CN105693759B - The method for preparing chloropropyl alkylalkoxy silane using pathway reaction device - Google Patents
The method for preparing chloropropyl alkylalkoxy silane using pathway reaction device Download PDFInfo
- Publication number
- CN105693759B CN105693759B CN201610162597.9A CN201610162597A CN105693759B CN 105693759 B CN105693759 B CN 105693759B CN 201610162597 A CN201610162597 A CN 201610162597A CN 105693759 B CN105693759 B CN 105693759B
- Authority
- CN
- China
- Prior art keywords
- chloropropyl
- reaction device
- pathway reaction
- alcohol
- pathway
- 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.)
- Active
Links
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 115
- 230000037361 pathway Effects 0.000 title claims abstract description 59
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 229910000077 silane Inorganic materials 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 28
- -1 chloropropyl Chemical group 0.000 title claims abstract description 26
- 125000005055 alkyl alkoxy group Chemical group 0.000 title claims abstract description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 68
- 235000019441 ethanol Nutrition 0.000 claims abstract description 49
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000010521 absorption reaction Methods 0.000 claims abstract description 28
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 25
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 25
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000007789 gas Substances 0.000 claims abstract description 19
- YHRUOJUYPBUZOS-UHFFFAOYSA-N 1,3-dichloropropane Chemical compound ClCCCCl YHRUOJUYPBUZOS-UHFFFAOYSA-N 0.000 claims abstract description 15
- 230000032050 esterification Effects 0.000 claims abstract description 9
- 238000005886 esterification reaction Methods 0.000 claims abstract description 9
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 241000196324 Embryophyta Species 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000000460 chlorine Substances 0.000 claims description 8
- 229910052801 chlorine Inorganic materials 0.000 claims description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 6
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 4
- 229910052715 tantalum Inorganic materials 0.000 claims description 4
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 4
- 235000007164 Oryza sativa Nutrition 0.000 claims description 3
- 239000004809 Teflon Substances 0.000 claims description 3
- 229920006362 Teflon® Polymers 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 210000003298 dental enamel Anatomy 0.000 claims description 3
- 235000009566 rice Nutrition 0.000 claims description 3
- 240000007594 Oryza sativa Species 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 15
- 230000009467 reduction Effects 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 16
- 239000012043 crude product Substances 0.000 description 12
- 229960004756 ethanol Drugs 0.000 description 9
- 239000012535 impurity Substances 0.000 description 9
- 238000012545 processing Methods 0.000 description 8
- 239000013067 intermediate product Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 239000006227 byproduct Substances 0.000 description 6
- OOXSLJBUMMHDKW-UHFFFAOYSA-N trichloro(3-chloropropyl)silane Chemical compound ClCCC[Si](Cl)(Cl)Cl OOXSLJBUMMHDKW-UHFFFAOYSA-N 0.000 description 6
- KSCAZPYHLGGNPZ-UHFFFAOYSA-N 3-chloropropyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)CCCCl KSCAZPYHLGGNPZ-UHFFFAOYSA-N 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 238000010924 continuous production Methods 0.000 description 4
- 229960000935 dehydrated alcohol Drugs 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- KNTKCYKJRSMRMZ-UHFFFAOYSA-N 3-chloropropyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)CCCCl KNTKCYKJRSMRMZ-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- IJAAVDUFBXLLQL-UHFFFAOYSA-N CCO[SiH](CCCCl)OCC Chemical compound CCO[SiH](CCCCl)OCC IJAAVDUFBXLLQL-UHFFFAOYSA-N 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- CAXZYJLKQUXPBS-UHFFFAOYSA-N dichloro(3-chloropropyl)silane Chemical compound ClCCC[SiH](Cl)Cl CAXZYJLKQUXPBS-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- SLZVJHXZTOTIGX-UHFFFAOYSA-N 3-chloropropylsilicon Chemical compound [Si]CCCCl SLZVJHXZTOTIGX-UHFFFAOYSA-N 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- HICCMIMHFYBSJX-UHFFFAOYSA-N [SiH4].[Cl] Chemical compound [SiH4].[Cl] HICCMIMHFYBSJX-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- UHZZMRAGKVHANO-UHFFFAOYSA-M chlormequat chloride Chemical compound [Cl-].C[N+](C)(C)CCCl UHZZMRAGKVHANO-UHFFFAOYSA-M 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- VOVKNAOBZXBVMN-UHFFFAOYSA-N dichloro(3-chloropropyl)silicon Chemical compound ClCCC[Si](Cl)Cl VOVKNAOBZXBVMN-UHFFFAOYSA-N 0.000 description 1
- YQGOWXYZDLJBFL-UHFFFAOYSA-N dimethoxysilane Chemical compound CO[SiH2]OC YQGOWXYZDLJBFL-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000021050 feed intake Nutrition 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000010808 liquid waste Substances 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- VIKNJXKGJWUCNN-XGXHKTLJSA-N norethisterone Chemical compound O=C1CC[C@@H]2[C@H]3CC[C@](C)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3CCC2=C1 VIKNJXKGJWUCNN-XGXHKTLJSA-N 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000002572 peristaltic effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/188—Preparation; Treatments not provided for in C07F7/20 by reactions involving the formation of Si-O linkages
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
Abstract
The purpose of the present invention is provide a kind of method for preparing chloropropyl alkylalkoxy silane using pathway reaction device for industrial mass production chloropropyl alkylalkoxy silane, make chloropropyl chlorine-containing silane and excessive alcohol that esterification occur in pathway reaction device and prepare chloropropyl alkylalkoxy silane, in which: (1) chloropropyl chlorine-containing silane general structure (a) are as follows: ClC3H6SiClnR3‑n；In formula, R is methyl or ethyl, n=1,2 or 3；(2) alcohol is methanol or ethyl alcohol, and is entered in pathway reaction device with gas phase；(3) the pathway reaction device is at least connected with an after-treatment device and hydrogen chloride absorption device.Solves the problems such as enlarge-effect, adjusting of yield difficulty of large scale consersion unit, reduction is even a cancellation the disadvantage that large scale equipment belt comes.
Description
Technical field
The present invention relates to use chloropropyl chlorine-containing silane and alcohol that esterification occurs to prepare chloropropyl alkylalkoxy silane
Method, the method for more particularly preparing chloropropyl alkylalkoxy silane using pathway reaction device.
Background technique
It is that the method that esterification prepares chloropropyl alkylalkoxy silane, which occurs, using chloropropyl chlorine-containing silane and alcohol
Know, if 3- chloropropyl trichloro-silane and ethanol synthesis prepare 3- chloropropyl triethoxysilane, 3- chloropropyl trichloro-silane with
Methanol reaction preparation 3- r-chloropropyl trimethoxyl silane, 3- chloropropyl dichlorosilane react preparation 3- chloropropyl first with methanol
Base dimethoxysilane, 3- chloropropyl dichlorosilane and ethanol synthesis prepare 3- chloropropyl diethoxy silane.It should
Class esterification can generate byproduct hydrogen chloride, and hydrogen chloride and raw alcohol, which can react, generates water, and the higher side reaction of temperature is more
Fastly, hydrogen chloride coexists time longer side reaction with raw alcohol and is more obvious；And water is to have to product chloropropyl alkylalkoxy silane
Harmful, it will cause product hydrolysis polymerization, the impurity polymer content of product is high, has an impact to product yield, quality；So chlorine
Change hydrogen and coexist that the time is longer, coexisting temperature is higher with raw alcohol, chloropropyl alkylalkoxy silane is more unfavorable to preparing.In order to disappear
Subtract coexisting for hydrogen chloride and raw alcohol, as early as possible drive hydrogen chloride from reaction system away, generally using negative pressure means or uses other
Gas takes away hydrogen chloride gas, such as inert gas, or adds excessive alcohol and generate alcohol gas.
Currently, there are two ways to industrial mass production chloropropyl alkylalkoxy silane, one is still reaction interval is raw
It produces, another kind is tower reaction continuous production.The autoclave Batch Process period drives chlorination away to tens of hours up to a few hours in time
The method of hydrogen is excessively, in logical nitrogen, reaction process to add one kind or several of the means such as alkali neutralization hydrogen chloride using raw alcohol
Kind, these means bring consequences are the problems such as alcohol consumption are big, gas entrainment silane causes liquid waste processing difficult, and hydrogen chloride
Still have certain time of contact with raw alcohol, above-mentioned means can only partial reduction harmful substance water formation, it is thick after reaction
Still there are apparent condensate and excessive alcohol in product, need to distill product from crude reaction.Tower continuous production,
The time of contact of chloropropyl chlorine-containing silane and alcohol is limited, and reaction is difficult in the short time sufficiently, so generally using packed tower, alcohol mistake
Amount, counter current contacting, tower top go out the modes such as hydrogen chloride and increase reaction sufficient degree, these bring liquid flooding, entrained liquid, excessive again
The problems such as difficult containing sour ethyl alcohol, is similarly that crude reaction also needs to post-process, need to distill product；And this is continuous
Production method feeds intake production at the beginning, the streaking one of crude product, and the operation a period of time that needs to feed intake reaches to each technological parameter
The crude product of stabilised quality can be just produced after desired value.Then, both the above method is transported in conventional large scale equipment
Row, even small device is run, the product yield for the production that goes into operation every time is also all more than several tonnage grades, and yield difficulty is turned down, this is right
Market dosage is small may be monthly several hundred kilograms even tens kilograms product such as 3- chloropropylmethyldimethoxysilane,
For 3- chloropropyl diethoxy silane etc., the waste in a kind of cost will cause.In addition, such esterification is from experiment
Room lab scale is to industrial mass production, since equipment size variation makes it have apparent enlarge-effect, cause to change the line of production operating difficulties and
Period of changing the line of production is long.
Pathway reaction device has been disclosed technology, and development is very fast in recent years, has benefited from the maturation of its processing technology.But
The big industrial production that pathway reaction device is applied to chloropropyl alkylalkoxy silane is but rarely reported, at least has no its realization
Real mass production.
Summary of the invention
Technical problem: a kind of using logical the purpose of the present invention is being provided for industrial mass production chloropropyl alkylalkoxy silane
The method that road reaction unit prepares chloropropyl alkylalkoxy silane, chloropropyl chlorine-containing silane and excessive gas phase alcohol, using logical
Road reaction unit occurs esterification and prepares chloropropyl alkylalkoxy silane, solves the amplification effect of large scale consersion unit
It answers, the problems such as yield difficulty is adjusted, reduction is even a cancellation the shortcomings that large scale consersion unit is brought.
Technical solution: to achieve the above object, the invention provides the following technical scheme:
The method for preparing chloropropyl alkylalkoxy silane using pathway reaction device of the invention, makes chloropropyl silicon containing chlorine
Esterification occurs in pathway reaction device and prepares chloropropyl alkylalkoxy silane for alkane and excessive alcohol, in which:
(1) chloropropyl chlorine-containing silane general structure (a) are as follows:
ClC3H6SiClnR3-n... ... ... ..(a)
In formula, R is methyl or ethyl, n=1,2 or 3；
(2) alcohol is methanol or ethyl alcohol, and is entered in pathway reaction device with gas phase；
(3) the pathway reaction device is at least connected with an after-treatment device and hydrogen chloride absorption device.
Preferably, the material in the channel is that the channel surface that tantalum material or reaction stream touch plates enamel or uses Teflon
Dragon processing.
Preferably, it is equipped with filter device before the pathway reaction device or pathway reaction device is equipped with filtering function.
Preferably, the hydrogen chloride absorption device is in parallel with after-treatment device, or is successively pathway reaction device, rear place
Manage device, hydrogen chloride absorption device.
Preferably, the hydrogen chloride absorption device is the absorption plant of no less than two-stage, the absorption of first order absorption plant
Liquid is water, and the absorbing liquid of other absorption plants is one or more of mixing of water, sodium hydrate aqueous solution or other aqueous slkalis.
Preferably, the chloropropyl chlorine-containing silane and alcohol, on the basis of reaction mass ratio, alcohol is excessive.
Preferably, the alcohol excessive 0.01% ~ 10%, more preferable 0.05% ~ 2%.
Preferably, reaction temperature is 0 DEG C -300 DEG C.
Preferably, reaction temperature is 10 DEG C -180 DEG C.More preferable 30 DEG C -150 DEG C.
Preferably, the channel equivalent diameter of pathway reaction device is at 100 microns -1 centimetre, more preferably in 1 millimeter of -10 milli
Rice.
Preferably, the passage length of pathway reaction device is at several meters-tens meters.
The channel size of pathway reaction device described in the method for the present invention refers to 1 micron-several centimeters of channel, preferably
It is that the present invention carries out in 100 microns -1 centimetre of pathway reaction device in equivalent diameter.
The channel of pathway reaction device described in the method for the present invention has collet heat-exchange device, can make in channel
Reaction stream temperature is stablized in the desired range.
Chloropropyl chlorine-containing silane and byproduct hydrogen chloride described in the method for the present invention all contain elemental chlorine, to stainless steel,
Carbon steel material has corrosion, and the pathway reaction device service life of these materials is short, so the material of lane device of the invention is excellent
It plates enamel or is handled with Teflon in the channel surface for selecting tantalum material or reaction stream to touch.
Hydrogen chloride absorption device described in the method for the present invention can be large-sized equipment, such as film-falling absorption tower, filler
Tower etc. is also possible to channel absorption plant, such as micro-channel absorber.The effect of after-treatment device is received to crude reaction
Collection, or the equipment as distillation process and neutralization step simultaneously；It is collected preferably as crude product, the equipment of distillation and neutralization.
Pathway reaction device described in the method for the present invention has no less than one reaction zone, and reaction zone channel is usually all
With micro-structure.Micro-structure is the mixing and collision opportunity (probability) in order to improve reaction stream, and carries out special processing to channel,
Such as the channel table mask that there is inner member or channel to extend in different forms or touch with reaction stream in channel is defective
Deng.Pathway reaction device can also have other areas, such as filtering area, preheating zone, pre-mix zone, these regions have at least one function
Energy.Pathway reaction device can also have other function, such as filtering function, pre- heat function, pre-mixing function, these functions can divide
It does not realize in a region, can also realize at least two or more function in a region.
Method of the present invention, reaction can be in single pathway reaction device or multiple channels in series or in parallel
It is carried out in reaction unit.Described device channel can have various forms of cross sections, such as circle, ellipse, quadrangle, more
The shapes such as side shape, heart.Conversion (equivalence) diameter in channel can be 1 micron-several centimeters, preferably at 100 microns -1 centimetre, more
It is preferred that at 1 millimeter -10 millimeters.The length in above-mentioned apparatus channel theoretically makes reaction proceed to production concentration almost unchanged, and one
As at 1 centimetre-hundreds of meters, preferably in several meters-tens of rice.
To water, moisture-sensitive, serious conditions can be generated for chloropropyl chlorine-containing silane described in the method for the present invention and product
Solid bits, which block pipeline, influences production, in order to avoid the unnecessary downtime, so being more preferably before pathway reaction device
There are filter device or pathway reaction device that there is filtering function, preferably has filter device before pathway reaction device.
Chloropropyl chlorine-containing silane described in the method for the present invention and alcohol enter above-mentioned logical after can mixing in other devices
Road reaction, can also respectively enter hybrid reaction in above-mentioned lane device, other devices here refer to mixed function
Large-sized equipment or microreactor or lane device.Lane device of the invention has the micro-structure of mixed function, so
Raw material chloropropyl chlorine-containing silane and alcohol, which can be directly entered in lane device, to react, and does not need to be pre-mixed in advance.
It is excellent into hybrid reaction in above-mentioned lane device after raw material can preheat in other devices in the method for the present invention
It is selected in after being preheated in other devices and enters in pathway reaction device.
Chloropropyl chlorine-containing silane described in the method for the present invention and the intermediate products not being esterified completely all contain chlorine, to subsequent
The material of processing equipment has a particular/special requirement, and post-treatment operations program is complicated, feeds intake excess it is advantageous to alcohol, makes chloropropyl containing chlorine
Silane and the intermediate products not being esterified completely can sufficiently react；On the basis of reaction mass ratio, preferred alcohols excessive 0.01% ~
10%, more preferable 0.05% ~ 2%.
In the method for the present invention, reaction is carried out in microchannel, and the hydrogen chloride gas for reacting generation is difficult through negative pressure
Means are carried over system, if very big pressure cannot will be generated in system in time by the hydrogen chloride discharge system of generation.If alcohol
Enter channel with gas phase, the volume of gas phase can be compressed, and isometric ethyl alcohol at most generates isometric chlorine
The case where changing hydrogen, not will cause high pressure in channel, equipment material, processing and the production operation that not will cause channel have spy
It is different to require.It is that alcohol is entered in channel with gas phase and reacted in this way.
The utility model has the advantages that compared with prior art, the invention has the following advantages that
(1) method of the present invention is channel-type reaction, can with continuous production, can continuous and steady operation a couple of days to number
Month；
(2) pathway reaction is also referred to as microreactor, and have the advantages that microreactor equipment: heat and mass is fast, technological parameter
Such as temperature is easy to control, changes small, safe operation, and the small land occupation of equipment volume is few etc.；
(3) elasticity of output is big, can flexible arrangement production, produce several grams to tens of thousands of tons products as needed；
(4) channel-type reacts, and heat and mass is fast, enlarge-effect of not changing the line of production, operation of changing the line of production from laboratory to industrial production
It is easy.
(5) pathway reaction device is used, the residence time is short in the channel for reaction stream, almost inhibits the pair of hydrogen chloride and alcohol
Reaction, byproduct condensation body content is low, and product quality and yield are improved；
(6) pathway reaction device has the function of strengthening mixing, and it is abundant that reaction stream contacts fast reaction in the channel, impurity
" intermediate products not being esterified completely " content is low, and gas entrained liquids are few, and alcohol consumption is low, the three wastes are few, by-product salt
Sour impurity is few；
(7) pathway reaction device, sufficiently, impurity is few in crude product for reaction stream reaction, for the not high specification of quality requirement, after
Continuous processing can only distill out impurity and retained product, shorten post-processing working hour.
Detailed description of the invention
Fig. 1 ~ Fig. 3 is the schematic diagram for implementing pathway reaction device of the invention.
Fig. 1 is Flapper type pathway reaction device schematic diagram.
Fig. 2 is undaform pathway reaction device schematic diagram.
Fig. 3 is flat heart-type pathway reaction device schematic diagram.
Specific embodiment
It is intended to that the present invention is explained in greater detail by following embodiment, but is not intended to limit subject of the present invention.
Fig. 1 ~ Fig. 3 is the schematic diagram for implementing pathway reaction device of the invention, it is intended that illustrates the appearance of channel micro-structure, but this
Invention is not limited to that these pathway reaction devices are used only.
The pathway reaction device that following embodiment is selected is tantalum material, flat heart-type, and conversion diameter is 8 millimeters in channel, long
Degree is 75 meters, and the heat medium of pathway reaction device is oil bath heating, and cooling medium is chilled brine, after pathway reaction device according to
Secondary to connect the collection device with refrigerating function and secondary chlorination hydrogen absorption plant, absorbing liquid is respectively that water and sodium hydroxide are water-soluble
Liquid.Raw material chloropropyl chlorine-containing silane and alcohol pass through filtration treatment before entering pathway reaction device.
Comparative example 1 prepares 3- chloropropyl triethoxysilane using intermittent reaction
Reaction unit is three-necked flask of the 1000mL with stirring, thermometer and reflux, successively water receiving absorption after the branch pipe that flows back
With sodium hydrate aqueous solution absorption plant.Add 212g 3- chloropropyl trichloro-silane (content 98.9%) into three-necked flask, it will be warm
Degree is raised to 60 DEG C and starts that 160g dehydrated alcohol (content 99.6%) is added dropwise, and for control reaction temperature at 85 DEG C -95 DEG C, knot is added dropwise in ethyl alcohol
2h is kept the temperature after beam, is then cooled to 30 DEG C or less.Crude product is taken to do gas chromatographic detection, ethanol content 8.3% in crude product, not completely
Intermediate products content 0.6%, the 3- chloropropyl triethoxysilane content of esterification are 86.8%, polymer content 1.6%；Water absorbs
Hydrochloric acid in device is white opacity liquid.
Comparative example 2 prepares 3- chloropropyl triethoxysilane using tower successive reaction
Reaction unit be internal diameter 4cm, length 2m, the interior packed tower for filling Θ ring plastics, under connect 1000mL three-necked flask conduct
Reception device, tower top go out hydrogen chloride gas, are followed by that the water jet absorption plant of tiny structure can be formed.Dehydrated alcohol (content
99.6%) enter packed tower from lower feed inlet with steam condition, 3- chloropropyl trichloro-silane (content 98.9%) from enterprising material mouth with
Liquid condition enters packed tower, with peristaltic pump control feed material feed rates, keep dehydrated alcohol: 3- chloropropyl trichloro-silane with
Mass ratio 152:212 charging controls 65 DEG C -70 DEG C of tower top temperature, takes from time liquid of three-necked flask after stable operation half an hour
Sample does gas chromatographic detection, ethanol content 4.9%, the intermediate products content 0.4% not being esterified completely, three second of 3- chloropropyl in crude product
Oxysilane content is 90.6%, polymer content 0.8%；Hydrochloric acid in water absorption plant is micro- turbid liquid.
Embodiment 1 prepares 3- chloropropyl triethoxysilane
Raw material chloropropyl trichloro-silane (content 98.9%) is preheated to 60 DEG C, dehydrated alcohol (content 99.6%) is heated to form
Alcohol vapour, two kinds of raw materials are entered in pathway reaction device with mass ratio 212:140 to be reacted, and the flow velocity for controlling reaction stream is
30Kg/h, reaction temperature are 120 DEG C, take crude product to do gas chromatographic detection from collection device, take hydrochloric acid sample from water absorption plant
Product observe appearance, and testing result is ethanol content 0.6%, the intermediate products content 0.2% not being esterified completely, 3- chlorine third in crude product
Ethyl triethoxy silicane alkane content is 96.9%, polymer content < 0.1%；Hydrochloric acid in water absorption plant is transparent, without Suspension hydrolysis
Silane.
Embodiment 2 prepares 3- chloropropylmethyldimethoxysilane
Raw material chloropropyl dichlorosilane (content 99.2%) is preheated to 50 DEG C, anhydrous methanol (content 99.8%) added
At methanol steam, two kinds of raw materials are entered in pathway reaction device with mass ratio 191.5:65 to be reacted heat, controls reaction stream
Flow velocity is 30Kg/h, reaction temperature is 115 DEG C, takes crude product to do gas chromatographic detection from collection device, takes from water absorption plant
Hydrochloric acid sample observation appearance, testing result be, methanol content 0.4% in crude product, the intermediate products content 0.2% not being esterified completely,
3- chloropropylmethyldimethoxysilane content is 98.9%, polymer content < 0.1%；Hydrochloric acid in water absorption plant is transparent,
Without Suspension hydrolysis silane.
It is obtained by above-mentioned comparison, the present invention uses pathway reaction device, and the residence time is short in the channel for reaction stream, almost
The side reaction of hydrogen chloride and alcohol is inhibited, byproduct condensation body content is low, and product quality and yield are improved.Pathway reaction
Device has the function of strengthening mixing, and reaction stream contacts that fast reaction is abundant in the channel, and " what is be not esterified completely intermediate produces impurity
Product " content is low, and gas entrained liquids are few, and alcohol consumption is low, the three wastes are few, and by-product hydrochloric acid impurity is few.Pathway reaction device, reaction stream
Sufficiently, impurity is few in crude product, and for the not high specification of quality requirement, subsequent processing only can distill out impurity and retain for reaction
Product shortens post-processing working hour.
Claims (3)
1. a kind of method for preparing chloropropyl alkylalkoxy silane using pathway reaction device, which is characterized in that make chloropropyl
Esterification occurs in pathway reaction device and prepares chloropropyl alkylalkoxy silane for chlorine-containing silane and excessive alcohol, in which:
(1) chloropropyl chlorine-containing silane general structure (a) are as follows:
ClC3H6SiClnR3-n……………..(a)
In formula, R is methyl or ethyl, n=1,2 or 3；
(2) alcohol is methanol or ethyl alcohol, and is entered in pathway reaction device with gas phase；Chloropropyl chlorine-containing silane and alcohol, with anti-
On the basis of answering mass ratio, alcohol excess 0.01%-10%；
(3) the pathway reaction device is at least connected with an after-treatment device and hydrogen chloride absorption device；
(4) the channel equivalent diameter of pathway reaction device is at 100 microns -1 centimetre；The passage length of pathway reaction device is several
- tens meters of rice；The material in channel is that the channel surface that tantalum material or reaction stream touch is plated enamel or handled with Teflon；It is logical
It is equipped with filter device before road reaction unit or pathway reaction device is equipped with filtering function；
(5) reaction temperature is 10 DEG C -180 DEG C.
2. the method according to claim 1 for preparing chloropropyl alkylalkoxy silane using pathway reaction device, special
Sign is that the hydrogen chloride absorption device is in parallel with after-treatment device, or be successively pathway reaction device, after-treatment device,
Hydrogen chloride absorption device.
3. the method according to claim 1 for preparing chloropropyl alkylalkoxy silane using pathway reaction device, special
Sign is that the hydrogen chloride absorption device is the absorption plant of no less than two-stage, and the absorbing liquid of first order absorption plant is water,
The absorbing liquid of his absorption plant is one or more of mixing of water, sodium hydrate aqueous solution or other aqueous slkalis.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610162597.9A CN105693759B (en) | 2016-03-22 | 2016-03-22 | The method for preparing chloropropyl alkylalkoxy silane using pathway reaction device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610162597.9A CN105693759B (en) | 2016-03-22 | 2016-03-22 | The method for preparing chloropropyl alkylalkoxy silane using pathway reaction device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105693759A CN105693759A (en) | 2016-06-22 |
| CN105693759B true CN105693759B (en) | 2019-04-26 |
Family
ID=56232237
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610162597.9A Active CN105693759B (en) | 2016-03-22 | 2016-03-22 | The method for preparing chloropropyl alkylalkoxy silane using pathway reaction device |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105693759B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107551967B (en) * | 2017-08-11 | 2020-05-05 | 上海交通大学 | Microchannel device for microreactors |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102199168A (en) * | 2010-03-25 | 2011-09-28 | 日照岚星化工工业有限公司 | Novel synthetic technology of gamma-chloropropyl triethoxysilane |
| US20130053567A1 (en) * | 2010-03-04 | 2013-02-28 | Kyoto University | Method for producing silylenol ethers |
| WO2013123213A1 (en) * | 2012-02-16 | 2013-08-22 | Dow Corning Corporation | Method of reducing a halosilane compound in a microreactor |
-
2016
- 2016-03-22 CN CN201610162597.9A patent/CN105693759B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130053567A1 (en) * | 2010-03-04 | 2013-02-28 | Kyoto University | Method for producing silylenol ethers |
| CN102199168A (en) * | 2010-03-25 | 2011-09-28 | 日照岚星化工工业有限公司 | Novel synthetic technology of gamma-chloropropyl triethoxysilane |
| WO2013123213A1 (en) * | 2012-02-16 | 2013-08-22 | Dow Corning Corporation | Method of reducing a halosilane compound in a microreactor |
| CN104203962A (en) * | 2012-02-16 | 2014-12-10 | 道康宁公司 | Method of reducing halosilane compound in microreactor |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105693759A (en) | 2016-06-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| RU2009107980A (en) | INSTALLATION AND METHOD OF CONTINUOUS INDUSTRIAL PRODUCTION OF FLUORALKYL CHLOROSILANE | |
| CN105601661B (en) | The method for preparing mercaptosilane coupling agents using pathway reaction device | |
| CN105732986B (en) | A kind of technique preparing Methyl Hydrogen Polysiloxane Fluid | |
| CN105693759B (en) | The method for preparing chloropropyl alkylalkoxy silane using pathway reaction device | |
| CN107089952A (en) | The method that 5 Flucytosines are prepared using micro passage reaction | |
| CN110117216A (en) | A kind of continuous flow preparation method of 2,6- diethyl -4- methyl bromobenzene | |
| CN109593030A (en) | A kind of α, the preparation method of alpha-single chloro acetophenone compounds | |
| CN102502566A (en) | Technology for synthesizing lithium hexafluorophosphate | |
| CN208883750U (en) | A kind of serialization prepare glycine around pipe reaction device | |
| CN110156631A (en) | A kind of continuous flow preparation method of 2,6- diethyl -4- methylaniline diazonium salt | |
| CN106905189B (en) | Microreactor system and method for bis- (propionitrile) the ether synthesis of ethylene glycol | |
| CN110841585A (en) | Benzyl cyanide production device and use method thereof | |
| CN116462655A (en) | Process for preparing chloroethylene carbonate | |
| CN111116437A (en) | Method and apparatus for producing 2-hydroxy-4-methylthiobutyric acid and intermediate thereof | |
| CN113501841B (en) | Method for continuously preparing sulfur-containing silane coupling agent | |
| CN105597508B (en) | Method is absorbed and utilized in a kind of poly- methyltriethoxysilane reaction end gas | |
| CN105198913B (en) | Method for preparing chloromethyl trichlorosilane | |
| CN107522638A (en) | Prepare the microreactor and method of o-methyl formate benzene sulfonamide | |
| CN105693760B (en) | The method for preparing polysulfide silanes coupling agent using pathway reaction device | |
| CN109081772B (en) | Process and device capable of effectively improving chlorination reaction production efficiency of 4-chloro-3, 5-dimethylphenol | |
| CN109364869A (en) | A kind of device of gas-liquid countercurrent method continuous production chloro thing | |
| CN111675607A (en) | Method for producing trimethyl orthoacetate through differential circulation and continuous production | |
| CN106673978B (en) | 3,5- Dichloro-2-pentanone is continuously synthesizing to method | |
| CN103819480A (en) | Continuous production technology for tetra-aryl-bi-metal porphyrin | |
| CN110590556A (en) | Preparation method of fluorine-containing asymmetric chain carbonate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP01 | Change in the name or title of a patent holder | ||
| CP01 | Change in the name or title of a patent holder |
Address after: No. 226, Chongfu Road, Nanjing Chemical Industrial Park, Nanjing, Jiangsu 210047 Patentee after: Nanjing Shuguang Fine Chemical Co.,Ltd. Address before: No. 226, Chongfu Road, Nanjing Chemical Industrial Park, Nanjing, Jiangsu 210047 Patentee before: NANJING SHUGUANG FINE CHEMICAL CO.,LTD. |