CN101307070A - Method for preparing aminoalkyl silanes method for preparing epoxy silanes - Google Patents
Method for preparing aminoalkyl silanes method for preparing epoxy silanes Download PDFInfo
- Publication number
- CN101307070A CN101307070A CNA2007101821316A CN200710182131A CN101307070A CN 101307070 A CN101307070 A CN 101307070A CN A2007101821316 A CNA2007101821316 A CN A2007101821316A CN 200710182131 A CN200710182131 A CN 200710182131A CN 101307070 A CN101307070 A CN 101307070A
- Authority
- CN
- China
- Prior art keywords
- silane
- catalyzer
- alkyl
- general formula
- iii
- 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
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to a method for preparing epoxy silane through the reaction of hydrogen silane and allyl glycidyl ether under the condition of an existing catalyst, in particular to a method for preparing epoxy silane of formula I, particularly 3-glycidyl oxygen propyl tri-alkoxy silane of formula I, wherein in the formula I, OR<1-3> having groups such as R<1>, R<2> and R<3> mutually independently represent alkoxyl or aryloxy, and R' can represent alkyl and y equal to 0 or 1. The method is carried out through the reaction of the allyl glycidyl ether of formula II and the hydrogen silane of formula III under the condition of the existing catalyst. In the formula III, OR<1-3> having groups such as R<1>, R<2> and R<3> mutually independently represent alkoxyl or aryloxy, and R' can represent alkyl and y equal to 0 or 1. In addition, the invention also relates to a method for preparing epoxy silane. The method is carried out through the reaction of hydrogen silane and allyl glycidyl ether under the condition of the existing catalyst, and a succeeding aftertreatment of obtained crude products.
Description
Technical field:
The present invention relates to by the method for hydrogen silane (Hydrogensilan) with allyl glycidyl ether prepared in reaction epoxy silane under the catalyzer existence condition.Especially, the present invention relates to the 3-glycidyl oxygen base propyl trialkoxy silane of the method for the epoxy silane of a kind of preparation formula I, particularly general formula I,
H
2C(O)CHCH
2-O-(CH
2)
3Si(R′)
y(OR
1-3)
3-y (I)，
Wherein has radicals R
1, R
2And R
3OR
1-3Represent alkoxyl group or aryloxy independently of each other, and R ' represents that alkyl and y equal 0 or 1, the allyl glycidyl ether of through type II under the catalyzer existence condition
CH
2(O)CHCH
2-O-CH
2CH＝CH
2 (II)
With the hydrogen silane reaction of general formula III,
HSi(R′)
y(OR
1-3)
3-y (III)，
Has radicals R in the formula (III)
1, R
2And R
3OR
1-3Represent alkoxyl group or aryloxy independently of each other, R ' expression alkyl and y equal 0 or 1, and also relate to a kind of under the catalyzer existence condition by hydrogen silane with the allyl glycidyl ether reaction and follow the method that the wherein resulting thick product of aftertreatment prepares epoxy silane.
Background technology:
In the organosilane chemistry, the epoxy silane of general formula I and particularly 3-glycidyl oxygen base propyl trialkoxy silane are important Industrial intermediates or finished products.They can for example be used as binding agent in matrix material, for example in japanning and fiber glass industry, in casting technique and binding agent industry.3-glycidyl oxygen base propyl trialkoxy silane (I) in applying opticglass also tool play a very important role.
The trialkoxy silane (III) (" H-silane " of epoxy silane (I) such as 3-glycidyl oxygen base propyl trialkoxy silane by having hydrogen atom; Hydrogen silane) prepares according to the hydrosilylation reactions shown in the following molecular balance formula with allyl glycidyl ether (II).
CH
2(O)CHCH
2OCH
2CH＝CH
2+HSi(OR)
3→CH
2(O)CHCH
2O(CH
2)
3Si(OR)
3
Wherein, radicals R is at R
1, R
2Or R
3Category in and represent alkyl especially.If the R=methyl, then that preparation is 3-glycidyl oxygen base propyl trimethoxy silicane (GLYMO; γ-isomer), be 3-glycidyl oxygen base propyl-triethoxysilicane (GLYEO if the R=ethyl then prepares; γ-isomer).
Except catalyzer, unreacted raw material and isomerized allyl glycidyl ether and tetraalkoxysilane, two kinds of isomer as the epoxy silane of by product still can appear in this reaction:
-2-glycidyl-Oxy-1-methyl-ethyl-Trimethoxy silane (β-isomer; Different-GLYMO), it is also referred to as is different 3-glycidyl oxygen base propyl trialkoxy silane or 2-glycidyl oxygen base (Glycidoy) sec.-propyl Trimethoxy silane,
And eight member ring heterocyclic compound, " cyclic alkoxy silane ", it is that cyclic action by epoxy silane forms,
-1-two-methoxyl group-sila (sila)-2,5-two oxa-s-3-methoxyl group-methyl-cyclooctane (" ring-GLYMO ").
Some other by product is glycidyl oxygen base trialkoxy silane, propyl trialkoxy silane, 1-methyl ethylene glycidyl ether and a high boiling material composition.
Hydrogen silane (H-silane) can be continuous or discontinuous with the hydrosilylation reactions of the unsaturated compound that contains the two keys of C=C two key, particularly terminal C=C, in any case and all will carry out existing under the condition of noble metal catalyst.3-glycidyl oxygen base propyl trialkoxy silane is usually in homogeneous system and making (referring to such as EP0277023, EP0288286, JP128763 and DE2159991) with six platinum chlorides (IV)-acid under as the catalyzer condition.For example, put down in writing a kind of hydrogen silane of using among the EP0288286 on the homogeneous phase platinum catalyst and under pure existence condition, as chloroplatinic acid (H
2PtCl
66H
2O) in Virahol under the condition, the method for hydrosilylation terminal unsaturation epoxy compounds is with the β-isomer that suppresses not expect or the keyed jointing effect of different-GLYMO.The shortcoming of homogeneous catalysis method is that temperature control is difficult between the reaction period, needs of having to separate remove catalyzer and since target product when under homogeneous phase dissolved catalysts influence and/or owing to temperature, controlling neglectful " breaking " meeting successive reaction cause and form by product more consumingly.Particularly when catalyzer also together enters in the distillation purification process, during distilling, will form above-mentioned 3-glycidyl oxygen base propyl trialkoxy silane (γ-isomer) isomer and dimer and the tripolymer that forms it.In addition, described method is not to be free from chloride method when using chloroplatinic acid, and this will cause quality product impaired and for example promote that trialkoxy silane is decomposed into tetraalkoxysilane.
In EP0548974, put down in writing heterogeneous noble metal catalyst, be rhodium and platinum, and they are as metal or contain the compound form use of metal as solid support material, the catalyst mode that for example contains precious metal with homogeneous, colloid, they can be used for preparing 3-glycidyl oxygen base propyl trialkoxy silane.In addition, also put down in writing the noble metal complexes that anchors on the non-metal carrier, for example platinum is fixed on gac or the aluminum oxide, and they can for example be used for the dehydrogenative condensation effect of methyl alcohol and Trimethoxy silane.
The catalyzer based on rhodium that is used to prepare 3-glycidyl oxygen base propyl trialkoxy silane has been described, the more definite catalyzer of saying so and being used for homogeneous phase and being used for heterogeneous catalysis among the EP0262642.Rhodium catalyst is used for the yield that homogeneous catalysis can obtain about 70% 3-glycidyl oxygen base propyl trialkoxy silane, and yield is 70 to 80% when being used for containing the heterogeneous catalysis of 5% rhodium equally on the gac as carrier.So rhodium catalyst should be less for the susceptibility of nitrogen compound at the former than the advantage of platinum catalyst, the loss of activity that yield will improve and catalyzer suffers of 3-glycidyl oxygen base propyl trialkoxy silane is also less thus.
Put down in writing prevailingly among the US-A4736049 with platinic compound or metal platinum and come homogeneous phase or heterogeneous catalysis and at general formula R CONR
1R
2The carboxylic acid amides existence condition under the hydrosilylation reactions that carries out.Just mentioned the platinum that is carried on the charcoal as carried catalyst.The existence of carboxylic acid amides generally can help ideal β-catalyzer and just mention the platinum that is carried on the charcoal.The existence of carboxylic acid amides generally can help the formation of ideal β-adducts (β-isomer).But, according to EP0262642, for prepare these Special Circumstances of 3-glycidyl propyl trialkoxy silane with platinum catalyst for, nitrogen compound be can reduce quality and therefore regard unfavorable factor as.
The thick product of hydrosilylation will come aftertreatment by means of distillation column usually.Generally speaking, the last handling process formula is very expensive and waste time and energy.Also confirmablely in addition be during the distillation aftertreatment, always then to form " organoalkoxysilane of cyclisation " (ring-GLYMO).
The boiling point of target product " epoxy silane " and " epoxy silane of cyclisation " is distinguished very little, and the time of batch distillation obviously will prolong, and utilize distillation column come separating for several times " cyclisation epoxy silane " industrial also be infeasible.But need separating for several times from principal product " epoxy silane of cyclisation " again, to obtain the highest epoxy silane purity.In addition, also can form the high boiling material of not expecting of significant proportion under this distillation condition, they can reduce the yield of epoxy silane.
The object of the invention:
The object of the invention be to provide a kind of better, simple as far as possible catalysis process, particularly a kind of heterogeneous catalysis method is used to prepare 3-glycidyl oxygen base propyl trialkoxy silane.In addition, the object of the invention also is to provide a kind of method for preparing epoxy silane, and its defective should avoid the thick product of described those aftertreatments as far as possible the time.
According to the present invention, these purposes can solve by the described technical scheme of claims.
According to a first aspect of the invention, this purpose can solve astoundingly by the following method, promptly in order to prepare the epoxy silane of general formula I, and the allyl glycidyl ether of formula II and the hydrogen silane of general formula III are reacted, and separating catalyst and epoxy silane.
H
2C(O)CHCH
2-O-(CH
2)
3Si(R’)
y(OR
1-3)
3-y (I)
In general formula I, OR
1-3Expression has the radicals R of representing alkyl or aryl independently of each other
1, R
2And R
3Group OR
1, OR
2To OR
3Group OR
1, OR
2To OR
3Can equate or difference.In addition, R
1Be the alkyl, particularly methyl with 1 to 4 C atom, wherein y represents numerical value 0 or 1.
Allyl glycidyl ether is represented by formula II.
CH
2(O)CHCH
2-O-CH
2CH＝CH
2 (II)
The compound of formula II also can be referred to as alkyl glycidyl base ether, alkyl-2,3-epoxypropyl ether or 1-(alkoxyl group)-2,3-epoxy group(ing) propane.
In the hydrogen silane of general formula III, OR
1-3Expression has the radicals R of representing alkyl or aryl independently of each other
1, R
2And R
3Group OR
1, OR
2To OR
3Group OR
1, OR
2To OR
3Can equate or difference.In addition, R ' is the alkyl, particularly methyl with 1 to 4 C atom, and wherein y represents numerical value 0 or 1.
HSi(R’)
y(OR
1-3)
3-y (III)
Especially, can prepare the epoxy silane of general formula I via the inventive method, 3-glycidyl oxygen base propyl trialkoxy silane especially preferably,
H
2C(O)CHCH
2-O-(CH
2)
3Si(R’)
y(OR
1-3)
3-y (I)，
Wherein, in formula I, have identical or represent the radicals R of straight chain, side chain, cyclic alkyl or aryl independently of one another
1, R
2Or R
3OR
1-3Expression alkoxyl group or aryloxy, R ' expression alkyl and y equal 0 or 1, even the allyl glycidyl ether of this method formula II
CH
2(O)CHCH
2-O-CH
2CH＝CH
2 (II)
Hydrogen silane with general formula III
HSi(R’)
y(OR
1-3)
3-y (III)，
At catalyzer, particularly react under the heterogeneous platinum catalyst existence condition,
Wherein, in the formula III, have identical or represent the radicals R of straight chain, side chain, cyclic alkyl or aryl independently of one another
1, R
2And R
3OR
1-3The expression alkoxyl group, R ' expression alkyl and y equal 0 or 1.In the preferable methods variant, can use platinum (the 0)-catalyzer that is attached on the non-metal carrier material as catalyzer.Wherein can save the use carboxylic acid amides.
The inventive method is attached a series of surprising advantage:
-opposite with the hydrosilylation effect of homogeneous catalysis, loss can not appear in catalyzer, and catalyzer also needn't be incorporated in the reaction and needn't remove from reaction mixture via corresponding reinforced system.
-owing to minimized the formation of by product, the selectivity of formation 3-glycidyl propyl trialkoxy silane (I) is with regard to＞90%.
-catalyzer and all compositions all are no muriatic, and the trend that just trialkoxy silane (III) is decomposed into tetraalkoxysilane has thus been reduced to minimum.
-temperature can be controlled well, and this helps optionally optimization.If temperature is up to about 140 ℃, then only can form very a spot of high boiling straight chain and lower boiling cyclic side products.
-platinum only need be present on the solid support material with the very small concentration of 0.01 to 1 quality %.
-in addition, the price of platinum also is starkly lower than rhodium.
-catalyzer can be in simple mode by with platinum (II)-or the solution impregnation of platinum (IV)-compound or spray solid support material drying, and then in nitrogen atmosphere platinum (II) or platinum (IV)-compound is reduced into Pt (0) and makes.
-suppressed the formation of heterogeneous ring compound (V) reliably, because homogeneous phase dissolved catalyzer can not enter into still-process.
-therefore, this reaction mixture can separate more simply, because needn't isolate heterogeneous ring compound (V).
-useful allyl glycidyl ether (II) is isomerizated into to 1-methyl ethylene-glycidyl ether in homogeneous reaction system effect has dropped to minimum, thereby makes and utilize a spot of allyl glycidyl ether (II) promptly enough.
-under no carboxylic acid amides condition, carrying out this method, this has just simplified the acquisition of pure hydrosilylation product.
Therefore alkyl in the trialkoxy silane (III)---and also be at 3-glycidyl oxygen base propyl trialkoxy silane (I)---preferably has straight chain, side chain or the cyclic alkyl of 1 to 8 carbon atom, and especially preferably methyl or ethyl.Trimethoxy can commercially availablely obtain as allyl glycidyl ether (II) equally with triethoxyl silane or make by trichlorosilane and methyl alcohol or alcoholic acid reaction.Except trialkoxy silane, as the hydrogen silane composition also can consider such as-but be not-methyl dialkoxy silicane, particularly Trimethoxy silane, triethoxyl silane, methyl dimethoxysilane, methyldiethoxysilane, three-positive propoxy silane, three-n-butoxy silane, three-isopropoxy silane, methyl two-positive propoxy silane, methyl two-isopropoxy silane, methyl two-n-butoxy silane, three-isobutoxy silane, methyl two-isobutoxy silane, phenyl dimethoxy silane.
Pt (0)-composition raw-material that is suitable as carried catalyst be arbitrarily, preferred water-soluble but or also dissolve in platinum (II) in other solvents-or platinum (IV)-compound, as platinum (II)-nitrate, platinum (III)-acetylacetonate, platinum I (V)-muriate, platinum I (V)-acetate, chlordene platinum (IV)-acid and they for example with the complex compound of symmetry-divinyl tetramethyl disiloxane formation.The suitable carriers material is such as gac, aluminum oxide, precipitation or incinerating silicon-dioxide, silicate, magnesium oxide and natural or synthetic zeolite.The solid support material of high surface area preferably, thus make the catalyzer of finally making have 10 to 400m
2The specific surface area of/g, this value is according to utilizing N
2The method of-adsorbing Brunauer, Emmett and Teller records [" BET "-Methode; P.W.Atkins, Physical Chemistry, the 4th edition, 779 pages are played Oxford University Press (1986)].
For being prepared, adopt platinum (II) preferably-or the aqueous solution of common 0.1 to 10 mass percent concentration of platinum (IV)-compound flood or spray solid support material.Advantageously so calculate the amount and/or the concentration of solution, platinum (the 0)-content of the feasible catalyzer of finally making is 0.01 to 1 mass percent, preferred 0.02 to 0.2 mass percent.The platinum of more umbers can't have infringement, but also can not bring corresponding advantages.After dipping, drying contains the catalyst precursor of platinic compound, for example in 80 ℃ airflow, and by importing hydrogen down and platinic compound is reduced to elements platinum (0) at 80 to 140 ℃, and make catalyzer thus.Reductive action is also promptly carried out in the reactor of hydrosilylation reactions preferably in position.
Hydrosilylation reactions preferably the condition of not using inert solvent jointly and 20 to 200 ℃, particularly carry out under 60 to 160 ℃ the temperature.Under low temperature more, too small for its speed of reaction of feasible method, and under higher temperature, can form the byproduct of significant quantity.This method can be carried out under normal atmosphere (1bar is absolute).But, particularly for the solid support material of fine particle, can make it percolation and cross catalyst area, method is to use higher pressure, and it is absolute for example to be up to 20bar.Be generally 1 to 100 minute in the following residence time of described temperature, particularly 10 to 30 minutes.Raw material (Edukte) mol ratio (II) and (III) can change in very wide scope, and usually in 0.1 to 10, particularly 0.25 to 4 scope.
Hydrosilylation effect of the present invention will be carried out on the solid-state catalyzer (fixed bed) being set to preferably.What be suitable as reactor is for example to have or do not have round-robin tubular reactor, tube bundle reactor, framework reactor or cross-stream reactor.Described method can be such as carrying out continuously, and mode is that catalyzer is arranged in the vertical tubular reactor of placing, and makes initial substance flow through the catalyzer of indirect heating to temperature of reaction with itself or form of mixtures respectively.In discrete method variant, reaction mixture is being turned back on the catalyzer via an outer loop through after catalyst fixed bed, and the fixed bed of flowing through once more.Repeat this program for a long time, until reaching required degree of conversion.By this way be divided into some time section total residence time corresponding to number of cycles.In all cases, reaction mixture all will be decomposed into its each component by continuous or discrete distillation, and this and do not rely on the type of reaction process.
Utilize method of the present invention can obtain transformation efficiency and be up to 100% 3-glycidyl oxygen base propyl trialkoxy silane (I), and space-time yield is up to 1.000mol/ (hg
Pt) and selectivity for being up to 95%.According to this method preferred preparation especially following these:
-3-glycidyl oxygen base propyl trimethoxy silicane (GLYMO),
-3-glycidyl oxygen base propyl-triethoxysilicane (GLYEO),
-3-glycidyl oxygen base propyl group three-positive propoxy silane,
-3-glycidyl oxygen base propyl group three-isopropoxy silane,
-3-glycidyl oxygen base propyl group three-n-butoxy silane, perhaps
-3-glycidyl oxygen base propyl group three-isobutoxy silane.
Following examples are in order to set forth method of the present invention rather than range of application of the present invention to be limited the range of application described in claims.
Embodiment
1. embodiment:
Embodiment 1.1
Having outer loop and wherein exist in the tubular reactor of catalyst bed in discontinuous operation, make infeed raw material allyl glycidyl ether (II) (AGE) and Trimethoxy silane (III) (TMOS), reaction generates 3-glycidyl oxygen base propyl trimethoxy silicane (I) (GLYMO); Recycle pump is responsible for making the material catalyst bed of flowing through from the top down.Use the 11.2g gac that contains 0.1 quality % platinum as catalyzer, it passes through with platinum (the II)-nitrate aqueous solution Immesion active carbon of 5 mass percents and at hydrogen stream (8h, under 100 ℃) in reduction platinum (II) compound and obtaining, and use 342g Trimethoxy silane (III) (2.8mol) and the mixture (3.05mol) formed of 348g allyl glycidyl ether (II) as raw material.Be reflected at 120 ℃ of following isothermals and carry out, all be 3s the duration of contact of catalyzer in each circulation.Form after the 75min and select to be produced as 92.2% 3-glycidyl oxygen base propyl trimethoxy silicane (I).Listed after the reaction end composition that reaction mixture records according to vapor-phase chromatography in the following table:
| Material | Consumption (g) |
| Trimethoxy silane (III) | 49.0 |
| Allyl glycidyl ether (II) | 12.2 |
| 3-glycidyl oxygen base propyl trimethoxy silicane (I) | 522.3 |
| 1-methyl ethylene glycidyl ether | 80.45 |
| Different-3-glycidyl oxygen base propyl trimethoxy silicane (IV) | 8.25 |
| Tetramethoxy-silicane | 17.8 |
Do not form high boiling composition, equally do not form heterogeneous ring compound (V) yet.Space-time yield is 158mol GLYMO/ (hg
Pt).
Embodiment 1.2
Not having outer loop and volume is 170cm
3The fixed-bed reactor of operate continuously in, under 120 ℃ and pressure, make allyl glycidyl ether (II) (AGE) (TMOS) react generation 3-glycidyl oxygen base propyl trimethoxy silicane (I) (GLYMO) with Trimethoxy silane (III) at 3bar.Fill in the fixed-bed reactor with the 70g gac that contains 0.02 quality % platinum as catalyzer, its catalyzer that also is similar to embodiment 1 makes like that.With 2,326mol/h Trimethoxy silane (TMOS) and 2,561mol/h allyl glycidyl ether (AGE) imports in the fixed-bed reactor.Therefore AGE is 1.1: 1 to the mol ratio of TMOS.Import raw material with liquid phase and via charge pump.Listed the composition of the reaction mixture that vapor-phase chromatography records (initial logistics) in the following table:
| Material | Consumption (g/h) |
| Trimethoxy silane (III) | 28.4 |
| Allyl glycidyl ether (II) | 8.5 |
| 3-glycidyl oxygen base propyl trimethoxy silicane (I) | 454.7 |
| 1-methyl ethylene glycidyl ether | 59.8 |
| Different-3-glycidyl oxygen base propyl trimethoxy silicane (IV) | 9.1 |
| Tetramethoxy-silicane | 19.3 |
The transformation efficiency of Trimethoxy silane is 90%, is 91.9% about the selectivity of required GLYMO (I).Selectivity about different GLYMO is 1.83%, is 6.05% about the selectivity of tetramethoxy-silicane.Do not form the height composition that boils, equally do not form heterocycle isomer GLYMO (V) yet.The residence time on the catalyzer is 16.8min, and the space-time yield of GLYMO is 137.4mol/ (hg
Pt).Discontinuous or continuously distillation come the aftertreatment reaction mixture, unreacted TMOS and AGE are returned again lead in the reactor simultaneously.
According to a further aspect of the invention, be surprised to find, when the allyl glycidyl ether of aftertreatment from formula II
CH
2(O)CHCH
2-O-CH
2CH＝CH
2 (II)
Hydrogen silane with general formula (III)
HSi(R’)
y(OR
1-3)
3-y (III)，
Reaction under the catalyzer existence condition is so that during the thick product of epoxy silane of epoxy silane of preparation general formula (I),
H
2C(O)CHCH
2-O-(CH
2)
3Si(R’)
y(OR
1-3)
3-y (I)，
Just can advantageously avoid starting described those defectives, and catalyzer and epoxy silane be separated particularly preferably in before the aftertreatment,
In formula (III), has radicals R
1, R
2And R
3OR
1-3Represent that independently of each other alkoxyl group or aryloxy and R ' can represent that alkyl and y equal 0 or 1,
In formula (I), has radicals R
1, R
2And R
3OR
1-3Represent that independently of each other alkyl or aryl and R ' can represent that alkyl and y equal 0 or 1.
According to the present invention, in order to prepare the epoxy silane of general formula I, to under the catalyzer existence condition, make the allyl glycidyl ether reaction of the hydrogen silane and the formula II of general formula III, and aftertreatment is the thick product of gained wherein, and method is in the first step catalyzer to be removed from thick product and crude product mixture that then the distillation aftertreatment is discharged by catalyzer in fact in second step.
Preferably utilize distillation column to distill the thick product that aftertreatment is substantially free of catalyzer.By absorption or reduction hydrosilylation catalysts is removed away from the thick product of epoxy silane comparatively suitably.
The method according to this invention can be met the epoxy silane of higher degree requirement.
Therefore another aspect of the present invention theme also is a kind ofly to react under the hydrosilylation catalysts existence condition by the hydrogen silane of formula III and the allyl glycidyl ether of formula II, and the thick product that obtains therein of the aftertreatment method of coming the epoxy silane of preparation formula I, wherein catalyzer is removed from thick product and then distilled thick product.
In the methods of the invention, can select for use such as---but being not to have only---Trimethoxy silane, triethoxyl silane, methyl dimethoxysilane, methyldiethoxysilane, three-positive propoxy silane, three-n-butoxy silane, three-isopropoxy silane, methyl two-positive propoxy silane, methyl two-isopropoxy silane, methyl two-n-butoxy silane, three-isobutoxy silane, methyl two-isobutoxy silane, phenyl dimethoxy silane, the diethylamino phenyl TMOS, phenyl two-positive propoxy silane, phenyl two-isopropoxy silane, phenyl two-n-butoxy silane or phenyl two-isobutoxy silane are as the hydrogen silane composition.
In this hydrosilylation method, can select for use alkyl glycidyl base ether as the alkene composition.But also can replace alkyl glycidyl base ether in a similar fashion, under situation about using, on H-silane, carry out catalytic hydrosilylation reactions such as the glycidyl methacrylate of (2, the 3-epoxypropyl) methacrylic ester.And this chemical process itself should be known.
In the methods of the invention, the epoxy silane of the general formula I of preferred preparation wherein, has radicals R
1, R
2And R
3OR
1-3Expression independently of each other has straight chain, side chain or the cyclic alkyl of 1 to 8 C atom or has the aryl of 6 to 12 C atoms, especially preferably:
-3-glycidyl oxygen base propyl trimethoxy silicane (GLYMO),
-3-glycidyl oxygen base propyl-triethoxysilicane (GLYEO),
-3-glycidyl oxygen base propyl group three-positive propoxy silane,
-3-glycidyl oxygen base propyl group three-isopropoxy silane,
-3-glycidyl oxygen base propyl group three-n-butoxy silane, or
-3-glycidyl oxygen base propyl group three-isobutoxy silane.
Preferably use noble metal catalyst based on platinum (Pt), palladium (Pd), rhodium (Rh) or iridium (Ir) as hydrosilylation catalysts in the method for the invention.Can use homogeneous phase or heterogeneous catalyzer.
Hydrosilylation reactions carries out under known condition own.According to the present invention, from the thick product that so obtains, can remove generally amount concentration in precious metal this moment and reach＜catalyzer of 10mg/kg, and the distillation aftertreatment do not contain the thick product of catalyzer in fact, for example utilize the post distillation.
Preferably can from thick product, remove catalyzer by absorption.Adsorption will be carried out in solid adsorbent bed suitably.But also solid adsorbent can be joined in the pending thick product, Gu and then by filtering or being separated by other liquid/methods.
Preferred use mean particle size is 1 to 30mm sorbent material, especially preferably has those of 5 to 20mm granularities.Used in the methods of the invention sorbent material has 10 usually to 1500m
2The internal surface area of/g.
Especially, can select gac for use, such as the silicic acid of calcining or precipitated silicate, aluminum oxide, titanium dioxide, zirconium white or zeolite and fluoropolymer resin are as sorbent material.But also can use other to be suitable as the material of sorbent material.Also can use the mixture of solid adsorbent in the methods of the invention.More suitable, also can use neutral sorbent material, in addition, used sorbent material also should be water-free in fact in the inventive method.
Preferably using internal surface area (BET) in the methods of the invention is 150 to 1400m
2/ g, preferred especially 600 is to 1400m
2/ g, preferred extremely especially 1000 is to 1500m
2The sorbent material of/g.
In the methods of the invention, preferably adsorb in 0 to 120 ℃ temperature range, particularly preferably in 10 to 50 ℃, the utmost point is particularly preferably in carrying out under 10 to 25 ℃ of temperature.
The described thick product of aftertreatment of the present invention can carry out under reduced pressure.In the methods of the invention, preferably 0.5 to 5bar absolute, preferred especially 0.7 to 2bar is absolute, adsorbs under preferred extremely especially 1.0 to the 1.5bar absolute pressure.
The thick residence time of product on adsorbent bed or sorbent material is 5 minutes to 2 hours more suitably, and be 10 to 60 minutes preferred duration of contact, and the preferred especially time period is 15 to 45 minutes.
Also can catalyzer be precipitated from thick product in the inventive method and separate out and from thick product, remove thus by reductive action.Can be as reductive agent such as using powder or blocky metallic zinc, they can easily be removed from thick product again.
The method of the application of the invention can obtain following advantage:
-when the distillation aftertreatment, can obtain the epoxy silane purity of particularly extra high 〉=99%, because during distilling, can at utmost suppress to continue to generate " epoxy silane of cyclisation " (=" cyclic organoalkoxysilane ").
Therefore flow process also improves the distillation ability in the middle of shortening during-distillation aftertreatment.
-amount of the high boiling material of formation is littler during distilling, and therefore improved the productive rate of distillatory epoxy silane.
-can import in the last handling process that has the precious metal removal process through the noble metal catalyst of absorption.
-can be just like when utilizing thin layer evaporator aftertreatment epoxy silane crude mixture, understanding the sort of epoxy silane loss phenomenon that occurs.
-do not need to add auxiliary agent, so that catalyst deactivation.
-the very little and technical costs of energy consumption is seldom in the catalyzer removal process of absorption.
Come exhaustive this one side of the present invention by following examples, but it is not to be that claims protection domain is limited.
2. embodiment:
Embodiment 2.1
Guiding the thick product of GLYMO-that contains 12ppm Pt content to pass by having mean diameter under 20 ℃ is the adsorbent bed that the granulating activated carbon of 1.5mm is formed.The precompressed of adsorbent bed is that 1.1bar is absolute.Adsorbent bed is filled 100cm
3Volume, the quality of activated carbon is 50.0g, the ratio in space is about 60%.Adsorbent bed is of a size of: internal diameter 22mm, long 320mm.Utilize the volume flow of 200Nml/h epoxy silane also therefore to have, determine that Pt content is 2ppm in the elutant in the adsorbent bed residence time of last 18 minute.Therefore, the Pt content of epoxy silane has descended 84%.Record according to the GC analytical method, epoxy silane does not change on adsorbent bed.
In the batch distillation post, the epoxy silane coarse products after the absorption purification is distilled aftertreatment, 99.4% epoxy silane purity can be provided.Under identical final condition, can only obtain 98.6% purity with the epoxy silane coarse products of not purifying through absorption.The mass balance of each fraction shows, if do not adsorb purification epoxy silane-crude mixture and add catalyzer when distillation, then will then form the epoxy silane of the cyclisation of not expecting when distillation.On the contrary, if before distillation absorption purification epoxy silane, then epoxy silane that can follow-up formation cyclisation during distilling.
Embodiment 2.2
Guiding the thick product of GLYMO-that contains 12ppm Pt content to pass the adsorbent bed of forming by the activated carbon of cylindrical shape (mean diameter 2mm, mean length 12mm) under 20 ℃.The precompressed of adsorbent bed is that 1.05bar is absolute.Adsorbent bed is filled 200cm
3Volume, the quality of activated carbon is 100.0g, the ratio in space is about 65%.Adsorbent bed is of a size of: internal diameter 30mm, long 300mm.Utilize the volume flow of 200Nml/h epoxy silane also therefore to have, determine that Pt content is 1ppm in the elutant in the adsorbent bed residence time of last 39 minute.Therefore, the Pt content of epoxy silane has descended 92%.Record according to the GC analytical method, epoxy silane does not change on adsorbent bed.
As among the embodiment 2.1, after the thick product of absorption purification epoxy silane, when following batch distillation, in still-process, can not continue to form the epoxy silane of cyclisation again.After absorption is purified, when fractionation by distillation, can obtain 99.5% epoxy silane purity, and under the condition of not adsorbing purification epoxy silane-crude mixture, in the distillation last handling process, under same boundary conditions, can only obtain 98.5% purity.
Embodiment 2.3
Guiding the thick product of GLYMO-that contains 3ppm Pt content to pass the adsorbent bed of forming by the activated carbon of granulating (mean diameter 1.5mm) under 20 ℃.The precompressed of adsorbent bed is that 1.05bar is absolute.Adsorbent bed is filled 100cm
3Volume, the quality of activated carbon is 48.1g, the ratio in space is about 60%.Adsorbent bed is of a size of: internal diameter 20mm, long 320mm.At the volume flow of 80Nml/h epoxy silane and therefore have under adsorbent bed this condition of the residence time of last 45 minute, in the elutant Pt content for to be lower than＜the detection threshold value of 1ppm.Also be that platinum almost completely is removed.Record according to the GC analytical method, epoxy silane does not change on adsorbent bed.
As among the embodiment 2.1, after the thick product of absorption purification epoxy silane, when following batch distillation, in still-process, can not continue to form the epoxy silane of cyclisation again.After absorption is purified, when fractionation by distillation, can obtain 99.5% epoxy silane purity, and under the condition of not adsorbing purification epoxy silane-crude mixture, in the distillation last handling process, under same boundary conditions, can only obtain 98.5% purity.
Embodiment 2.4
In the batch distillation process, from the 400g elutant of the epoxy silane content that contains 0.10% (corresponding to the epoxy silane of 0.4g cyclisation) cyclisation from embodiment 2.3, remove the thing (20% corresponding to 80g) that easily boils, and under unlimited height reflux conditions, kept 170 ℃ of temperature and the absolute pressure of 63mbar 48 hours.Utilize gas-chromatography to come the test column substrate after 48 hours time again, the epoxy silane umber of cyclisation is 0.125% at this moment, corresponding to 0.4g.Under distillation condition and when not having homogeneous catalyst, there is not the epoxy silane of follow-up formation cyclisation.
Embodiment 2.5
In the batch distillation process, from from embodiment's 2.3 and do not go through adsorption and have the 400g epoxy silane crude mixture of epoxy silane content of 0.10% (corresponding to 0.4g) cyclisation and remove the thing that easily boils (20% corresponding to 80g), and under unlimited height reflux conditions, kept 170 ℃ of temperature and the absolute pressure of 63mbar 48 hours.Utilize gas-chromatography to come the test column substrate after 48 hours time again, the epoxy silane umber of cyclisation is 0.45% at this moment, corresponding to 1.44g.Also promptly under distillation condition and when having homogeneous catalyst, the follow-up epoxy silane that forms cyclisation, more definite theory, the amount of the epoxy silane of cyclisation rises 3.6 times and has arrived 1.44g from 0.4g.
Claims (26)
1. method for preparing the epoxy silane of general formula I,
H
2C(O)CHCH
2-O-(CH
2)
3Si(R’)
y(OR
1-3)
3-y (I)，
Wherein has radicals R
1, R
2And R
3OR
1-3Separate expression alkoxyl group or aryloxy, R ' expression alkyl and y equal 0 or 1,
It is by the allyl glycidyl ether in catalyzer existence condition Formula Il
CH
2(O)CHCH
2-O-CH
2CH＝CH
2(II)
With the hydrogen silane reaction of general formula III,
HSi(R’)
y(OR
1-3)
3-y (III)，
Has radicals R in the formula (III)
1, R
2And R
3OR
1-3Separate expression alkoxyl group or aryloxy, R ' expression alkyl and y equal 0 or 1,
It is characterized in that catalyzer separates before aftertreatment with epoxy silane.
2. special the method for claim 1 is characterized in that, the allyl glycidyl ether of through type II in heterogeneous, the catalytic hydrosilylation reactions of platinum
CH
2(O)CHCH
2-O-CH
2CH＝CH
2(II)
With the trialkoxy silane reaction of general formula III,
HSi(R’)
y(OR
1-3)
3-y (III)，
Have identical in the formula (III) or represent the radicals R of straight chain, side chain, cyclic alkyl or aryl independently of each other
1, R
2Or R
3OR
1-3Expression alkoxyl group or aryloxy, R ' expression alkyl and 1 to 4 C atom and y equal 0 or 1,
The epoxy silane, particularly 3-glycidyl oxygen base propyl trialkoxy silane of preparation general formula I,
H
2C(O)CHCH
2-O-(CH
2)
3Si(R’)
y(OR
1-3)
3-y (I)，
Have identical in the formula (I) or represent the radicals R of straight chain, side chain, cyclic alkyl or aryl independently of each other
1, R
2Or R
3OR
1-3Expression alkoxyl group or aryloxy, R ' expression alkyl and 1 to 4 C atom and y equal 0 or 1.
3. method as claimed in claim 2 is characterized in that, as platinum (the O)-catalyzer of catalyzer working load on the non-metal carrier material.
4. method as claimed in claim 2 is characterized in that radicals R
1, R
2And R
3Expression straight chain side chain, cyclic have the alkyl of 1 to 8 C atom and/or have the aryl of 6 to 12 C atoms.
5. method as claimed in claim 2 is characterized in that radicals R
1, R
2And R
3Identical and expression methyl or ethyl.
6. method as claimed in claim 2 is characterized in that, allyl glycidyl ether (II) and trialkoxy silane (III) use with 0.1 to 10 mol ratio.
7. method as claimed in claim 2 is characterized in that, mol ratio is 0.25 to 4.
8. method as claimed in claim 2 is characterized in that, the mass fraction of platinum is 0.01 to 1.0% on the catalyzer, and solid support material is made up of gac, aluminum oxide or silicon-dioxide and the specific surface area of catalyzer is 10 to 400m
2Between/the g.。
9. method as claimed in claim 8 is characterized in that, the mass fraction of platinum is 0.02 to 0.1% on the catalyzer.
10. method as claimed in claim 8 is characterized in that catalyzer is halide not.
11. method as claimed in claim 2 is characterized in that, is reflected under temperature between 20 to 200 ℃ and 1 to the 20bar absolute pressure to carry out.
12. method as claimed in claim 11 is characterized in that, temperature is between 60 to 160 ℃.
13. method as claimed in claim 2 is characterized in that, reacts in the tubular reactor that has or do not have circulation loop, tube bundle reactor, framework reactor or cross-stream reactor and on catalyst fixed bed.
14. the method that is used to prepare the epoxy silane of general formula I particularly as claimed in claim 1, it is by existing the allyl glycidyl ether reaction of the hydrogen silane that makes general formula I I under the condition of catalyzer and general formula III, and aftertreatment wherein the thick product of gained carry out, it is characterized in that, catalyzer is removed from thick product and then distilled thick product.
15. method as claimed in claim 14 is characterized in that, by absorption catalyzer is removed from thick product.
16. method as claimed in claim 14 is characterized in that, adsorbs in solid adsorbent beds.
17. method as claimed in claim 16 is characterized in that, the use mean particle size is 1 to 30mm sorbent material.
18. method as claimed in claim 16 is characterized in that, using internal surface area is 10 to 1500m
2The sorbent material of/g.
19. method as claimed in claim 16 is characterized in that, uses anhydrous basically sorbent material as sorbent material.
20. method as claimed in claim 16 is characterized in that, uses gac, silicic acid, aluminum oxide, titanium oxide, zirconium white, zeolite or fluoropolymer resin as sorbent material.
21. method as claimed in claim 15 is characterized in that, adsorbs under the temperature of 0 to 120 ℃ of scope.
22. method as claimed in claim 15 is characterized in that, adsorbs in 0.5 to 5bar absolute pressure range.
23., it is characterized in that the thick residence time of product on sorbent material or adsorbent bed is 5 minutes to 2 hours as the described method in one of claim 15 or 16.
24. method as claimed in claim 14 is characterized in that, separates out catalyzer by precipitate reduction.
25. method as claimed in claim 24 is characterized in that, uses metallic zinc as reductive agent.
26. method as claimed in claim 14 is characterized in that, uses to have OR
1-3The epoxy silane of general formula I, radicals R wherein
1, R
2And R
3Identical or represent that independently of one another straight chain, side chain or cyclic have the alkyl of 1 to 8 C atom, or have the aryl of 6 to 12 C atoms, and use the hydrogen silane of general formula III, wherein OR
1-3Has radicals R
1, R
2And R
3It is identical or represent the aryl that straight chain, side chain or cyclic have the alkyl of 1 to 8 C atom or have 6 to 12 C atoms independently of one another.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007101821316A CN101307070A (en) | 2007-05-15 | 2007-05-15 | Method for preparing aminoalkyl silanes method for preparing epoxy silanes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007101821316A CN101307070A (en) | 2007-05-15 | 2007-05-15 | Method for preparing aminoalkyl silanes method for preparing epoxy silanes |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101307070A true CN101307070A (en) | 2008-11-19 |
Family
ID=40123772
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2007101821316A Pending CN101307070A (en) | 2007-05-15 | 2007-05-15 | Method for preparing aminoalkyl silanes method for preparing epoxy silanes |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101307070A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112236493A (en) * | 2018-04-06 | 2021-01-15 | 欧提腾股份有限公司 | Flexible and foldable abrasion resistant photopatternable silicone hardcoats |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6100408A (en) * | 1998-02-09 | 2000-08-08 | Huels Aktiengesellschaft | Process for preparing 3-glycidyloxypropyltrialkoxysilanes |
| US6402961B1 (en) * | 1999-07-23 | 2002-06-11 | Degussa Ag | Process for preparing epoxysilanes |
-
2007
- 2007-05-15 CN CNA2007101821316A patent/CN101307070A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6100408A (en) * | 1998-02-09 | 2000-08-08 | Huels Aktiengesellschaft | Process for preparing 3-glycidyloxypropyltrialkoxysilanes |
| US6402961B1 (en) * | 1999-07-23 | 2002-06-11 | Degussa Ag | Process for preparing epoxysilanes |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112236493A (en) * | 2018-04-06 | 2021-01-15 | 欧提腾股份有限公司 | Flexible and foldable abrasion resistant photopatternable silicone hardcoats |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2766337B1 (en) | Ethyl acetate production | |
| CN105555754A (en) | Isomerization method for bis(amino-methyl)cyclohexane | |
| JPWO2006121081A1 (en) | High purity acetonitrile and method for producing the same | |
| JPH11315083A (en) | Production of 3-glycidyloxypropyltrialkoxysilane | |
| Margitfalvi | On the Role of Modifier-Substrate Interactions in Different Heterogeneous Catalytic Asymmetric Hydrogenation Reactions | |
| CN101307070A (en) | Method for preparing aminoalkyl silanes method for preparing epoxy silanes | |
| US6402961B1 (en) | Process for preparing epoxysilanes | |
| CN1224621C (en) | Tetrahydrofuran refining process | |
| CN107987044B (en) | Method for preparing valerolactone | |
| KR100543496B1 (en) | Method for Producing Hexanediol | |
| JP3959993B2 (en) | Method for producing 1,4-butanediol | |
| TWI547478B (en) | Method for producing n-propyl acetate and method for producing allyl acetate | |
| JP2004182643A (en) | METHOD FOR MANUFACTURING alpha-HYDROXYCARBOXYLATE | |
| CN1105978A (en) | Process for producing highly purified acetic acid | |
| CN101182292B (en) | Hydrogenation process for high-purity naphthalenedicarboxylic acid | |
| JP7483681B2 (en) | Synthesis of chromanol derivatives | |
| CN105085137B (en) | The method of purification of organic solvent normal octane | |
| KR101819023B1 (en) | Refining mehtod for crude propylene oxide product and preparation method for propylene oxide | |
| JP2021534164A (en) | Synthesis of chromanol derivatives | |
| JP2002363132A (en) | Method for 2,2,4-trimethyl-1,3-pentanediol diisobutyrate production | |
| JP5144138B2 (en) | Process for producing α-methylene-β-alkyl-γ-butyrolactone | |
| CN103373934A (en) | Catalytic synthesis method of chiral intermediate for carbapenem and penem medicaments | |
| CN1060463C (en) | Hydroxy alkyl aldehyde making method | |
| CN112888678A (en) | Synthesis of chromanol and 2-methyl-1, 4-naphthoquinone derivatives | |
| CN103396383A (en) | Preparation method of chiral epoxy compound |
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 |