CN101307068A - Method for preparing aminoalkyl silanes - Google Patents
Method for preparing aminoalkyl silanes Download PDFInfo
- Publication number
- CN101307068A CN101307068A CNA2007101288660A CN200710128866A CN101307068A CN 101307068 A CN101307068 A CN 101307068A CN A2007101288660 A CNA2007101288660 A CN A2007101288660A CN 200710128866 A CN200710128866 A CN 200710128866A CN 101307068 A CN101307068 A CN 101307068A
- Authority
- CN
- China
- Prior art keywords
- alkyl
- atom
- amine
- general formula
- ammonia
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Abstract
The invention relates to a method for preparing amino-alkyl-silane R<1>R<2>N-(CH2)y-Si(OR<3>)3-nR<4>n, in particular to a method for preparing animo-propyl-alkyloxy-silane or alkoxy-silyl-propyl-amine, and an application of a circular reactor to prepare the amino-alkyl-silane. In particular, the invention relates to a preparation of 3-animo-propyl-trialkoxy-silane or gamma-animo-propyl-trialkoxy-silane. Moreover, the invention also relates to a method for preparing amino-functionalized organosilane. The method comprises the following steps of: making haloid-functionalized organosilane (X-(CH2)y-Si(OR<3>)3-nR<4>n) react with excessive amine or organic amine (HNR<1>R<2>) under pressure; distilling the excessive amine or the organic amine; feeding the mixture of acquired products into a crystallizer to separate ammonium halide or organic hydrogen-amine halide, and residual amine or organic amine in the crystallizer; and obtaining the amino-functionalized organosilane. The amino-functionalized organosilane is called amino silane.
Description
Technical field
The present invention relates to a kind of method for preparing aminoalkylsilane, the preparation method of aminopropyl organoalkoxysilane or alkoxysilyl propyl group amine especially, and use annular reactor (Schlaufenreaktor) to prepare this aminoalkylsilane.Especially, the present invention relates to the preparation of 3-aminopropyl trialkoxy silane or γ-aminopropyl trialkoxy silane.In addition, the invention still further relates to the preparation method of the organosilane of amino-functional, it reacts under pressure by the functional organosilane of halogen and excess ammonia or organic amine, and then distill out excess of ammonia or organic amine, the products therefrom mixture feeds in the crystallizer, wherein ammonium halide or organic halogenation hydrogen amine and residue ammonia or organic amine separate therein, afterwards, obtain the organosilane of amino-functional.The organosilane of following amino-functional is also referred to as aminosilane.
Background technology
Aminosilane is with a wide range of applications.For example, it can be used for the glass fibre polishing or be used in foundary industry as processing aid, and same, it can be used as tackiness agent and is used for elastomerics, thermoplastics, thermosetting resin, for example is used to prepare the resin of shelf-stable.From using as tackiness agent, to using as surface-modifying agent, up to being used as linking agent, its range of application is expanded.Its Application Areas extends to hygienic articles, polymer concrete, the building field that aerospace industry, automotive industry, insulated cable, pipeline, japanning, artificial marble are made, for example building construction and road building or casting technique by electronic industry.
The method that is used to prepare aminoalkylsilane is known, 3-aminopropyl triethoxysilane (AMEO for example, γ-An Bingjisanyiyangjiguiwan), wherein, the chlorine alkyl silane is as 3-chloropropyl triethoxysilane (CPTEO, γ-chloropropyl triethoxysilane), itself and excess of ammonia or organic amine preferably react with 1: 80 to 1: 20 ratio with 1: 100 to 1: 10 liquid fraction.Ammonia or organic amine are excessive many more, and the amount of by product is few more.Except desirable uncle aminoalkylsilane, also can form as the secondary amine of undesirable by product and tertiary amine (two-(tri-alkoxy first silicon propyl group) amine, HN[(CH
2)
n-Si (R ')
x(OR
3-x)]
2Perhaps three (tri-alkoxy first silicon propyl group) amine, N[(CH
2)
n-Si (R ')
x(OR
3-x)]
3, n=3, x=0,1 or 2, R '=methyl, phenyl, the alkyl of R=1-4 carbon atom).React in autoclave, temperature is 50 ℃-200 ℃, especially is 50 ℃-90 ℃, for example T=90 ℃, and the p=50 bars absolute, time=6h carries out in batches.When known temperature, pressure for example can be set to the 36-50 crust
DefinitelyAnd it is higher.Then, volatilization or evaporation and step-down discharge excess of ammonia, and ammonium chloride produces crystallization mostly.Volatilization process generally needs consuming time greater than 10 hours.The separation of ammonium chloride from crude product realizes by filtering usually.(DE-OS 2749316, DE-OS2753124) then to distill crude product.The organosilane that is known that aminofunctional is for a long time prepared by the functionalized organosilane of chlorine and ammonia or organic amine, and formed ammonium acid fluoride or formed organic chloride hydrogen amine are separated (DE-PS1023462).DE-PS1023462 has put down in writing a kind of method that is used to prepare (alkoxymethyl)-2 silicon propyl group amine, and its reaction by ammonia and γ-chloropropyl organoalkoxysilane prepares.Can obtain single-, two-and three-((alkoxymethyl)-2 silicon propyl group)-amine as reaction product.By the reaction gained list-, two-and the ratio of three-aminopropyl organoalkoxysilane can regulate by the ratio of used ammonia amount and halogen propyl group organoalkoxysilane.
In described method, its shortcoming is that during the product mixtures step-down, the grume of being made up of ammonium chloride or hydrogenchloride amine (Anbackung) appears on the sidewall and agitator of synthesis reactor, and can have a negative impact to the heat transmission in view of volatilization process.Precipitation and grume often need equipment to stop work, and must close, emptying, open synthesis reactor, add entry with the fouling of dissolving ammonium salt, perhaps mechanically discharge from caking, then drying and closing again.
In addition, shortcoming also is, also obviously contains the muriate of hydrolyzable and non-hydrolysable according to the aforesaid method products therefrom.In the product reduction of chloride content need other expensive post-processing steps (EP0741137A1, EP0702017A1).Therefore, EP0741137A1 discloses a kind of method, reacts by adding metal alkoxide with ammonia or the nonreactive chlorine functional organosilane of Organoalkyl amine.EP0702017 discloses a kind of residual nitrogen functional organosilane and has been dissolved in improving one's methods of metal alkoxide reaction in the alcohol.Then, the metal chloride that forms is separated.
DE19513976A1 discloses a kind of method that lacks chlorine or the functionalized organosilane of free from chloride ammonia for preparing equally, it is by the functionalized organosilane of chlorine and organic amine or ammonia react, and formed like this organic chloride hydrogen of separation or ammonium chloride, in addition, the amount of organic chloride hydrogen or ammonium chloride reacts by the metal alkoxide that interpolation is dissolved in the alcohol, especially alkali metal alkoxide or alkaline-earth metal alkyl oxide separate formed chlorination metal and prepared ammonia functional organosilane.The functionalized organosilane of ammonia according to this method preparation can be represented with following general formula:
(A)H
2N-CH
2-CH
2-CH
2-SiR
1 y(OR)
3-y
The alkyl of R=1-4 carbon atom and R
1=methyl or phenyl and y=0,1 or 2
(B)[(R
1O)
3Si-(CH
2)
n]
mNH
3-m-n(CH
2-CH
2-NH
2)
p
R
1The alkyl of=1-3 carbon atom, n=2 or 3, p=0 or 1 and m=1,2 or 3
(C)[(R
1O)
3Si-(CH
2)
n]-(NH-CH
2-CH
2)
p-NH
2
R
1The alkyl of=1-3 carbon atom, n=2 or 3 and p=2,3 or 4
(D)H
pNR[(CH
2SiR
m(OR)
3-m)]
2-p
N=1,2 or 3, m=0 or 1, p=0 or 1 and the alkyl of R=1-3 carbon atom
(E)RNH-(CH
2)
pNH
1-mR
m-(CH
2)
n-SiR
m(OR)
3-m
N=1,2 or 3, m=0 or 1, p=2 or 3 and the alkyl of R=1-3 carbon atom
Chlorine organosilane as raw material (Edukte) is represented with following general formula:
(F)Cl-(CH
2)
n-SiR
m(OR)
3-m
N=1,2 or 3, m=0,1 or 2 and the alkyl of R=1-3 carbon atom and the amine of following general formula
(G)H
nN(R)
3-n
The alkyl of R=1-3 carbon atom and n=1,2 or 3
(H)NH
2-CH
2-CH
2-(NH-CH
2-CH
2)
n-NH
2
N=0,1,2 or 3 and/or
(J)R
1NH-CH
2-CH
2-NHR
2
R
1And R
2The alkyl of=1-3 carbon atom.
From the functionalized organosilane of ammonia, will react formed organic chloride hydrogen or ammonium chloride after separating, handle with the metal alkoxide that is dissolved in the alcohol, so that also the remaining muriate composition of Cun Zaiing further precipitates.
The shortcoming of preceding method is to add the metal alkoxide that is dissolved in alcohol that is used for separating organic chloride hydrogen or ammonium chloride, to form separable metal chloride.
In addition, EP0849271A2 3-aminopropyl trialkoxy silane (γ-aminopropyl trialkoxy silane) is disclosed and with the mixture of primary and secondary aminosilane by continuous mode by 3-chloropropyl trialkoxy silane (γ-chloropropyl trialkoxy silane) and ammonia preparation.Preferred preparation be the 3-aminopropyl triethoxysilane.The reaction of mixing, raw material and extraction are carried out under the pressure of 5-60 bars absolute usually.Conventional temperature of reaction increases to 50 ℃-170 ℃, especially 60 ℃-110 ℃, passes through different warm areas in case of necessity.At the most 100 ℃ the time, stop to reactive moieties the stage of 3-aminopropyl trialkoxy silane hydrochloride in temperature.The reaction preference that forms primary amine is improved, and the reaction preference that forms secondary amine (two-(tri-alkoxy silicomethane propyl group) amine) reduces.When temperature surpassed 110 ℃, 3-aminopropyl trialkoxy silane hydrochloride and ammonia react generated ammonium acid fluoride and 3-aminopropyl trialkoxy silane.Reaction is preferably carried out in the reactor of＜110 ℃ and＞110 ℃ of two warm areas.The ratio of ammonia and alkoxy compound is 10: 1 to 300: 1, especially 30: 1 to 100: 1.
But shortcoming is, being under 100 times of excess of ammonias and the extra afterreaction condition to the chloropropyl trialkoxy silane, at 120 ℃, by primary, the second month in a season and tertiary amine groups silane only obtains the thick silane mixture of maximum 95% productive rate.
For product separates, except the ammonium chloride that distillation and precipitation separation go out, other pressure extraction also is essential.
DE19652642A1 relate to a kind of γ of preparation-aminopropyl trialkoxy silane and with the continuation method of primary and secondary aminosilane mixture, its reaction by γ-chloropropyl trialkoxy silane and ammonia prepares, wherein a) γ-chloropropyl trialkoxy silane and ammonia at first mix with the content ratio of hope, b) with mixture heating up to temperature of reaction, c) make the pressure reactor experience be enough to the residence time of complete reaction, wherein mixture can experience a plurality of warm areas, d) then, reaction mixture, e) product (γ-aminopropyl trialkoxy silane or mixture) separates and f from two-phase mixture) ammonia is back to reactor mutually.
The shortcoming of the described method of DE19652643A1 is that the salt of formation can't be separated independently, thereby reduces the amount of waiting to remove solvent/salt mixtures.
The invention task
Therefore, task is to provide another to prepare the method for aminoalkylsilane.Special feature of the present invention has been to provide a kind of improved method of the 3-of preparation aminopropyl organoalkoxysilane.Especially, the present invention has finished this task, and promptly it provides a kind of possibility, the ammonium halide that is produced in the time of can further being reduced in preparation ammonia functional organosilane or the tendency of organic halogenation hydrogen amine grume.
According to the present invention, described task is finished according to the description of claim.
Surprisingly, find that according to a first aspect of the invention can prepare aminoalkylsilane with simple and economic mode, condition is:
-in the first step of method, halogenated alkyl silane, 3-chloropropyl triethoxysilane (CPTEO) for example reacts in liquid phase with the organic amine of excess ammonia or excessive use,
-in second step of method, ammonia or organic amine reduction vaporization, wherein the major portion of excess ammonia or organic amine is all overflowed, and the major part of ammonium chloride or hydrogenchloride amine is preferably all, is dissolved in the liquid phase to remain,
Second step of-method products therefrom mixture is delivered to the 3rd step of method, and it operates in low stress level of second step of ratio method, and ammonium chloride or hydrogenchloride amine crystallize out,
-subsequently, crystalline ammonium chloride or hydrogenchloride amine separate from crude product, and
-by distillation aftertreatment crude product.
Therefore, theme of the present invention is by the ammonia of the organosilane of general formula I I and general formula III or nitrogen compound reaction, thus the method for the aminoalkylsilane of preparation general formula I,
R
1R
2N-(CH
2)
y-Si(OR
3)
3-nR
4 n (I)，
R
1=aryl, aralkyl, wherein alkyl has 1-8 C atom, especially has 5-8 C atom, and perhaps straight chain, branching or cyclic has alkyl, especially 5-8 C atom of 1-8 C atom, perhaps H, R
2=aryl, aralkyl, wherein alkyl has 1-8 C atom, especially has 5-8 C atom, and straight chain, branching or cyclic has alkyl, especially 5-8 C atom of 1-8 C atom, perhaps H, R
3=straight chain, branching or cyclic has the alkyl of 1-8 C atom, aryl or aralkyl, and wherein alkyl has 1-8 C atom, R
4=straight chain, branching or cyclic has the alkyl of 1-8 C atom, aryl or aralkyl, and wherein alkyl has 1-8 C atom, y=1,2,3 or 4 and n=0,1,2 or 3,
X-(CH
2)
y-Si(OR
3)
3-nR
4 n (II)，
Wherein X=Cl, Br, I or F, R
3=straight chain, branching or cyclic has the alkyl of 1-8 C atom, aryl or aralkyl, and wherein alkyl has 1-8 C atom, R
4=straight chain, branching or cyclic has the alkyl of 1-8 C atom, aryl or aralkyl, and wherein alkyl has 1-8 C atom, wherein R
3And R
4Can be identical or different, y=1,2,3 or 4 and n=0,1,2 or 3,
HNR
1R
2 (III)，
R
1=aryl, aralkyl, wherein alkyl has 1-8 C atom, especially has 5-8 C atom, and straight chain, branching or cyclic has alkyl, especially 5-8 C atom of 1-8 C atom, perhaps H, R
2=aryl, aralkyl, wherein alkyl has 1-8 C atom, especially has 5-8 C atom, and perhaps straight chain, branching or cyclic has alkyl, especially 5-8 C atom, perhaps H, wherein R of 1-8 C atom
1And R
2Can be identical or different,
Wherein specifically
-in the first step of method, the organic amine of the organosilane of general formula I I and excess of ammonia or general formula III reacts in liquid phase,
-in second step of method, ammonia or organic amine reduction vaporization, and ammonium chloride or hydrogenchloride amine solvent be in liquid phase and remain,
Second step of-method products therefrom mixture is delivered to the 3rd step of method, and it operates in low stress level of second step of ratio method, and ammonium chloride or hydrogenchloride amine crystallize out,
-subsequently, solid ammonium chloride or hydrogenchloride amine separate from crude product, and
By distillation aftertreatment crude product.
In the methods of the invention, that preferably use as the organosilane of general formula I I is 3-chlorine alkylalkoxy silane (γ-chlorine alkylalkoxy silane), for example:
3-chloropropyl triethoxysilane (γ-chloropropyl triethoxysilane),
3-r-chloropropyl trimethoxyl silane (γ-r-chloropropyl trimethoxyl silane),
3-chloropropylmethyldimethoxysilane (gamma-chloropropylmethyldimethoxysilane) or,
3-chloropropyl methyldiethoxysilane (γ-chloropropyl methyldiethoxysilane).
But, can also use other chlorine alkylalkoxy silanes in the methods of the invention, for example:
3-chloropropyl diethyl methoxy silane (γ-chloropropyl diethyl methoxy silane) or
3-chloropropyl ethyl propyl Ethoxysilane (γ-chloropropyl ethyl propyl Ethoxysilane).
In the method for the invention, as preferably ammonia, methylamine, ethamine or the diethylamine that N component or nitrogen compound use that contain of general formula III.
The method according to this invention can for example be as the product preparation in simple and particularly economic mode:
-3-aminopropyl triethoxysilane (γ-An Bingjisanyiyangjiguiwan),
-3-aminopropyl trimethoxysilane (γ-An Bingjisanjiayangjiguiwan),
-3-aminopropyl methyldiethoxysilane (γ-aminopropyl methyldiethoxysilane) or
-N-methyl-3-aminopropyl trimethoxysilane (N-methyl-γ-An Bingjisanjiayangjiguiwan),
It only is several more than listing.
Usually, in the method for the invention, the organosilane of general formula I I and the ammonia of general formula III or organic amine are added to pressure reactor with liquid form, wherein advantageously, the mol ratio of chlorine alkylalkoxy silane and ammonia or organic amine is adjusted into 1: 10 to 1: 100, is preferably 1: 10 to 1: 50.In the first step, reaction is generally at 25 to＜100 crust
DefinitelyPressure finish down and under 50 to＜110 ℃ the temperature, wherein, almost finished whole reactions, promptly Fan Ying scope is about 95-100%.In addition, most ammonium chloride or hydrogenchloride amine all are dissolved in the liquid phase and remain.Surpass 99%, ammonium chloride that forms in the reaction of especially preferred 99.9-100% or hydrogenchloride amine solvent are in the liquid phase of the first step and remain.Next the products therefrom mixture was delivered to for second step, and wherein second step was moved being starkly lower than under the pressure of the first step.Here advantageously, the ammonia of existing obvious content is flashed (abgeflasht) or is removed, and for example, is converted to the 15-20 crust from 50 when operation
Definitely, the 50-80 weight % of excess ammonia or organic amine.
Be that (bars absolute)＞10 are to＜50 crust preferably at pressure
Definitely, more preferably 11-35 clings to
Definitely, most preferably be the 13-25 crust
Definitely, especially 15-20 clings to
Definitely, and temperature is＞10 to＜110 ℃, and more preferably 20-95 ℃, most preferably be 30-85 ℃, when especially being 35-80 ℃, carrying out for second step, thereby ammonium chloride or hydrogenchloride amine almost all are dissolved in the liquid phase, the problem that can avoid solid to overstock thus as possible.Usually, evaporation time is drawn by the structure of the excess ammonia amount of reaction and excess amine amount and employed evaporation equipment, evaporation area or the like and equipment therefor.Therefore, in the method for the invention, the almost solids-free process by in second step has produced bigger degree of freedom, to select to be used for the suitable device of suitable and cost of described evaporative process.Therefore, in second step, the advantageously 0.1-4 hour product residence time, preferably 0.1-2 hour, 0.1-1 hour in particular.
The 3rd step (crystallizer that for example has agitator) was moved under the pressure below the second EOS pressure usually, was preferably the 1-6 crust
Definitely, wherein ammonium chloride or the hydrogenchloride amine solubleness in product mixtures descends, and thus, in the mode of special saving, it deposits with crystallized form.The operating temperature in the 3rd step is generally 20-60 ℃.Solid can separate from product in a manner known way, then carries out aftertreatment by distillation.
Usually, method of the present invention is as described below and carry out:
In the first step, the organosilane of general formula I I and excess ammonia or organic amine react in liquid phase, and formed here product mixtures was delivered to for second step, wherein reduction vaporization ammonia or organic amine, and the ammonium chloride that forms or hydrogenchloride amine solvent are in liquid phase.Then, the product mixtures in second step was delivered to for the 3rd step, and it operates in than low stress level of second step.Ammonium chloride or hydrogenchloride amine crystallize out and separate from crude product.For example, can be accomplished by filtration separation.Pressure is being arranged or do not having under the pressure condition and finish filtration.Then, the gained crude product carries out aftertreatment by distillation.
The inventive method is characterised in that following advantage:
-to compare with those of DE-PS2749316 or DE-OS2753124, the operating time of the inventive method is they half at least, thereby plant capacity can be double.
Grume in the-synthesis reactor no longer occurs usually.
In-the second step, deposition solid hardly, thus for ammonia or organic amine in the main amount of correct position evaporation, can be with in the energy introducing method.
The pressure rating of-the inventive method makes in wide method scope uses step 2 or 3 respectively relatively at preceding step cost equipment more suitably.
-based on respectively with respect to step before and the ammonia amount that reduces or the amount of organic amine can be used littler equipment equally.
1, embodiment:
The present invention further sets forth by following examples:
Embodiment 1.1
The preparation of 3-aminopropyl triethoxysilane (γ-An Bingjisanyiyangjiguiwan)
In being equipped with the autoclave of agitator, with the reaction within 6 hours under 48-50 crust and about 100 ℃ of the 3-chloropropyl triethoxysilane (γ-chloropropyl triethoxysilane) of 7.5kg (31.1mol) and 24kg (1412mol) ammonia.During this period of time, by the GC-analyser, can detect the 3-chloropropyl triethoxysilane of trace in formed 3-aminopropyl triethoxysilane crude product (γ-An Bingjisanyiyangjiguiwan), the ammonium chloride of formation is dissolved in excess ammonia or the formed aminosilane crude product with this understanding fully.
Then, the interior material of autoclave uncooled and that pressure forms down is delivered to other pressurized vessel (flash vaporization process) by blow-off valve, thereby simultaneously most of excess of ammonia is distilled under pressure, wherein, the pressure in the evaporation element is adjusted into about 18-20 crust.
After autoclave is transferred to first evaporation element fully, close flash valve at reactant, progressively autoclave is reduced pressure, use raw material (Edukten) to fill and heating afterwards again with water-cooled or 40 ℃ of refrigerative refrigerants.
Material in first evaporation element is heated to 50-60 ℃ by circulating evaporator, and the ammonia that distillation is removed other is about 15 crust until surplus pressure.After about 1 hour, about 70% of excess ammonia is removed from the aminosilane crude mixture, dissolved ammonium chloride can not be precipitated out with solid form from crude product.The aminosilane crude product of residual about 60 ℃ of temperatures is without cooling and be delivered to for the 3rd step under pressure again, in the promptly so-called crystallizer.Be similar to the unitary flash vaporization process of first distillation.In crystallizer, in flash vaporization process, surplus pressure is adjusted to the 3-5 crust.Flash vaporization process in the crystallizer stir at the same time with heating container in carry out under formed aminosilane crude product/salt mixture condition.
With respect to autoclave, first evaporation element of emptying is further emptying decompression not, and can refill when the surplus pressure of about 12-15 crust.
Afterwards, all aminosilane crude products all are delivered to crystallizer, and residual ammonia distills under lasting stirring and heating condition to be removed, and wherein, are pressed in the crystallizer and reduce to about 1 crust under 20 ℃ of internal conditions gradually.In this process, remaining ammonium chloride is precipitated out from the aminosilane crude product with crystallized form, by whipping process, keeps with form of suspension.The pressure emptying of crystallizer finished after about 3-4 hour.Then, crude mixture is expelled in the storage vessel, remaining ammonia emptying in exhaust system.Mass transport in the storage vessel is to Filter dryer, and the aminosilane crude product separates with ammonium chloride, and filter cake washs with scavenging solution (for example toluene, gasoline, hexane or the like) with ordinary method, and filtrate is separated into single material by vacuum distilling.
After distillation finishes, obtain the 3-aminopropyl triethoxysilane of 6.05-6.4kg, the determined purity of gas-chromatography is about 98.5-99.0GC-WLDFL%, and chloride content is 20-50ppm.
The productive rate of 3-aminopropyl triethoxysilane (after the distillation) is about 88-92%.The ammonia liquor that reclaims during pressure distillation or vacuum distilling or the amount of scavenging solution are reused for preparation 3-aminopropyl triethoxysilane.
Embodiment 1.2
The preparation of 3-aminopropyl trimethoxysilane (γ-An Bingjisanjiayangjiguiwan)
Similar to Example 1, with the reaction within 6 hours under 48-50 crust and about 100 ℃ of the 3-r-chloropropyl trimethoxyl silane (γ-r-chloropropyl trimethoxyl silane) of 6.2kg (31.1mol) and 24kg (1412mol) ammonia, then, described according to embodiment 1, excess of ammonia is removed by two flash vaporization processes and pressure distillation.After distillation is purified under filtration and the vacuum, obtain the 3-aminopropyl trimethoxysilane of 4.8-5.1kg, the determined purity of gas-chromatography is about 98.4-99.0WLDFL%, and chloride content is 20-65ppm.Productive rate after the distillation is 86-91%.
Embodiment 1.3
The preparation of 3-aminopropyl methyldiethoxysilane (γ-aminopropyl methyldiethoxysilane)
According to embodiment 1,3-chloropropyl methyldiethoxysilane (γ-chloropropyl methyldiethoxysilane) and 24kg (1412mol) ammonia react with 6.6kg (31.1mol), excess of ammonia is removed by pressure distillation and flash vaporization process, and the 3-aminopropyl methyldiethoxysilane of formation is separated with vacuum distilling by filtration.
(productive rate: 90-93%), the determined purity of gas-chromatography is 98.7-99.3GC-WLDFL% to the 3-aminopropyl methyldiethoxysilane of gained 5.4-5.5kg, and chloride content is 16-45ppm.
According to a second aspect of the invention, be surprisingly found out that, can prepare the aminoalkylsilane of general formula I with simple and economic especially mode,
R
1R
2N-(CH
2)
y-Si(OR
3)
3-nR
4 n (I)，
Wherein, R
1=aryl, aralkyl, wherein alkyl has 1-8 C atom, especially has 5-8 C atom, and perhaps straight chain, branching or cyclic has alkyl, especially 5-8 C atom of 1-8 C atom, perhaps H, R
2=aryl, aralkyl, wherein alkyl has 1-8 C atom, especially has 5-8 C atom, and perhaps straight chain, branching or cyclic has alkyl, especially 5-8 C atom of 1-8 C atom, perhaps H, R
3=straight chain, branching or cyclic has the alkyl of 1-8 C atom, aryl or aralkyl, and wherein alkyl has 1-8 C atom, preferable methyl or ethyl, R
4=straight chain, branching or cyclic has the alkyl of 1-8 C atom, aryl (newly) or aralkyl, and wherein alkyl has 1-8 C atom, is preferably methyl, y=1,2,3 or 4 and n=0,1,2 or 3,
Particularly prepare 3-aminopropyl trimethoxysilane (AMMO, γ-An Bingjisanjiayangjiguiwan) or 3-aminopropyl triethoxysilane (AMEO, γ-An Bingjisanyiyangjiguiwan), wherein, the nitrogen compound reaction of the organosilane of general formula I I and ammonia or general formula III
X-(CH
2)
y-Si(OR
3)
3-nR
4 n (II)，
Wherein X=Cl, Br, I or F, preferred X=Cl, R
3=straight chain, branching or cyclic has the alkyl of 1-8 C atom, aryl or aralkyl, and wherein alkyl has 1-8 C atom, preferably methyl or ethyl, R
4=straight chain, branching or cyclic has the alkyl of 1-8 C atom, aryl or aralkyl, and wherein alkyl has 1-8 C atom, preferably methyl, wherein R
3And R
4Can be identical or different, y=1 or 2 or 3 or 4 and n=0 or 1 or 2 or 3,
3-chloropropyl triethoxysilane (CPTEO, γ-chloropropyl triethoxysilane) for example,
The nitrogen compound of general formula (III) is:
HNR
1R
2 (III)
R
1=aryl, aralkyl, wherein alkyl has 1-8 C atom, especially has alkyl, especially 5-8 the C atom that 5-8 C atom or straight chain, branching or cyclic have 1-8 C atom, perhaps H, R
2=aryl, aralkyl, wherein alkyl has 1-8 C atom, especially has 5-8 C atom, and perhaps straight chain, branching or cyclic has alkyl, especially 5-8 C atom, perhaps H, wherein R of 1-8 C atom
1And R
2Can be identical or different, the especially excessive existence of the nitrogen compound of ammonia or general formula III.
According to the present invention, the halogenated alkyl silane of general formula I I and the excess nitrogen compound of excess ammonia or general formula III react with liquid phase in annular reactor, and its back also can be called as annular reactor, particularly in the ejector nozzle annular reactor.
(it is used for the halogenated alkyl silane of general formula I I by using annular reactor, especially the nitrogen compound of chlorine alkyl silane and ammonia or general formula III reacts in liquid phase), compare with reactor described in the prior art (stirred pot), it has obviously improved the mixing of reacted constituent or product component, and realizes outstanding temperature control purpose.In addition, the mixed effect by reaction according to the present invention realizes has further reduced the hydrogen halide ammonium, and especially ammonium chloride or hydrogenchloride amine form the tendency of grume.Based on shorter equipment stand-by time, this can be used as economical especially and therefore notes as extra advantage.
General discontinuous the carrying out of method of the present invention promptly carries out in batches.But method of the present invention also can be moved continuously.
The method according to this invention, products therefrom are characterised in that the chloride content of hydrolyzable and non-hydrolysable is especially little.Thus, in advantageous method, can save other post-processing step.
Therefore theme of the present invention also is a kind of method for preparing the general formula I aminoalkylsilane,
R
1R
2N-(CH
2)
y-Si(OR
3)
3-nR
4 n (I)，
Wherein, R
1=aryl, aralkyl, wherein alkyl has 1-8 C atom, especially has 5-8 C atom, and perhaps straight chain, branching or cyclic has alkyl, especially 5-8 C atom of 1-8 C atom, perhaps H, R
2=aryl, aralkyl, wherein alkyl has 1-8 C atom, and perhaps straight chain, branching or cyclic has alkyl, especially 5-8 C atom of 1-8 C atom, perhaps H, especially preferably R
1And R
2=H, R
3=straight chain, branching or cyclic has the alkyl of 1-8 C atom, aryl or aralkyl, and wherein alkyl has 1-8 C atom, preferable methyl or ethyl, R
4=straight chain, branching or cyclic has the alkyl of 1-8 C atom, aryl or aralkyl, and wherein alkyl has 1-8 C atom, is preferably methyl, y=1 or 2 or 3 or 4 and n=0 or 1 or 2 or 3,
This method is carried out in the following way: reacts in liquid phase by the haloalkyl silane of general formula I I and the excess nitrogen compound of excess ammonia or general formula III,
X-(CH
2)
y-Si(OR
3)
3-nR
4 n (II)，
Wherein X=Cl, Br, I or F, preferred X=Cl, R
3=straight chain, branching or cyclic has the alkyl of 1-8 C atom, aryl or aralkyl, and wherein alkyl has 1-8 C atom, preferably methyl or ethyl, R
4=straight chain, branching or cyclic has the alkyl of 1-8 C atom, aryl or aralkyl, and wherein alkyl has 1-8 C atom, preferably methyl, wherein R
3And R
4Can be identical or different, y=1 or 2 or 3 or 4 and n=0 or 1 or 2 or 3,
The excess nitrogen compound of general formula III is:
HNR
1R
2 (III)，
R
1=aryl, aralkyl, wherein alkyl has 1-8 C atom, especially has 5-8 C atom, and perhaps straight chain, branching or cyclic has alkyl, especially 5-8 C atom of 1-8 C atom, perhaps H, R
2=aryl, aralkyl, wherein alkyl has 1-8 C atom, especially has 5-8 C atom, and perhaps straight chain, branching or cyclic has alkyl, especially 5-8 C atom, perhaps H, wherein R of 1-8 C atom
1And R
2Can be identical or different, next after-treatment products mixture, especially, the method for preparing the general formula I aminoalkylsilane is the nitrogen compound reaction by the haloalkyl silane of general formula I I and excess ammonia or general formula III, it is characterized in that, be reflected in the annular reactor and carry out.
Theme of the present invention is to use the aminoalkyl organoalkoxysilane of annular reactor with the preparation general formula I in addition, it passes through haloalkyl silane, especially the nitrogen compound of the chlorine alkyl silane of general formula I I and ammonia or general formula III reacts and gets, particularly or one of preferably according to Claim 8-14, more preferably according to claim 9 or 10 according to claim 1.
Therefore, method of the present invention is preferably carried out like this, promptly
In-the first step, haloalkyl silane, especially the nitrogen compound of chlorine alkyl silane and excess ammonia or general formula III in annular reactor with liquid phase reaction, ammonia or amine reduction vaporization, excess ammonia or the most of effusion of volatilization amine, ammonium halide or organic halogenation hydrogen amine, especially ammonium chloride or hydrogenchloride amine solvent remain in liquid phase fully
The product mixtures that-the first step obtains was delivered to for second step, and it operates in the stress level lower than the first step, and ammonium halide or organic halogenation hydrogen amine, especially ammonium chloride or hydrogenchloride amine crystallize out,
-then, the crystal salt that contains ammonium halide or organic halogenation hydrogen amine, especially ammonium chloride or ammonia chloride is separated from crude product, and
-by distillation aftertreatment crude product.
In the method for the invention, preferred 3-chlorine alkylalkoxy silane (γ-chlorine alkylalkoxy silane) uses as organosilane or the haloalkyl silane of general formula I I, for example:
3-chloropropyl triethoxysilane (γ-chloropropyl triethoxysilane),
3-r-chloropropyl trimethoxyl silane (γ-r-chloropropyl trimethoxyl silane),
3-chloropropylmethyldimethoxysilane (gamma-chloropropylmethyldimethoxysilane) or,
3-chloropropyl methyldiethoxysilane (γ-chloropropyl methyldiethoxysilane).Can also use other chlorine alkylalkoxy silanes in the methods of the invention, for example: 3-chloropropyl diethyl methoxy silane (γ-chloropropyl diethyl methoxy silane) or 3-chloropropyl ethyl propyl Ethoxysilane (γ-chloropropyl ethyl propyl Ethoxysilane).
What preferably use as the nitrogen compound that contains N composition or general formula III in the methods of the invention, is ammonia.But, for example can also use methylamine, thereby when using the 3-r-chloropropyl trimethoxyl silane, obtain N-methyl-3-aminopropyl trimethoxysilane (N-methyl-γ-An Bingjisanjiayangjiguiwan).
The method according to this invention, can as the product with relative higher yields and can prepare in simple and economic especially mode in addition preferably-but be not limited thereto-
3-aminopropyl triethoxysilane (γ-An Bingjisanyiyangjiguiwan),
3-aminopropyl trimethoxysilane (γ-An Bingjisanjiayangjiguiwan),
3-aminopropyl methyldiethoxysilane (γ-aminopropyl methyldiethoxysilane) and
3-aminopropyl methyl dimethoxysilane (γ-aminopropyl methyl dimethoxysilane).
In order to implement method of the present invention, at first the organosilane of general formula I I and the nitrogen compound of ammonia or general formula III are joined in the annular reactor with liquid form usually.Here suitable is that with haloalkyl silane, especially the mol ratio of the nitrogen compound of chlorine alkyl silane and ammonia and general formula III is adjusted into 1: 10 to 1: 50.Reaction in the first step in annular reactor, is that 40 to＜100 bars absolute and temperature are to finish under the 85-140 ℃ of condition at pressure generally promptly.Reaction is close to fully usually.Generally, can be by residence time conditioned reaction.In the methods of the invention, reaction was preferably carried out 2-12 hour, especially preferably carried out 4-6 hour.Thereby pressure preferably mainly is 45-75 bars absolute, especially preferably 50-62 bars absolute.Suitable is, the temperature that is reflected at of the present invention is 85-105 ℃, especially carry out 88-98 ℃ the time, and reaction operates in and is adjusted into the pressure that is fit to liquid-phase condition.Therefore, based on used haloalkyl silane, especially based on used chlorine alkyl silane, transformation efficiency can reach 〉=99.95 weight %, especially 〉=99.98 weight % usually.Ammonium salt or amine salt generally remain, and especially ammonium chloride or hydrogenchloride amine almost completely are dissolved in the liquid phase.Preferably surpass 99%, the salt that forms in reaction that is preferably 99.9-100% especially remains, and ammonium halide or organic halogenation hydrogen amine, especially chloride leach are in the liquid phase of the first step.The products therefrom mixture for example can be delivered to for second step, and wherein second step operated in obviously than under the low pressure of the first step.Here suitable is, has flashed away or removed the ammonia or the volatilization amine of obvious amount, and for example the 50-80 weight % of excess ammonia is in operation and changes the 15-20 bars absolute into from 50.
The operation in second step, be＞10 to＜50 bars absolute preferably at pressure, be preferably the 11-35 bars absolute especially, the most special 13-25 bars absolute that is preferably, especially be the 15-20 bars absolute, and temperature is＞10 to＜110 ℃, be preferably 20-95 ℃ especially, be preferably 30-85 ℃ the most especially, especially carry out under 35-80 ℃ the condition, make ammonium halide or organic halogenation hydrogen amine, especially ammonium chloride or hydrogenchloride amine at first substantially all be dissolved in the liquid phase and remain, can avoid the solid deposition problems in an advantageous manner thus.Here common, evaporation time is drawn by the structure of the excess ammonia amount of reaction and employed evaporation equipment, evaporation area or the like and equipment therefor.
Then, generally carry out the crystallization of salt, especially muriatic crystallization.Suitable is under the end pressure after pressure is lower than evaporation step, to be preferably the 1-6 crust
DefinitelyCarry out, wherein ammonium halide or organic halogenation hydrogen amine, the especially ammonium chloride solubleness in product mixtures descends, and deposits with crystallized form in the mode of special saving.The operating temperature of crystallisation step is generally 20-60 ℃.Solid can separate (" saltouing ") in a manner known way, then liquid phase is carried out aftertreatment by distillation.
The aminoalkyl organoalkoxysilane prepared according to the present invention advantageously contain usually＜the hydrolyzable chlorination thing of 50 ppm by weight or halogenide and＜the non-hydrolysable muriate or the halogenide of 100 ppm by weight.
The structure of annular reactor and operation scheme are generally for example from Ullmann ' sEncyclopedia, and learn the 6th edition (1999).
2. embodiment
Common following enforcement method of the present invention:
The nitrogen compound of the organosilane of general formula I I and excess ammonia or general formula III reacts with liquid phase in annular reactor.Then, can vaporized ammonia or evaporable amine, halogen, especially ammonium chloride or hydrogenchloride amine crystallize out, and separate from crude product.For example can realize separating by filtering.Filtration can have pressure or not have under the pressure and carry out.Then, the gained crude product carries out aftertreatment by distillation.The step mode " is saltoutd " and " distillation " all is that those skilled in the art itself are known.
The key of the inventive method is annular reactor and the reaction of generation therein.Annular reactor, referring to Fig. 1, it for example can be made of annular reactor (B1), heat exchanger (W1) and pump (P1).Reaction capacity is generally by specific installation and the decision of the pipeline that links to each other, and is expressed as the integral body of annular reactor.By in sampling receptacle (B1) syringe being set, the material in the described ejector nozzle ring loop reactor can mix extraly and consumingly by the jet that comes out from pump (P1).4/1 circulation ratio (absorbed dose/ejaculation amount) need not be bigger cost just can realize.At this moment two relative ejector nozzles of preferred use, can offset total fluid pulse in further mixing.
Generally at first inserting annular reactor with the nitrogen compound of ammonia or general formula III produces with starting.Then, add second raw material, haloalkyl silane, for example CPTEO.Afterwards, off-response body system, (W1) rises to temperature of reaction by external heat exchanger, for example 85-110 ℃.Usually make pump (P1) starting operation.Usually in total overall reaction cycle period maintenance operation.Under above-mentioned temperature of reaction, preferably pressure is adjusted into the 40-100 bars absolute.High speed of reaction generally needs high temperature.Therefore, the temperature dependency of the vapour pressure by ammonia or corresponding amine, high pressure forcibly is access in.With respect to stirred pot, in annular reactor, mostly be very easy to the configuration sealing property, and be favourable therefore because needn't have stir shaft through this housing (
).In addition, stirred pot can also omit conventional electromagnetic clutch.
The reaction capacity of annular reactor generally can be by packingless closed pump circulation, for example by being in charge of power-driven pump.In the method for the invention, in case the reaction beginning, heat exchanger (W1) is adjusted to " cooling " from " heating ".By external heat exchanger (W1), the temperature form of reaction shows very efficiently.This is an advantage for conventional stirred pot method, wherein can occur the heat exchange of relative mistake on wall.
Generally speaking, we can say, use method of the present invention, the more known more very favorable mixed high-voltage reaction chamber than so far can be provided.This cost of can reducing investment outlay especially is up to 30%.
Figure below is further explained the present invention, is not limited to these embodiments.
Fig. 1: Fig. 1 schematically shows a kind of preferred implementation of annular reactor.
Other parts according to the present invention are surprisingly found out that, in simple and economical mode, can avoid ammonium halide or organic halogenation hydrogen amine in crystallizer, to lump, to be the functionalized organosilane of halogen and excess ammonia or organic amine react in liquid phase having under pressure and the temperature condition prerequisite, then excess ammonia or organic amine evaporation are removed, ammonium halide or organic halogenation hydrogen amine are dissolved in the liquid phase fully basically and remain thus, the gained liquid phase is delivered in the crystallizer, wherein in crystallizer, preset organic or silicon organic liquid or aforesaid liquid mixture, and crystallizer operates in the stress level lower than above-mentioned step of reaction, residual volume with ammonia or organic amine distills thus, randomly also to introduce the energy of controlled temperature, for example ammonium halide or organic halogenation hydrogen amine are separated with crude product by filtering, the functionalized organosilane of pure ammonia obtains from crude product with known way own, for example by the follow-up distillation that can carry out under normal pressure or decompression.
In addition, can save a large amount of essential so far equipment part hydro-peening processes with simple and economical advantageous manner in the method for the invention, this equipment part hydro-peening process water carries out and then needs the equipment drying of costliness.
Therefore theme of the present invention also is to prepare the method for the functionalized organosilane of ammonia of general formula I
R
1R
2N-(CH
2)
y-Si(OR
3)
3-nR
4 n (I)，
Wherein, R
1=aryl, aralkyl, wherein alkyl has 1-8 C atom, perhaps has the alkyl or the H of 1-8 C atom, R
2=aryl, aralkyl, wherein alkyl has 1-8 C atom, perhaps has the alkyl or the H of 1-8 C atom, R
3=have the alkyl of 1-8 C atom, aryl or aralkyl, wherein alkyl has 1-8 C atom, R
4=have the alkyl of 1-8 C atom, aryl or aralkyl, wherein alkyl has 1-8 C atom, y=1,2,3 or 4 and n=0,1,2 or 3,
This method is following carries out: react in liquid phase by the organosilane of general formula I I and the nitrogen compound of ammonia or general formula III,
X-(CH
2)
y-Si(OR
3)
3-nR
4 n (II)，
X=Cl, Br, I or F, especially Cl, Br or I, R
3=have the alkyl of 1-8 C atom, aryl or aralkyl, wherein alkyl has 1-8 C atom, R
4=have the alkyl of 1-8 C atom, aryl or aralkyl, wherein alkyl has 1-8 C atom, wherein R
3And R
4Can be identical or different, y=1,2,3 or 4 and n=0,1,2 or 3,
The nitrogen compound of general formula (III) is:
HNR
1R
2 (III)，
R
1=aryl, aralkyl, wherein alkyl has 1-8 C atom, perhaps has the alkyl or the H of 1-8 C atom, R
2=aryl, aralkyl, wherein alkyl has 1-8 C atom, perhaps has the alkyl or the H of 1-8 C atom, wherein R
1And R
2Can be identical or different, especially pass through the functionalized organosilane of ammonia of prepared in reaction general formula I, this reaction is reacted in liquid phase under pressure and temperature condition for the organosilane of general formula I I and the nitrogen compound of excess ammonia or general formula III or the organic amine of general formula III, then evaporate excess ammonia or organic amine, thus, ammonium halide or organic halogenation hydrogen amine are dissolved in the liquid phase fully and remain, the gained liquid phase is delivered to crystallizer, wherein in crystallizer, preset organic or organic liquid of silicon or described mixtures of liquids, crystallizer operates in the stress level lower than the previous reaction stage, distill the residual volume of ammonia or organic amine, ammonium halide or organic halogenation hydrogen amine separate with crude product, obtain the functionalized organosilane of ammonia.
Be preferably used as general formula I I the functionalized organoalkoxysilane of halogen material be but to be not limited thereto:
3-r-chloropropyl trimethoxyl silane (γ-r-chloropropyl trimethoxyl silane),
3-chloropropyl triethoxysilane (γ-chloropropyl triethoxysilane),
3-chloropropylmethyldimethoxysilane (gamma-chloropropylmethyldimethoxysilane) or
3-chloropropyl methyldiethoxysilane (γ-chloropropyl methyldiethoxysilane).
But can also use other chlorine alkylalkoxy silanes (γ-chlorine alkylalkoxy silane), for example: 3-chloropropyl diethyl methoxy silane (γ-chloropropyl diethyl methoxy silane) or 3-chloropropyl methyl-propyl Ethoxysilane (γ-chloropropyl methyl-propyl Ethoxysilane).
For the organoalkoxysilane of the organic amino alkyl functionalization for preparing general formula I, can be as the organic amine of general formula III for example be but to be not limited thereto: methylamine, dimethylamine, ethamine, diethylamine or propylamine.
The method according to this invention, the preferred compound for preparing following general formula I in an advantageous manner:
-3-aminopropyl trimethoxysilane (γ-An Bingjisanjiayangjiguiwan),
-3-aminopropyl triethoxysilane (γ-An Bingjisanyiyangjiguiwan),
-3-aminopropyl methyl dimethoxysilane (γ-aminopropyl methyl dimethoxysilane),
-3-aminopropyl methyldiethoxysilane (γ-aminopropyl methyldiethoxysilane),
-N-methyl-3-aminopropyl trimethoxysilane (N-methyl-γ-An Bingjisanjiayangjiguiwan),
-N-methyl-3-aminopropyl triethoxysilane (N-methyl-γ-An Bingjisanyiyangjiguiwan),
This is several examples of only enumerating.
In the method for the invention, preferably as organic liquid be (i) aromatics or aliphatic hydrocrbon or their mixture or (ii) with Siliciumatom on the corresponding alcohol of alkoxyl group or the mixture of (iii) forming by these alcohol or hydrocarbon or hydrocarbon mixture or (iv) target product self or the mixture of forming by target product and hydrocarbon or hydrocarbon mixture or (v) target product in the crystallizer and hydrocarbon or hydrocarbon mixture and alcohol.
In the method for the invention, preferably as composition (i) be aromatic hydrocarbon and have with the Si atom on the fatty alcohol of the corresponding alkoxyl group of alkoxyl group or their mixture.What especially be used as hydrocarbon is toluene.
In the method for the invention, preferably as composition (ii) be methyl alcohol, ethanol, n-propyl alcohol or phenylcarbinol, preferably as composition (iii) be methyl alcohol-hexanes mixtures, ethanol-toluene mixture, ethanol-sherwood oil mixture, methyl alcohol-hexanaphthene mixture or n-propyl alcohol-toluene mixture, preferably as composition (iv) be the 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane-toluene mixture or 3-aminopropyl methyldiethoxysilane-toluene-octane mixture, and preferably as composition (v) be 3-aminopropyl triethoxysilane-hexanes mixtures, 3-aminopropyl trimethoxysilane-toluene-carbinol mixture or 3-aminopropyl methyldiethoxysilane-ethanol-toluene-hexanaphthene mixture.
In addition, in the method for the invention, the liquid phase of the product mixtures that is generated by reaction or the liquid phase of spissated product mixtures under agitation condition, are passed into below the surface that is preset at liquid in the crystallizer suitably, preferably with below the tangent surface of crystallizer inwall.
Liquid phase in the organic liquid that presets preferably is-10～120 ℃ in temperature, particularly preferably in 0～100 ℃, most preferably feeds under 10～60 ℃ of conditions.
It is the 0.1-15 bars absolute at pressure preferably that crude mixture is passed in the organic liquid, is preferably the 1-10 bars absolute especially, most preferably is under the 2-6 bars absolute condition and carries out.Suitable is that afterwards, by feed liquid phase in organic liquid, the gained mixture is to stir 0.1-5 hour under the 2-6 bars absolute at pressure.
In the method for the invention, preferably realize energy input by direct electrically heated or by thermal medium.
What especially preferably use as thermal medium is gaseous state or fluent meterial, especially water.
Suitable is, in the method for the invention, the heat input that is used to heat crystallizer is adjusted by the preset temp of independently pressure water thermal cycling, wherein, adjustment is used for the preset temp of the thermal cycling of crystallizer heating, for example two overcoat well heaters or semicanal shock heat device, and temperature is adjusted into 20-100 ℃, be preferably 22-60 ℃, most preferably be 25-50 ℃.
3. embodiment
Common following enforcement method of the present invention:
At first the organic amine with functionalized organosilane of the halogen of general formula I I and excess ammonia general formula III reacts in liquid phase under pressure and temperature condition.Then evaporate excess ammonia or organic amine under pressure, wherein formed ammonium halide or organic halogenation hydrogen amine advantageously are dissolved in the liquid phase fully and remain.The gained liquid phase is delivered to crystallizer, wherein presets organic in crystallizer or organic liquid of silicon or described mixtures of liquids, and crystallizer operates in the stress level lower than the previous reaction stage.Thus, distill the residual volume of ammonia or organic amine, randomly also will feed the energy of controlled temperature.Also can cooling crystallizer.Ammonium halide that forms in the crystallizer or organic halogenation hydrogen amine can separate from crude product, for example by filtering, can obtain the functionalized organosilane of pure ammonia in a manner known way from crude product.Generally can under normal pressure or reduced pressure, distill.
The method according to this invention and the distillation of preferably under reduced pressure, carrying out, the highly purified aminosilane that can prepare, preferably 〉=98GC-WLD%, it has low chloride content, preferably≤100 ppm by weight Cl has low chromatic number, and is preferred＜10APHA, as the water transparent liquid, and it has outstanding hydrolysis property.
This high purity ammonia base silane preferably uses in fiber glass industry.
Use method of the present invention, but a kind of simple effectively also economic simultaneously possibility is provided, it has avoided luming in crystallizer in the enforcement of described method.
Claims (27)
1. the method for preparing the aminoalkylsilane of general formula I,
R
1R
2N-(CH
2)
y-Si(OR
3)
3-nR
4 n (I)，
R wherein
1=aryl, aralkyl, wherein alkyl has 1-8 C atom, and straight chain, branching or cyclic has the alkyl or the H of 1-8 C atom,
R
2=aryl, aralkyl, wherein alkyl has 1-8 C atom, and straight chain, branching or cyclic has the alkyl or the H of 1-8 C atom,
R
3=straight chain, branching or cyclic has the alkyl of 1-8 C atom, aryl or aralkyl, and wherein alkyl has 1-8 C atom,
R
4=straight chain, branching or cyclic has the alkyl of 1-8 C atom, aryl or aralkyl, and wherein alkyl has 1-8 C atom,
Y=1,2,3 or 4 and
N=0,1,2 or 3,
The aminoalkylsilane of this general formula I prepares by the organosilane of general formula I I and the nitrogen compound reaction of ammonia or general formula III,
X-(CH
2)
y-Si(OR
3)
3-nR
4 n (II)，
X=Cl, Br, I or F,
R
3=straight chain, branching or cyclic has the alkyl of 1-8 C atom, aryl or aralkyl, and wherein alkyl has 1-8 C atom,
R
4=straight chain, branching or cyclic has the alkyl of 1-8 C atom, aryl or aralkyl, and wherein alkyl has 1-8 C atom, wherein R
3And R
4Can be identical or different,
Y=1,2,3 or 4 and
N=0,1,2 or 3,
The nitrogen compound of general formula III is:
HNR
1R
2 (III)，
R
1=aryl, aralkyl, wherein alkyl has 1-8 C atom, and perhaps straight chain, branching or cyclic has the alkyl or the H of 1-8 C atom,
R
2=aryl, aralkyl, wherein alkyl has 1-8 C atom, and perhaps straight chain, branching or cyclic has the alkyl or the H of 1-8 C atom,
R wherein
1And R
2Identical or different.
2. the described method of claim 1 is characterized in that,
-in the first step of method, the organic amine of the organosilane of general formula I I and excess of ammonia or general formula III reacts in liquid phase,
-in second step of method, ammonia or organic amine reduction vaporization, ammonium chloride or hydrogenchloride amine solvent in liquid phase and remain,
Second step of-method products therefrom mixture is delivered to the 3rd step of method, and it operates in low stress level of second step of ratio method, and ammonium chloride or hydrogenchloride amine crystallize out,
-subsequently, ammonium chloride or hydrogenchloride amine separate from crude product, and
-by distillation aftertreatment crude product.
3. claim 1 or 2 described methods is characterized in that, in the first step be reflected at 25 to＜100 the crust
DefinitelyPressure carry out down and under 50 to＜110 ℃ the temperature.
4. claim 1 or 2 described methods is characterized in that, being reflected in second step＞10 to＜50 crust
DefinitelyPressure carry out down and under 10 to＜110 ℃ the temperature.
5. the described method of claim 2 is characterized in that, the product mean residence time in second step is adjusted to 0.1-4 hour.
6. claim 1 or 2 described methods is characterized in that, the 3rd step was lower than under the second step terminal pressure condition at pressure carries out.
7. the described method of claim 6 is characterized in that, the 3rd step was the 1-6 crust at pressure
DefinitelyCarry out under the condition.
8. the described method of claim 1 is characterized in that, in order to prepare the aminoalkylsilane of general formula I, particularly R
1And R
2Be hydrogen simultaneously, when the haloalkyl silane of general formula I I, particularly X are chlorine, in liquid phase, react, then the after-treatment products mixture with the nitrogen compound of excess ammonia or general formula III.
9. claim 1 or 8 described methods is characterized in that, are reflected in the annular reactor and carry out.
10. the described method of claim 9 is characterized in that,
In-the first step, haloalkyl silane, especially the nitrogen compound of chlorine alkyl silane and excess ammonia or general formula III in annular reactor with liquid phase reaction, the nitrogen compound reduction vaporization of ammonia or general formula III, excess ammonia or the most of effusion of volatilization amine, ammonium halide or organic halogenation hydrogen amine, especially ammonium chloride or hydrogenchloride amine are dissolved in the liquid phase fully and remain
The product mixtures that-the first step obtains was delivered to for second step, and it operates in the stress level lower than the first step, and ammonium halide or organic halogenation hydrogen amine, especially ammonium chloride or hydrogenchloride amine crystallize out,
-then, crystallization ammonium halide or organic halogenation hydrogen amine, especially ammonium chloride or ammonia chloride separate from crude product, and
-by distillation aftertreatment crude product.
11. the described method of claim 9 is characterized in that, the temperature that is reflected in the annular reactor is 80-140 ℃ and carries out.
12. the described method of claim 9 is characterized in that, the pressure that is reflected in the annular reactor is that the 40-100 crust carries out.
13. the described method of claim 9 is characterized in that, the nitrogen compound mol ratio of composition haloalkyl silane and ammonia or general formula III is 1: 10 to 1: 50.
14. the described method of claim 9 is characterized in that, the capacity body of annular reactor (B1) (
) on be equipped with ejector nozzle.
15. the application of annular reactor in the aminoalkyl organoalkoxysilane of preparation general formula I, this preparation by general formula I I haloalkyl silane and the nitrogen compound of ammonia or general formula III according to claim 1 or especially carry out according to claim 10.
16. the described method of claim 1, it is used to prepare the functionalized organosilane of ammonia of general formula I, wherein, the organic amine of the functionalized organoalkoxysilane of the halogen of general formula I I and excess ammonia or general formula III reacts in liquid phase under pressure and temperature condition, then distill excess ammonia or organic amine, thus, ammonium halide or organic halogenation hydrogen amine are dissolved in the liquid phase fully and remain, the gained liquid phase is delivered to crystallizer, wherein in crystallizer, preset organic or organic liquid of silicon or described mixtures of liquids, crystallizer operates in the stress level lower than the previous reaction stage, distill the residual volume of ammonia or organic amine, ammonium halide or organic halogenation hydrogen amine separate with crude product, obtain the functionalized organosilane of ammonia.
17. the described method of claim 16, it is characterized in that, as organic liquid be (i) aromatics or aliphatic hydrocrbon or their mixture or (ii) with Siliciumatom on the corresponding alcohol of alkoxyl group or the mixture of (iii) forming by these alcohol or hydrocarbon or hydrocarbon mixture or (iv) target product self or the mixture of forming by target product and hydrocarbon or hydrocarbon mixture or (v) target product in the crystallizer and hydrocarbon or hydrocarbon mixture and alcohol.
18. the described method of claim 17 is characterized in that, as the hydrocarbon use is toluene.
19. the described method of claim 16 is characterized in that, the liquid phase of the product mixtures that is generated by reaction or liquid phase following feeding in the surface of liquid from be preset at crystallizer of spissated product mixtures.
20. the described method of claim 16 is characterized in that, under agitation condition, liquid phase is passed in the organic liquid that presets.
21. the described method of claim 16 is characterized in that, is under-10～120 ℃ of conditions liquid phase to be fed the liquid that presets in temperature.
22. the described method of claim 16 is characterized in that, is under the 0.1-15 bars absolute condition crude mixture to be passed in the organic liquid at pressure.
23. the described method of claim 16 is characterized in that, by liquid phase is passed in the organic liquid, the gained mixture is to stir 0.1-5 hour under the 2-6 bars absolute at pressure.
24. the described method of claim 16 is characterized in that, finishes energy input by direct electrically heated or thermal medium.
25. the described method of claim 16 is characterized in that, gaseous state or fluent meterial are as thermal medium.
26. the described method of claim 16 is characterized in that, by the preset temp of pressure water thermal cycling independently, can regulate and is used for the input of crystallizer heating heat.
27. the described method of claim 16 is characterized in that, is used for the preset temp of the thermal cycling of crystallizer heating, its scope is 20-100 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007101288660A CN101307068A (en) | 2007-05-18 | 2007-05-18 | Method for preparing aminoalkyl silanes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007101288660A CN101307068A (en) | 2007-05-18 | 2007-05-18 | Method for preparing aminoalkyl silanes |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101307068A true CN101307068A (en) | 2008-11-19 |
Family
ID=40123770
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2007101288660A Pending CN101307068A (en) | 2007-05-18 | 2007-05-18 | Method for preparing aminoalkyl silanes |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101307068A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102558219A (en) * | 2011-12-16 | 2012-07-11 | 山东轻工业学院 | Production process of tertiary amine silane |
| CN102558218A (en) * | 2011-12-16 | 2012-07-11 | 山东轻工业学院 | Method for preparing tertiary amine silane |
| CN102596972A (en) * | 2009-10-16 | 2012-07-18 | 道康宁公司 | Method of producing an aminoalkylalkoxysilane |
| CN105859766A (en) * | 2016-05-19 | 2016-08-17 | 南京齐正化学有限公司 | Method for solvent-free preparation of N, N-dimethyl-3-aminopropyltrimethoxysilane |
| CN107421843A (en) * | 2017-08-22 | 2017-12-01 | 中交四航工程研究院有限公司 | A kind of moisture detecting method of silane paste |
| CN114989210A (en) * | 2022-08-03 | 2022-09-02 | 淄博市临淄齐泉工贸有限公司 | Method for continuously preparing aminopropyl alkoxy silane |
-
2007
- 2007-05-18 CN CNA2007101288660A patent/CN101307068A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102596972A (en) * | 2009-10-16 | 2012-07-18 | 道康宁公司 | Method of producing an aminoalkylalkoxysilane |
| CN102596972B (en) * | 2009-10-16 | 2014-12-10 | 道康宁公司 | Method of producing an aminoalkylalkoxysilane |
| US9096622B2 (en) | 2009-10-16 | 2015-08-04 | Dow Corning Corporation | Method of producing an aminoalkylalkoxysilane |
| CN102558219A (en) * | 2011-12-16 | 2012-07-11 | 山东轻工业学院 | Production process of tertiary amine silane |
| CN102558218A (en) * | 2011-12-16 | 2012-07-11 | 山东轻工业学院 | Method for preparing tertiary amine silane |
| CN102558218B (en) * | 2011-12-16 | 2015-04-01 | 齐鲁工业大学 | Method for preparing tertiary amine silane |
| CN102558219B (en) * | 2011-12-16 | 2015-04-01 | 齐鲁工业大学 | Production process of tertiary amine silane |
| CN105859766A (en) * | 2016-05-19 | 2016-08-17 | 南京齐正化学有限公司 | Method for solvent-free preparation of N, N-dimethyl-3-aminopropyltrimethoxysilane |
| CN107421843A (en) * | 2017-08-22 | 2017-12-01 | 中交四航工程研究院有限公司 | A kind of moisture detecting method of silane paste |
| CN107421843B (en) * | 2017-08-22 | 2020-06-19 | 中交四航工程研究院有限公司 | Moisture detection method of silane paste |
| CN114989210A (en) * | 2022-08-03 | 2022-09-02 | 淄博市临淄齐泉工贸有限公司 | Method for continuously preparing aminopropyl alkoxy silane |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101307068A (en) | Method for preparing aminoalkyl silanes | |
| CN102762497B (en) | Process for producing cyclohexasilane compound | |
| US3467686A (en) | Preparation of organosilicon-nitrogen compounds | |
| CN101189246B (en) | Process for the production of isocyanatosilane and silylisocyanurate | |
| CN100384858C (en) | Producing and purifying method of bi (Tert-butyl amino) silane | |
| US4851558A (en) | Process for producing alkoxysilanes | |
| CN101597300B (en) | Method for the aqueous treatment of an amino-functional organosilane containing ammonium halides and/or organic amine hydrohalides | |
| CA1112657A (en) | Process for the production of aminoalkyl silanes | |
| US6423858B1 (en) | Manufacturing process for aminoalkyl silanes | |
| US9079926B2 (en) | Method for treating residues containing salt, produced during the production of amino-functional organosilanes | |
| WO2007034987A1 (en) | Method for producing ketimine structure-containing alkoxysilane | |
| US20120165564A1 (en) | Method for preparing purified aminosilane | |
| CN103619429B (en) | The method of trimethylsilyl amine is prepared by a chlorosilane and ammonia | |
| CN103342715B (en) | Preparation method of aminopropyl-containing organic oximido-silicon compound | |
| CN100465179C (en) | Prepn of isocyanate-containing alkyl silane or alkyl siloxane | |
| JP5589295B2 (en) | Nitrogen-containing silane compound powder and method for producing the same | |
| CN100386335C (en) | Preparation method of substituted diaryl phosphate | |
| US4234503A (en) | Method of preparing gamma aminopropyl alkoxy silanes | |
| CN111285896B (en) | Preparation method of bis (N-methylbenzamide) ethoxymethylsilane | |
| JP5264180B2 (en) | Method for continuously producing carbon-containing monoborosilazane, oligoborosilazane and / or polyborosilazane | |
| CN112430245A (en) | Synthesis system and synthesis method of silicon nitrogen heterocyclic aminosilane | |
| CN110862408A (en) | Synthesis method of N-alkyl aza-silacyclopentane and N-alkyl aza-silacyclopentane | |
| CN105218576B (en) | The preparation method of N (γ ＇ dimethylaminopropyls) γ aminopropyltriethoxy dimethoxysilanes | |
| CN101490020A (en) | Process for preparing triallyl cyanurate | |
| JP4801135B2 (en) | Method for producing aminoalkylsilane |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20081119 |