CN101195564B - Method for producing trichloro-acetic chloride with by-product in organic acyloxy silicone hydride production process - Google Patents
Method for producing trichloro-acetic chloride with by-product in organic acyloxy silicone hydride production process Download PDFInfo
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- CN101195564B CN101195564B CN2007101647184A CN200710164718A CN101195564B CN 101195564 B CN101195564 B CN 101195564B CN 2007101647184 A CN2007101647184 A CN 2007101647184A CN 200710164718 A CN200710164718 A CN 200710164718A CN 101195564 B CN101195564 B CN 101195564B
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Abstract
The invention discloses a method for preparing trichloroacetyl chloride by utilizing by-product in the production procedure of organic acyloxy radical silane. The by-product from the production procedure of organic acyloxy radical silane is contacted with chlorine gas under light source irradiation to do photo-chlorination reaction. The mass ratio of the by-product in the production procedure of organic acyloxy radical silane to chlorine gas is 1: 1-9. The photo-chlorination gas phase reaction temperature is 60-200 DEG C and the photo-chlorination reaction time is 1-24 h. The invention is not only simple and feasible in producing flow path, easy in industrialization, low in equipment investment cost, stable in operational security property, but also high in raw material conversion rate, less in impurity of reaction product, easy in purification and separation and the like.
Description
Technical field
The present invention relates to the synthetic field of meticulous organic products, relate in particular to a kind of method of utilizing by product in the organic acyloxy silicone hydride production process to prepare trichoroacetic chloride.
Background technology
Methyl triacetoxysilane, ethyl triacetoxysilane and vinyltriacetoxy silane are a class linking agent or coupling agents of single-component room-temperature vulcanized silicone rubber, and purposes is very extensive.General manufacturer is the above-mentioned quality products that obtains high purity and low chlorine ion content, all be that employing METHYL TRICHLORO SILANE and aceticanhydride, ethyl triacetoxysilane and aceticanhydride or vinyl trichloro silane and aceticanhydride are that raw material reaction obtains mostly in the production, its main chemical reactions equation is as follows respectively:
C
2H
5SiCl
3+3(CH
3CO)
2O→C
2H
5Si(OCOCH
3)
3+3CH
3COCl
CH
3SiCl
3+3(CH
3CO)
2O→CH
3Si(OCOCH
3)
3+3CH
3COCl
CH
2＝CHSiCl
3+3(CH
3CO)
2O→CH
2＝CHSi(OCOCH
3)
3+3CH
3COCl
By above-mentioned reaction formula as can be known, above technology is when obtaining the organic acyloxy silicone hydride product, correspondingly also produce a large amount of by products, wherein contain the Acetyl Chloride 98Min. about 90～97% in this by product, all the other major impurities are aceticanhydride, acetic acid, tri-methyl-chlorosilane or silicon tetrachloride.Since in the impurity for example the boiling point of tri-methyl-chlorosilane Acetyl Chloride 98Min. is separated with impurity with methods such as distillation are very difficult with Acetyl Chloride 98Min. is very approaching and form azeotrope easily with Acetyl Chloride 98Min..Just because of the existence of these impurity, make that the range of application of Acetyl Chloride 98Min. is restricted greatly in this by product.
Because Acetyl Chloride 98Min. is volatile and the strong impulse smell is arranged, corrodibility is very strong, and unprocessed discharging then can cause waste and contaminate environment.Rapid increase along with organosilicon macromolecule product usage quantity in the national economy life, the industrial scale of methyl triacetoxysilane, ethyl triacetoxysilane and vinyltriacetoxy silane is also in further expansion, also caused that a large amount of Acetyl Chloride 98Min. by products produces in the production process simultaneously.If these by products can not be utilized effectively, solve its outlet difficult problem, will have a strong impact on the ecotope generation, and be an impediment to the healthy Sustainable development of organosilicon industry.
Trichoroacetic chloride has very high chemically reactive, can with the multiple active olefin formation heterogeneous ring compound that reacts, being the main intermediate of preparation large-tonnage sterilant Chlorpyrifos series product, also is the important source material of preparation large-tonnage weedicide greenweed pyridine and other pesticide species.
Chinese patent CN1562941 discloses a kind of method for preparing trichoroacetic chloride with mother liquor of chloroacetic acid.It is that mother liquor of chloroacetic acid is distilled earlier the refining low-boiling-point substance impurity of removing under 140 ℃; Mother liquor of chloroacetic acid after refining feeds chlorine and carries out chloride under the sulfur monochloride effect, makes the acyl chlorides mixture, and rectifying separation gets monochloro-acetyl chloride, dichloroacetyl chloride mixture again; The mixture of acyl chloride reaction being that catalyzer, gac are to feed chlorine under the effect of promotor to carry out chlorination with the pyridine, is promptly made the tribromo-acetyl chlorine products after the rectifying.
It is the method for catalytic material synthesizing trichloroacetyl chlorine with the zellon that Chinese patent CN1323778 discloses a kind of.This method mainly is to be raw material with the zellon, adopts catalyzer, synthesizing trichloroacetyl chlorine under UV-irradiation.
It is the technology of raw material synthesizing trichloroacetyl chlorine under catalyst action and uviolizing with zellon and oxygen that Chinese patent CN1287996 discloses a kind of, it is in the photooxidation reaction device, add zellon and catalyzer, feed the oxygen of 0.01～10MPa under 110～150 ℃ of temperature, 4h～20h reacts completely synthesizing trichloroacetyl chlorine in the ultraviolet source radiation.
Chinese patent CN1260344 also discloses a kind of preparation method of trichoroacetic chloride, carry out as follows: (1) adds reactor with zellon, oxygen, catalyzer, be warming up to 180～260 ℃, after question response temperature in the kettle, the pressure-stabilisation, logical oxygen to 1.0～6.5MPa, in time remove reaction heat, logical then oxygen to reaction ends; (2) will react back feed liquid input chlorination tank, make that remaining zellon is converted into hexachloroethane in the system; (3) with feed liquid input rectifying still after the chlorination, separate and the collection trichoroacetic chloride.
Chinese patent CN1181370 has proposed a kind of preparation method of trichoroacetic chloride, and it comprises the steps: that (A) makes dichloroacetyl chloride with trieline oxidizing reaction under Diisopropyl azodicarboxylate, triethylamine effect, separates; (B) dichloroacetyl chloride chlorination reaction under pyridine, homologue or derivative effect is made trichoroacetic chloride; (C) get finished product through rectifying separation.
The most reactions steps complexity of above patent, and have in the processing condition that high pressure, reaction time are long, easily have shortcoming such as potential safety hazard in operational difficulty and the production process.Also caused simultaneously its reaction intermediate complicated with final product and separate comparatively shortcoming such as difficulty of purification.
Summary of the invention
The present invention is for solving the problem of outlet of by product Acetyl Chloride 98Min. in the organoacetoxysilane series products production process, simultaneously also for overcoming the deficiency of existing trichoroacetic chloride production technique.The method for preparing trichoroacetic chloride that a kind of cost is low, feed stock conversion is high is provided.
A kind of method of utilizing by product in the organic acyloxy silicone hydride production process to prepare trichoroacetic chloride, under the irradiation of ultraviolet lamp or incandescent light source, by product in the organic acyloxy silicone hydride production process contacted with chlorine carry out light chlorination gas-phase reaction, collecting reaction product, with the reaction product air distillation, collect 114～116 ℃ of fractions and obtain trichoroacetic chloride;
By product in the described organic acyloxy silicone hydride production process comprises that mainly mass content accounts for 90～97% Acetyl Chloride 98Min., and other impurity is aceticanhydride, acetic acid, tri-methyl-chlorosilane or silicon tetrachloride.
In the light chlorination gas-phase reaction, the consumption of the by product in the organic acyloxy silicone hydride production process is in Acetyl Chloride 98Min., and the mass ratio of Acetyl Chloride 98Min. and chlorine is 1: 1～9, and preferred 1: 3～6;
Light chlorination gas-phase reaction temperature is 60～200 ℃, preferred 60～120 ℃;
The light chlorination gas-phase reaction time is 1～24h; Preferred 3～8h.
The mass ratio of Acetyl Chloride 98Min. and chlorine in the by product, the flow of Acetyl Chloride 98Min. gas can be controlled with the quality that feeds intake by the rate of heating of Acetyl Chloride 98Min. in the reactor usually, and the mass rate of chlorine is then proofreaied and correct control metering afterwards by under meter.
Light chlorination gas-phase reaction device of the present invention comprises liquid chlorine cylinder, surge tank, spinner-type flowmeter, movable light source irradiating unit, reactor, packing tower, optical chlorinating reaction device, condenser and hydrogen chloride absorption device.
Load corrosion-resistant filling in the described packing tower, as glass spring etc.
Described smooth chlorination gas-phase reaction temperature is the temperature in the reactor.Wherein the temperature of reaction in the light chlorination Gas-phase reactor is mainly controlled by reactor heating intensity speed.
When reaction, the evaporating capacity of raw material can be controlled by heating unit in the reactor; Need to be furnished with filled column between reactor and the Gas-phase reactor, its purpose is to guarantee fully separating of raw material and final purpose product trichoroacetic chloride.The material of optical chlorinating reaction device Gas-phase reactor can adopt general glass, but also adopting quartz glass.The reactor light source can adopt ultraviolet lamp or incandescent light can guarantee that all successful reaction carries out, and the selection of light source power can change according to the concrete size of optical chlorinating reaction device; The distance of light source and reactor can move up and down and move left and right according to slide bar.
When the inventive method is implemented, to put into reactor by the load weighted Acetyl Chloride 98Min. of predetermined proportion earlier, form gas by heating vaporization back, in packing tower, enter Gas-phase reactor behind the thorough mixing with chlorine then from liquid chlorine cylinder, under ultraviolet lamp or incandescent light irradiation, in the optical chlorinating reaction device, carry out optical chlorinating reaction, generate dichloroacetyl chloride or trichoroacetic chloride.The mixing crude product that forms in the reaction is back in the reactor immediately, and reaction so circulation is carried out.As long as controlling the heating vaporization rate of reactor and chlorine well feeds flow, just can guarantee that 95～100% raw material Acetyl Chloride 98Min. is chlorinated fully and be trichoroacetic chloride that the by-product HCl gas of generation is absorbed by alkali lye.Question response 3～8h can remove other small amount of impurities that contains in the product by methods such as distillations after finishing, and obtains the higher product trichoroacetic chloride of purity.
The boiling point of tri-methyl-chlorosilane and Acetyl Chloride 98Min. is very approaching and form azeotrope easily with Acetyl Chloride 98Min. for example in the impurity separates Acetyl Chloride 98Min. with methods such as distillation are very difficult in the by product in the organic acyloxy silicone hydride production process with impurity.But Acetyl Chloride 98Min. is converted into after the trichoroacetic chloride, differs bigger with the boiling point of impurity such as tri-methyl-chlorosilane, is easy to separate the utilization that has solved by product.
The inventive method not only Production Flow Chart is simple and easy to do, easily industrialization, and equipment investment cost is low, and the operational safety performance is stable, and has the feed stock conversion height, and impurity is less in the reaction product, and advantages such as separation are easy to purify.
Description of drawings
Fig. 1 is the process flow diagram of the inventive method, among the figure:
1, liquid chlorine cylinder; 2, surge tank; 3, spinner-type flowmeter;
4, movable light source irradiating unit; 5, reactor; 6, packing tower;
7, optical chlorinating reaction device; 8, condenser; 9, hydrogen chloride absorption device
Embodiment
Among each embodiment adopted form from its mass content of by product in the organic acyloxy silicone hydride production process and be through the gas chromatography-mass spectrography analysis: Acetyl Chloride 98Min. 94.46%, aceticanhydride 0.23%, acetic acid is 0.17%, tri-methyl-chlorosilane 1.17%, silicon tetrachloride 2.98%.
Embodiment 1
Reaction unit as shown in Figure 1, it is the reactor light source that the inventive method adopts ultraviolet lamp.Add by product in the 700g organic acyloxy silicone hydride production process in the 1000ml reactor, the air in earlier logical a small amount of chlorine replacement(metathesis)reaction system is controlled temperature of reaction kettle then at 70 ℃, opens condensation reflux device.Treat reactor temperature in the system, reflux stable after, slowly open the chlorine valve, this moment, reaction was carried out immediately, light chlorination gas-phase reaction actuator temperature is to have drop to occur on the wall of 65 ℃ and reactor, tail gas is strongly-acid.Should control rate of heating this moment, makes backflow moderate, should control chlorine flowrate simultaneously, and the mass ratio that makes trichoroacetic chloride and chlorine is about 1: 4.Along with proceeding of reaction, the temperature in the Gas-phase reactor can constantly raise, stopped reaction when question response still temperature is increased to 118 ℃, and 8h has been carried out in reaction altogether.Get the product sample and carry out the gas chromatography-mass spectrography analysis, wherein do not contain Acetyl Chloride 98Min., dichloroacetyl chloride 5.23%, tetracol phenixin 2.15%, trichoroacetic chloride 92.34%.
Reaction product is carried out air distillation, 80～110 ℃ of cut recovery set usefulness, collecting 114～116 ℃ of cuts is the product trichoroacetic chloride, and product yield is 91.68%, and adopting its purity of gas chromatographic analysis is 99.93%.
Embodiment 2
Reaction unit as shown in Figure 1, adopting ultraviolet lamp is the reactor light source.Add by product in the 800g organic acyloxy silicone hydride production process in the 1000ml reactor, the air in earlier logical a small amount of chlorine replacement(metathesis)reaction system is controlled temperature of reaction kettle then at 72 ℃, opens condensation reflux device.Treat reactor temperature in the system, reflux stable after, slowly open the chlorine valve, this moment, reaction was carried out immediately, light chlorination gas-phase reaction actuator temperature is to have drop to occur on the wall of 67 ℃ and reactor, tail gas is strongly-acid.Should control rate of heating this moment, makes backflow moderate, should control chlorine flowrate simultaneously, and the mass ratio that makes trichoroacetic chloride and chlorine is about 1: 6.Along with the continuation fierceness of reaction is carried out, the temperature in the Gas-phase reactor can constantly raise.Stopped reaction when question response still temperature is increased to 120 ℃, 4h has been carried out in reaction altogether.Get the product sample and carry out the gas chromatography-mass spectrography analysis, wherein do not contain Acetyl Chloride 98Min., dichloroacetyl chloride 6.63%, tetracol phenixin 4.05%, trichoroacetic chloride 89.14%.
Reaction product is carried out air distillation, 80～110 ℃ of cut recovery set usefulness, collecting 114～116 ℃ of cuts is the product trichoroacetic chloride, and product yield is 88.47%, and adopting its purity of gas chromatographic analysis is 99.67%.
Embodiment 3
Reaction unit adopts incandescent light to be the reaction light source as shown in Figure 1.Add by product in the 700g organic acyloxy silicone hydride production process in the 1000ml reactor, the air in earlier logical a small amount of chlorine replacement(metathesis)reaction system is controlled temperature of reaction kettle then at 70 ℃, opens condensation reflux device.Treat reactor temperature in the system, reflux stable after, slowly open the chlorine valve, this moment, reaction was carried out immediately, the gas-phase reaction actuator temperature is to have drop to occur on the wall of 62 ℃ and reactor, tail gas is strongly-acid.Should control rate of heating this moment, makes backflow moderate, controls chlorine flowrate simultaneously, and the mass ratio that makes trichoroacetic chloride and chlorine is about 1: 6.Along with the continuation fierceness of reaction is carried out, the temperature in the Gas-phase reactor can constantly raise.Question response still temperature stops heating when being increased to 120 ℃, reaction is carried out getting the product sample behind the 8h and carried out the gas chromatography-mass spectrography analysis, does not contain Acetyl Chloride 98Min. in the product liquid, dichloroacetyl chloride 2.63%, tetracol phenixin 1.05% trichoroacetic chloride 96.11%.
Reaction product is carried out air distillation, 80～110 ℃ of cut recovery set usefulness, collecting 114～116 ℃ of cuts is the product trichoroacetic chloride, and product yield is 95.57%, and adopting its purity of gas chromatographic analysis is 99.84%.
Embodiment 4
Reaction unit as shown in Figure 1.Add by product in the 800g organic acyloxy silicone hydride production process in the 1000ml reactor, the air in earlier logical a small amount of chlorine replacement(metathesis)reaction system is controlled temperature of reaction kettle then at 70 ℃, opens condensation reflux device.Treat reactor temperature in the system, reflux stable after, slowly open the chlorine valve, this moment, reaction was carried out immediately, light chlorination gas-phase reaction actuator temperature is to have drop to occur on 60 ℃ and the wall of reactor, tail gas is strongly-acid.Should control rate of heating this moment, makes backflow moderate, should control chlorine flowrate simultaneously, and the mass ratio that makes trichoroacetic chloride and chlorine is about 1: 4.Along with the continuation fierceness of reaction is carried out, the temperature in the Gas-phase reactor can constantly raise.Question response still temperature stops heating when being increased to 120 ℃, reaction is carried out getting the product sample behind the 4h and carried out the gas chromatography-mass spectrography analysis, does not contain Acetyl Chloride 98Min. in the product liquid, dichloroacetyl chloride 8.63%, tetracol phenixin 4.05%, trichoroacetic chloride 87.14%.
Reaction product is carried out air distillation, 80～110 ℃ of cut recovery set usefulness, collecting 114～116 ℃ of cuts is the product trichoroacetic chloride, and product yield is 86.79%, and adopting its purity of gas chromatographic analysis is 99.76%.
Embodiment 5
Reaction unit as shown in Figure 1.In the 1000ml reactor, add by product in the 750g organic acyloxy silicone hydride production process, the air in earlier logical a small amount of chlorine replacement(metathesis)reaction system, the control temperature of reaction kettle is opened condensation reflux device at 65 ℃ earlier then.Treat reactor temperature in the system, reflux stable after, slowly open the chlorine valve, this moment, reaction was carried out immediately, light chlorination gas-phase reaction actuator temperature is to have drop to occur on the wall of 60 ℃ and reactor, tail gas is strongly-acid.Should control rate of heating this moment, makes backflow moderate, should control chlorine flowrate simultaneously, and the mass ratio that makes trichoroacetic chloride and chlorine is about 1: 5.Along with the continuation fierceness of reaction is carried out, the temperature in the Gas-phase reactor can constantly raise.Question response still temperature stops heating when being increased to 120 ℃, reaction is carried out getting the product sample behind the 8h and carried out the gas chromatography-mass spectrography analysis, does not contain Acetyl Chloride 98Min. in the product liquid, dichloroacetyl chloride 0.76%, tetracol phenixin 4.65%, trichoroacetic chloride 94.43%.
Reaction product is carried out air distillation, 80～110 ℃ of cut recovery set usefulness, collecting 114～116 ℃ of cuts is the product trichoroacetic chloride, and product yield is 93.77%, and adopting its purity of gas chromatographic analysis is 99.82%.
Claims (4)
1. method of utilizing by product in the organic acyloxy silicone hydride production process to prepare trichoroacetic chloride, it is characterized in that: under the irradiation of ultraviolet lamp or incandescent light source, by product in the organic acyloxy silicone hydride production process contacted with chlorine carry out light chlorination gas-phase reaction, collecting reaction product, with the reaction product air distillation, collect 114～116 ℃ of fractions and obtain trichoroacetic chloride; By product in the described organic acyloxy silicone hydride production process contains the Acetyl Chloride 98Min. of mass percent 90～97%; The Acetyl Chloride 98Min. in the by product in the organic acyloxy silicone hydride production process and the mass ratio of chlorine are 1: 1～9, and light chlorination gas-phase reaction temperature is 60～200 ℃, and the light chlorination gas-phase reaction time is 1～24h.
2. method according to claim 1 is characterized in that: the mass ratio of described Acetyl Chloride 98Min. and chlorine is 1: 3～6.
3. method according to claim 1 is characterized in that: described smooth chlorination gas-phase reaction temperature is 60～120 ℃.
4. method according to claim 1 is characterized in that: the described smooth chlorination gas-phase reaction time is 3～8h.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007101647184A CN101195564B (en) | 2007-12-07 | 2007-12-07 | Method for producing trichloro-acetic chloride with by-product in organic acyloxy silicone hydride production process |
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|---|---|---|---|
| CN2007101647184A CN101195564B (en) | 2007-12-07 | 2007-12-07 | Method for producing trichloro-acetic chloride with by-product in organic acyloxy silicone hydride production process |
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|---|---|
| CN101195564A CN101195564A (en) | 2008-06-11 |
| CN101195564B true CN101195564B (en) | 2011-06-01 |
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|---|---|---|---|
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5030753A (en) * | 1989-10-07 | 1991-07-09 | Hoechst Aktiengesellschaft | Process for the preparation of dichloro- or trichloroacetyl chloride |
| CN1323778A (en) * | 2000-05-12 | 2001-11-28 | 山东华阳科技股份有限公司 | Prepn. of trichloro-acetic chloride |
| CN1086689C (en) * | 1999-09-14 | 2002-06-26 | 中南工业大学 | Process for photooxidation synthesis of trichloro-acetyl chloride |
| CN1562941A (en) * | 2004-03-24 | 2005-01-12 | 大庆市富杰化工有限公司 | Method for preparing trichlorideacetyl chloride from mother liquor of chloroactic acid |
-
2007
- 2007-12-07 CN CN2007101647184A patent/CN101195564B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5030753A (en) * | 1989-10-07 | 1991-07-09 | Hoechst Aktiengesellschaft | Process for the preparation of dichloro- or trichloroacetyl chloride |
| CN1086689C (en) * | 1999-09-14 | 2002-06-26 | 中南工业大学 | Process for photooxidation synthesis of trichloro-acetyl chloride |
| CN1323778A (en) * | 2000-05-12 | 2001-11-28 | 山东华阳科技股份有限公司 | Prepn. of trichloro-acetic chloride |
| CN1562941A (en) * | 2004-03-24 | 2005-01-12 | 大庆市富杰化工有限公司 | Method for preparing trichlorideacetyl chloride from mother liquor of chloroactic acid |
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