silane from containing alkoxy groups, and avoids the problem of poor stability due to the alkoxy group in the preparation process of the oxime-removing room-curing organosilicon system.
Description
Technical field
The present invention relates to a kind of preparation method containing the organic oximino silane of aminopropyl, this hydroxyimino organosilicon compounds can as linking agent, coupling agent and additive, for seal gum or other industry.
Background technology
Hydroxyimino organosilicon compounds can as linking agent, and coupling agent and functional additive are applied to the curing cross-linked of organosilicon material, or the improvement of other performances and adjustment; Wherein room temperature curing type organosilicon material is at room temperature by under being exposed to air, is solidified into elastomerics with the water cross-linking reaction in air, and when exclusion of water, storage-stable.This series products is generally by mixing a certain proportion of diorganopolysiloxaneand and linking agent realizes; This organosilicon cross-linking agent has multiple hydrolysable group, such as alkoxyl group, oximido, amido, carboxyl etc.In addition, in a lot of situation, according to specific performance need, be necessary to add there is special organic group, and there are the silicoorganic compound of hydrolysable group;
Organic oximino silane is generally reacted by corresponding organochlorosilane and corresponding oxime and obtained, and in US3189576, such as described the reaction of a kind of chlorosilane or chlorine siloxanes and oxime, pyridine is used as neutralizing agent; US4918209 describes the synthetic method using ammonia as neutralizing agent; And in US4400527, US4380660, organic oxime, except being as except reactant, also plays the effect of acid absorber simultaneously;
The solidified nature of the excellence that aminosilane provides due to it and cementability, and be widely used in comprise room temperature vulcanization organosilicon system a lot of fields in the middle of, wherein just comprise amine propyl-triethoxysilicane and amine propyl trimethoxy silicane; And for the organic oximino silane containing amino, although it is proved can provide more excellent performance and stability in de-oxime type self-vulcanizing organosilicon systems, such as described in patent EP0760830, the uncertainty that the complicacy prepared due to it and product form, is not widely used;
In one is attempted, US470587 describe by aminopropyl trimethoxysilane and methyl ethyl ketone oxime in toluene reaction system, prepare corresponding oximido compound by heating.But due to the requirement of its heat-up time and temperature, expect high reaction conversion ratio, the quality of product is difficult to ensure; Similar, the preparation method of by product is removed under Chinese patent CN 102532186-A have employed the condition of decompression, improve reaction conversion ratio, reduce the generation of by product, but its reaction is also difficult to the alkoxyl group in raw material thoroughly to remove, and the product obtained one rolls into a ball formed mixture by different substituents often;
So this contains the method for amino oximido organosilane with regard to requiring a kind of preparation of forgoing above-mentioned drawback.
Summary of the invention
The object of the invention is to propose a kind of preparation method containing the organic oximino silane of amine propyl group, the method should can be used for the amino oximino silane of preparation high purity, and avoids introducing alkoxy grp to enter organosilicon systems;
In order to realize object of the present invention, following technical scheme is proposed:
A preparation method for organic oximido silicon compound containing amine propyl group, comprises step:
1) chloropropyl chlorosilane is mixed with organic amine, add acid-acceptor and react, and obtain the aminosilane containing amine propyl group;
2) with this kind of amine propyl amino silane for raw material, carry out reacting with organic oxime and obtain this kind of organic oximino silane of amine propyl group;
Described chloropropyl organochlorosilane is the compound that an available following molecular formula represents:
ClC
3H
6SiR
nCl
(3-n)；
Wherein, the saturated or unsaturated alkyl of the straight chain that R is made up of 1 to 20 carbon, side chain or ring-type, aryl, or this kind of alkyl containing other substituted radicals, aryl; N is the integer of 0 to 2.
Described organic amine is the compound that an available following molecular formula represents:
R
1 aH
（3-a）N；
Wherein, R
1the alkane be made up of 1 to 6 carbon; A is the integer of 0 to 2.
Described organic oxime is the compound that an available following molecular formula represents:
R
2R
3C=NOH；
Wherein, R
2, R
3the identical or different alkane be made up of 1 to 10 carbon;
Described acid-acceptor is alkaline matter, comprise organic amine, basic metal and oxide compound thereof or oxyhydroxide, alkaline earth metal oxide or oxyhydroxide, nitrogenous compound, in its add-on and chloropropyl organochlorosilane, the mol ratio of chlorine is greater than 1, is preferably between 1 and 50, is more preferably between 1.5 and 10;
The add-on of described organic oxime is 0.1 to 5 times of silazine link quantity in described amine propyl amino silane, is preferably 1 to 3 times, is more preferably 1.5 to 2 times;
In step 2, described amine propyl amino silane is raw material, and carrying out reacting with organic oxime is implement under the existence of one or more organic solvents, and this kind of organic solvent comprises alkane, aromatic hydrocarbons or ether, the weight ratio of its add-on and organic oxime consumption is in the scope of 50% to 200%;
R in the molecular formula of described organic amine
1methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-or the tertiary butyl; The nitrogenous compound of described acid-acceptor is ammonia, urea, triethylamine, pyridine;
Described step 1 also comprises reacts with organic amine first at ambient pressure by chloropropyl chlorosilane; Then by gained intermediate product mixture under certain temperature and pressure with the reaction of organic amine of the same race or not of the same race, thus form amine propyl group organic amino group silane, certain pressure wherein and temperature refer to, system pressure should between 14.5psi and 1450.3psi, and temperature of reaction should at 50 to 200 degrees Celsius;
Described step 1 comprises reacts chloropropyl chlorosilane with organic amine under certain temperature and pressure, thus form amine propyl group organic amino group silane, certain pressure wherein and temperature refer to: system pressure should between 14.5psi and 1450.3psi, and temperature of reaction should at 50 to 200 degrees Celsius.
According to the technical program, the reaction product of step 2 is purified by the mode of underpressure distillation, the organic amine that can discharge in first under low pressure removal system, then the organic solvent in flash distillation removing system, finally under reduced pressure remove unnecessary organic oxime, can target product be obtained;
High by amine propyl group organic oximino silane purity of this method synthesis preparation, not containing any alkoxy base, avoid de-oxime system room temperature silicone solidification of silicon composition the introducing of alkoxyl group.
Embodiment
For making the object, technical solutions and advantages of the present invention clearly understand, below in conjunction with specific embodiment, the present invention is described in more detail;
Except no special indicates, per-cent involved below is all weight percentage;
comparison example one,
Volume be 5 liters be equipped with reflux, 429 grams of (2.39 moles) amine propyl trimethoxy silicanes are added in the reactor of the receiving vessel of condensation tower and respective volume, 2.4 liters of toluene, the calcium oxide of 1.36 liters of (14.36 moles) methyl ethyl ketone oxime and 170 milligrams.Heat gained solution at ambient pressure to backflow, and keep reflux state 15 hours, about 407 grams of overhead products flow out in receiving vessel during this period, and head temperature remains on 65 degrees Celsius to 105 degrees Celsius.Adding 200 milliliters of toluene enters in reactor, continues heating and keeps backflow and distillate light constituent in 100 to 110 degrees Celsius of periods of head temperature.The thick product of gained through filtering, and carries out underpressure distillation except desolventizing and excessive reaction raw materials, obtains 728.6 grams of orange-yellow liquid, is equivalent to the productive rate of 96.56%; Through known wherein containing the methyl alcohol of 189.4 grams to the composition analysis distillating light constituent, be equivalent to the reaction conversion ratio of 82.3%.The structure of product is also confirmed by GCMS with composition, wherein containing amine dimethylamine oxygen ylmethyl ethyl ketoxime base silane (6.5%), and amine propylmethoxy dimethyl ethyl ketoximinosilanes (50.5%), and amine oxypropyl trimethyl ethyl ketoxime base silane (43%);
example one,
The first step ammoxidation device comprises 2 liters of glass reaction stills, above puts mechanical stirring device, reflux column, and temperature controls thermopair, nitrogen protection device.In this reactor, add 600 grams of (2.83 moles) chloropropyl trichlorosilicanes, normal hexane 900 milliliters, and start to stir.Pass into ammonia after 20 minutes in mixture, keep stirring (rotating speed 250 rpms), now system releases heat, and what control ammonia passes into flow, and maintenance system temperature is lower than 55 degrees Celsius.After having reacted, close ammonia import, maintain stirred at ambient temperature after 2 hours, after filtration, and underpressure distillation obtains intermediate product chloropropyl aminosilane mixture;
In stainless steel autoclave, add above-mentioned intermediate product, this stainless steel cauldron has top formula and stirs, heating jacket temperature controlling system, polytetrafluoroethyllining lining, pressure transmitter, purging valve, gas connection ports, sampling valve, rupture disk and automatic decompression valve.Under agitation, add 2.18 kilograms of (128.5 moles) ammonias, and at the pressure of 725psi, reaction 7 hours is carried out at the temperature of 100 degrees Celsius, with gas chromatograph-mass spectrometer, reaction mixture is detected, after having reacted, stop heating, in the process of lowering the temperature gradually, slowly system is reduced pressure, a large amount of remaining ammonia is now had to discharge from system, water of condensation is utilized to continue system to be cooled to while 0 degree Celsius, continue gradually delivery systme pressure to normal atmosphere, now be warming up to 50 degrees Celsius gradually, ammonia in removal system completely, now by-product ammonium chloride is separated out from system, in order to reduce chloride ion content, this process also can be the recrystallization process under 290psi pressure, the ammonium chloride of separating out, after filtering and being removed, obtains intermediate product amine propyl amino silane mixture,
Organic oximation reaction of second step is in 5 liters of glass reaction stills, add intermediate product amine propyl amino silane mixture, add 2 liters of normal hexanes and 803 grams of (9.3 moles) methyl ethyl ketone oxime again, under agitation, be heated to 50 degrees Celsius, nitrogen (20 milliliters of per minutes) is slowly passed in reaction system, maintain and stir with temperature after 3 hours, stop heating, after removing solvent and unnecessary methyl ethyl ketone oxime by underpressure distillation, obtain a light yellow transparent liquid (620.2 grams, 63.7%), analyzed by gas chromatograph-mass spectrometer, product consists of amine oxypropyl trimethyl ethyl ketoxime base silane, 92%, methyl ethyl ketone oxime, 5%, high boiling material, 3%,
example two,
(there is top formula stir at a stainless steel cauldron, heating jacket temperature controlling system, polytetrafluoroethyllining lining, pressure transmitter, purging valve, gas connection ports, sampling valve, rupture disk and automatic decompression valve) in, under agitation, add 600 grams of (2.83 moles) chloropropyl trichlorosilicanes, 2.33 kilograms of (137 moles) ammonias, and at the pressure of 725psi, reaction 10 hours is carried out at the temperature of 100 degrees Celsius, with gas chromatograph-mass spectrometer, reaction mixture is detected, after having reacted, stop heating, in the process of lowering the temperature gradually, slowly system is reduced pressure, a large amount of remaining ammonia is now had to discharge from system, water of condensation is utilized to continue system to be cooled to while 0 degree Celsius, continue gradually delivery systme pressure to normal atmosphere, now be warming up to 50 degrees Celsius gradually, ammonia in removal system completely, now by-product ammonium chloride is separated out from system, in order to reduce chloride ion content, this process also can be the recrystallization process under 290psi pressure, the ammonium chloride of separating out, after filtering and being removed, obtains intermediate product amine propyl amino silane mixture,
Organic oximation reaction of second step is with example one, and obtain a light yellow transparent liquid (353.5 grams, 36.3%) by purifying, analyzed by gas chromatograph-mass spectrometer, product consists of amine oxypropyl trimethyl ethyl ketoxime base silane, and 90.5%; Methyl ethyl ketone oxime, 4%; High boiling material, 5.5%;
Above-described specific embodiment; further detailed description has been carried out to object of the present invention, technical scheme and beneficial effect; be understood that; the foregoing is only specific embodiments of the invention; be not limited to the present invention; within the spirit and principles in the present invention all, any amendment made, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (8)
1. a preparation method for the organic oximido silicon compound of amine propyl group, is characterized in that comprising step:
1) chloropropyl chlorosilane is mixed with organic amine, add acid-acceptor and react, and obtain amine propyl amino silane;
2) with this kind of amine propyl amino silane for raw material, carry out reacting with organic oxime and obtain this kind of organic oximino silane of amine propyl group;
Above-described chloropropyl organochlorosilane is the compound that an available following molecular formula represents:
ClC
3H
6SiR
nCl
(3-n)；
Wherein, the saturated or unsaturated alkyl of the straight chain that R is made up of 1 to 20 carbon, side chain or ring-type, or R forms aryl by 1 to 20 carbon; N is the integer of 0 to 2;
Described organic amine is the compound that an available following molecular formula represents:
R1
aH
（3-a）N；
Wherein, the alkyl that is made up of 1 to 6 carbon of R1; A is the integer of 0 to 2;
Described organic oxime is the compound that an available following molecular formula represents:
R2R3C=NOH；
Wherein, R2, R3 are the identical or different alkyls be made up of 1 to 10 carbon.
2. preparation method according to claim 1, it is characterized in that, described acid-acceptor is alkaline matter, comprise nitrogenous compound, basic metal and oxide compound thereof or oxyhydroxide, alkaline earth metal oxide or oxyhydroxide, in its add-on and chloropropyl organochlorosilane, the mol ratio of chlorine is between 1 and 50.
3. preparation method according to claim 1, is characterized in that, the add-on of described organic oxime is 1 to 5 times of silazine link quantity in described amine propyl amino silane.
4. preparation method according to claim 1, it is characterized in that, in step 2, described amine propyl amino silane is raw material, carrying out reacting with organic oxime is implement under the existence of one or more organic solvents, this kind of organic solvent comprises alkane, aromatic hydrocarbons or ether, and the weight ratio of its add-on and organic oxime consumption is in the scope of 50% to 200%.
5. preparation method according to claim 1, is characterized in that, the R1 in the molecular formula of described organic amine is methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-or the tertiary butyl.
6. preparation method according to claim 2, the nitrogenous compound of described acid-acceptor is ammonia, urea, triethylamine, pyridine.
7. preparation method according to claim 1, is characterized in that, described step 1 also comprises reacts with organic amine first at ambient pressure by chloropropyl chlorosilane; Then by gained intermediate product mixture under certain temperature and pressure with the reaction of organic amine of the same race or not of the same race, thus form amine propyl group amino containing silane, certain pressure wherein and temperature refer to, system pressure should between 14.5psi and 1450.3psi, and temperature of reaction should at 50 to 200 degrees Celsius.
8. preparation method according to claim 1, it is characterized in that, described step 1 comprises reacts chloropropyl chlorosilane with organic amine under certain temperature and pressure, thus form amine propyl group amino containing silane, certain pressure wherein and temperature refer to: system pressure should between 14.5psi and 1450.3psi, and temperature of reaction should at 50 to 200 degrees Celsius.
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| CN104650128B (en) * | 2015-03-13 | 2017-10-10 | 山东大学 | A kind of preparation method of α amino tributanoximo silane |
| CN108239519B (en) * | 2018-01-02 | 2020-11-27 | 深圳市广业电子科技有限公司 | Fast-curing one-component room-temperature-curing organic silicon composition |
| CN108239103B (en) * | 2018-01-02 | 2020-09-01 | 深圳市广业电子科技有限公司 | Silicon nitrogen compound containing multi-oxime silicon |
| JP2022123183A (en) * | 2021-02-12 | 2022-08-24 | 信越化学工業株式会社 | Production method of room temperature-curable organopolysiloxane composition, room temperature-curable organopolysiloxane composition, adhesive, sealing material, and article |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3189576A (en) * | 1962-09-07 | 1965-06-15 | Dow Corning | Organosilicon intermediates containing silicon-bonded oxime radicals |
| US4918209A (en) * | 1987-03-05 | 1990-04-17 | Rhone-Poulenc Chimie | Production of oximinosilanes |
| CN102532186A (en) * | 2012-01-05 | 2012-07-04 | 北京天山新材料技术股份有限公司 | Method for preparing hydroxyimino organosilicon compounds |
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2013
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3189576A (en) * | 1962-09-07 | 1965-06-15 | Dow Corning | Organosilicon intermediates containing silicon-bonded oxime radicals |
| US4918209A (en) * | 1987-03-05 | 1990-04-17 | Rhone-Poulenc Chimie | Production of oximinosilanes |
| CN102532186A (en) * | 2012-01-05 | 2012-07-04 | 北京天山新材料技术股份有限公司 | Method for preparing hydroxyimino organosilicon compounds |
Non-Patent Citations (1)
| Title |
|---|
| Reaction of Organylalkoxysilanes with Ethanolamine and Disproportionation of Transetherification Products;V. A. Kovyazin et al.;《Russian Journal of General Chemistry》;20081231;第78卷(第2期);第236-243页 * |
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