CN1544403A - Improved 1,1,1,3,3-pentachloropropane and 1,1,1,3,3-pentachlorinbutane preparation method - Google Patents
Improved 1,1,1,3,3-pentachloropropane and 1,1,1,3,3-pentachlorinbutane preparation method Download PDFInfo
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- CN1544403A CN1544403A CNA2003101063885A CN200310106388A CN1544403A CN 1544403 A CN1544403 A CN 1544403A CN A2003101063885 A CNA2003101063885 A CN A2003101063885A CN 200310106388 A CN200310106388 A CN 200310106388A CN 1544403 A CN1544403 A CN 1544403A
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Abstract
The invention relates to an improved process for preparing 1,1,1,3,3-pentachloropropane and 1,1,1,3,3-pentachlorobutane comprising, (1) carrying out liquid phase telomeric reaction between raw material chloroethylene or 2-chloropropene and carbon tetrachloride in a reaction system comprising catalyst and reaction solvent, (2) evaporating chloroethylene or 2-chloropropene carbon tetrachloride solvent not completely reacted and leading into an absorption tower, reclaiming lower boiling chloroethylene or 2-chloropropene using absorbing agent, (3) reclaiming solid catalyst using conventional solid-liquid separation methods e.g. filtration and sedimentation, (4) preparing 1,1,1,3,3-pentachloropropane (HCC240) and 1,1,1,3,3-pentachlorobutane (HCC360) by distilling filtering liquid through vacuum distillation mode.
Description
Technical field
The present invention relates to a kind of preparation 1,1,1,3,3-pentachloropropane (HFC-240) and 1,1,1,3, the improvement preparation method of 3-pentachloro-butane (HFC-360).The technical field that belongs to the preparation of hydrogen fluorohydrocarbon homologue.
Background technology
1,1,1,3,3-pentachloropropane (hereinafter to be referred as HCC-240) and 1,1,1,3,3-pentachloro-butane (hereinafter to be referred as HCC-360) is preparation 1,1,1,3,3-pentafluoropropane (being called for short HFC-245fa) and 1,1,1,3, the raw material of 3-3-pentafluorobutane (hereinafter to be referred as HFC-365mfc).HFC-245fa, HFC-365mfc belong to hydrogen fluorohydrocarbon homologue, and its ODP value (atmospheric ozone consumption dive value) is zero, can be used for substituting foaming, the widely used CFC that atmospheric ozone layer is had destruction in cleaning field
s, HCFC
s, chloroparaffin.
HCC-240 and HCC-360 can make through telomerization in the presence of catalyzer and reaction solvent with vinylchlorid, 2-propenyl chloride and tetracol phenixin.Its principles of chemistry can be expressed with following chemical equation:
Can be further advance a reaction to generate its chemical equation such as dipolymer, trimer as follows owing to generating halides with unsaturated olefin:
N=1 ... single aggressiveness
N=2 ... dimer
N=3 ... tripolymer
Rotorn etc. reported once in " bulky molecular catalysis " 77-51-60 (1992) " composite transition metal catalysis tetracol phenixin and vinyl halides addition reaction " literary composition that the composite catalyst that adopts copper or molysite and n-Butyl Amine 99 to form reacted in acetonitrile solvent, prepare HCC240 with high yield.R.Rreidlinde etc. are at " Bull.Acace Sci " 1766-1769 (1979) " 2-propenyl chloride and CCL
4Telomerize " in the literary composition also report adopt similar reaction system to prepare HCC360 to have obtained satisfied result.Tadausz PiotoRygas etc. report the co-catalyst that adopts Cu salt and Tributylamine, trimethylammonium phosphamide, Tributyl phosphate ester to form in USP5902914, prepare HCC240 with similar telomerization.Buker etc. claim at USP6040487 and adopt nitrogen heterocyclic ring class such as imidazoles, tetrahydroglyoxaline, and azoles, the azoles quinoline, the catalyzer that pyrazoline etc. and, cupric salt are formed, the telomerization of carrying out vinylchlorid and tetracol phenixin in acetonitrile solvent prepares HCC240, yield 69%.
Adopt alkylamine, organophosphorus though the co-catalyst that nitrogen-containing heterocycle compound etc. and Cu salt are formed improves the transformation efficiency of reaction, selectivity greatly, adopts above-mentioned catalyzer still to have the difficulty that is difficult to overcome in the operation of actual process.The first, alkylamine, organophosphorus, heterocycle be the ligand unit price costliness not only of some molecular structure more complicated especially, is not easy to obtain, and often toxicity is bigger for this compounds simultaneously, and some still is a suspect carcinogen.The second, can form a kind of viscosity half decorating film after Cu salt etc. and the above-mentioned organic ligand complexing, in the operation of reality, except water etc. destroys, be difficult to from reactant, separate, so that catalyst recovery almost becomes is impossible.The 3rd, although the co-catalyst of compositions such as organic ligand that report adopts some more macromolecular boiling point to be higher than react object in some nearest patent documentation and Cu salt, can without with reaction the separating of object, the reaction object separates from reaction mixture by modes such as flash distillation, underpressure distillation, and residual catalyzer is directly applied mechanically.In fact at preparation HCC240, the especially polymeric boiling point of boiling point owing to object in the HCC360 process is very high, even adopt underpressure distillation also must operate under the high-temperature very much, and HCC240, HCC360 and polymer are in the presence of the co-catalyst that is concentrated, the operation of comparatively high temps can aggravate their decomposition and form the tar of thickness pitch prill shape, the amine in the composite catalyst that is concentrated simultaneously, organic phosphates, heterocyclic is joined and also can be decomposed rottenly through body, is formed with malodorous coking material.So not only make technological operation and become very difficult because tar exists, the efficient of the catalyzer of applying mechanically simultaneously also reduces greatly.
Summary of the invention
The objective of the invention is to avoid above-mentioned unfavorable factor, propose a kind ofly with vinylchlorid, 2-propenyl chloride, tetracol phenixin are feedstock production 1,1,1,3,3-pentachloropropane (HCC240) and 1,1,1,3, novel unique method of 3-pentachloro-butane (HCC360).Adopt a kind of novel unique reaction system among the preparation technology, this system is catalyzer with the cuprous chloride, and moment of dipole 〉=3.5 debye, specific inductivity are reaction solvent at the dipolar aprotic solvent of 40-55.Technical solution of the present invention:
Its processing step: (a) raw material vinylchlorid or 2-propenyl chloride and tetracol phenixin carry out the liquid phase telomerization in a reaction system of being made up of catalyzer and reaction solvent.(b) steam unreacted raw material vinylchlorid or 2-propenyl chloride tetracol phenixin and solvent completely after reaction finishes, and import an absorption tower, absorb with absorption agent and reclaim lower boiling vinylchlorid or 2-propenyl chloride.(c) reclaim the solid catalyzer with solid separation method commonly used such as filtration, sedimentation.(d) distill filtrate with the underpressure distillation mode and make 1,1,1,3,3-pentachloropropane (HCC240) and 1,1,1,3,3-pentachloro-butane (HCC360).(e) catalyzer of Hui Shouing and raw material tetracol phenixin, vinylchlorid or 2-propenyl chloride and absorption liquid can be recycled.
Advantage of the present invention: with vinylchlorid, 2-propenyl chloride, tetracol phenixin are feedstock production 1,1,1,3,3-pentachloropropane (HCC-240) and 1,1,1,3, in the reaction of 3-pentachloro-butane (HCC-360), adopt a kind of reaction system of forming at the non-proton dipole solvent of 40--55 scope greater than 3.5 debye, specific inductivity with catalyzer cuprous chloride and moment of dipole can obtain very satisfied reaction conversion ratio and selectivity.
Embodiment 1:
In the pressurized vessel of 1L liner F46 plastics, add the reaction solvent of 6mol, 0.015 cuprous chloride, stir.Add the tetracol phenixin of 6mol then, airtight, heat temperature raising to 130 ℃.Add vinylchlorid 3mol in batches, after finishing, kept 130 ℃ of temperature of reaction 4 hours.Reaction is cooled to room temperature after finishing, and sampling is analyzed with gas chromatograph.Reaction result such as table 1.Vinylchlorid changes the 2-propenyl chloride into and repeats aforesaid operations, range of reaction temperature 50--150 ℃; Reaction pressure scope: 0.1Mpa--1.5Mpa.Absorption operates in the 20%--1% scope to be carried out, and is preferably in the 10%--5% scope and reacts.
Result such as table 2.
Table 1, the differential responses system is to HCC240 preparation influence
| Sequence number | CuCl/ reaction solvent (mol/mol) | Solvent polarity (debye) | Specific inductivity | HCC240 selectivity (%) | Conversion rate of vinyl chloride (%) |
| ????1 | CuCl/ second eyeball/methyl-sulphoxide 0.05: 1: 1 | ????3.7 | ????43 | ????93 | ????90 |
| ????2 | CuCl/ second eyeball/ethylene carbonate ester 5: 85: 15 | ????3.7 | ????45 | ????95 | ????86 |
| ????3 | CuCl/DMF/ methyl-sulphoxide 0.05: 1: 1 | ????3.9 | ????43 | ????95 | ????92 |
Table 2, the differential responses system is to HCC360 preparation influence
| Sequence number | CuCl/ reaction solvent (mol/mol) | Solvent polarity (debye) | Specific inductivity | HCC360 selectivity (%) | 2-propenyl chloride transformation efficiency (%) |
| ????1 | CuCl/ second eyeball/methyl-sulphoxide 0.05: 1: 1 | ????3.7 | ????43 | ????95 | ????80 |
| ????2 | CuCl/ second eyeball/ethylene carbonate ester 5: 85: 15 | ????3.7 | ????45 | ????96 | ????86 |
| ????3 | CuCl/DMF/ methyl-sulphoxide 0.05: 1: 1 | ????3.9 | ????43 | ????95 | ????75 |
Embodiment 2:
The reaction mother liquor of embodiment 1 adds in the glass matrass of a 1L, and matrass is equipped with still head, prolong, receiving bottle.Adopt air distillation to steam raw material and partial solvent earlier, use underpressure distillation again instead and steam all solvents.Can find that solid separates out the mother liquor from distillation this moment, this mother liquor filters under the protection of drying nitrogen, the cuprous chloride of filter residue for reclaiming.The cuprous chloride, solvent, the raw material tetracol phenixin that reclaim add embodiment 1 described reactor again, and stirring heating is warming up to 130 ℃, adds vinylchlorid or 2-propenyl chloride 3mol in batches, 130 ℃ of thermotonuses 4 hours.Reaction finishes postcooling to room temperature, and sampling is analyzed with gas chromatograph.Range of reaction temperature 50--150 ℃; Reaction pressure scope: 0.1Mpa--1.5Mpa.Absorption operates in the 20%--1% scope to be carried out, and is preferably in the 10%--5% scope and reacts.Result such as table 3
Table 3, the influence that recovery CuCl, solvent prepare HCC240, HCC360
| Sequence number | Reaction system | HCC240 selectivity (%) | Conversion rate of vinyl chloride (%) | HCC360 selectivity (%) | 2-propenyl chloride transformation efficiency (%) |
| ????1 | CuCl/ second eyeball/methyl-sulphoxide | ????94 | ????90 | ????95 | ????78 |
| ????2 | CuCl/ second eyeball/ethylene carbonate ester | ????93 | ????89 | ????96 | ????85 |
| ????3 | The CuCl/DMF/ methyl-sulphoxide | ????95 | ????91 | ????95 | ????76 |
In above-mentioned example 1,2
The too small meeting of solvent polarity, specific inductivity that liquid phase telomerization system is formed can not disperse cuprous chloride well in system, thereby influences reactive activity, and reaction conversion ratio and selectivity are significantly reduced.Reaction system is formed the specific inductivity excessive (as＞55) of solvent, can cause vinylchlorid, and 2-propenyl chloride, specific inductivity such as tetracol phenixin, polar phase be to less reaction raw materials and solvent phase-splitting, and influences reaction conversion ratio and selectivity greatly.Dipolar aprotic solvent such as nitrile, acid amides, nitro-paraffin, alkyl sulfoxide, alkyl sulfone, sulfuric acid diester, sultones, carbonic diester, carbonic acid lactone etc. have the solvent of strong polarity and big specific inductivity, all are the good solvents of forming reaction system in the inventive method.In order both to satisfy the requirement of reaction system, less expensive again being easy to get, dissolvant of reaction system preferably with the mixed solvent of one or more compositions in one or more and methyl-sulphoxide in acetonitrile, Nitromethane 99Min., the dimethyl formamide, tetramethylene sulfone, methyl-sulfate, sulfuric acid glycol ester, methylcarbonate, the ethylene carbonate ester, can make the polarity of reaction solvent, the requirement that specific inductivity satisfies the inventive method by the proportioning of adjusting different solvents simultaneously easily.
Adopt the reaction system of the inventive method, after finishing, reaction can reclaim unreacted raw material vinylchlorid or 2-propenyl chloride tetracol phenixin and solvent completely by methods such as distillations easily, cuprous chloride as catalyzer is separated out from the distillation mother liquor, the solid separation method commonly used by filtration, sedimentation etc. reclaims, and the raw material of recovery, solvent, cuprous chloride can recycle easily.Low vinylchlorid of still-process mid-boiling point or 2-propenyl chloride can further import absorption unit CCl
4, the reaction solvent or both mixtures that adopt carry out solvent absorbing, absorption liquid also can be directly used in reaction.Because method of the present invention is rich in 1,1,1,3 in distillation, 3-pentachloropropane (HCC-240) or 1,1,1,3, during the filtrate of 3-pentachloro-butane (HCC-360), filtrate does not contain or contains very slightly cuprous chloride, so 1,1,1,3,3-pentachloropropane (HCC-240) or 1,1,1,3, the decomposition of 3-pentachloro-butane (HCC-360) in still-process seldom, acquisition 1 that can high yield, 1,1,3,3-pentachloropropane (HCC-240) or 1,1,1,3,3-pentachloro-butane (HCC-360).
The present invention 1,1,1,3,3-pentachloropropane and 1,1,1,3, and the preparation method of 3-pentachloro-butane, its telomerization mole ratio range:
CH
2＝CHCl(CH
2＝CClCH
3)/CuCl(mol/mol)，0.001--0.10
CH
2＝CHCl(CH
2＝CClCH
3)/CCl
4(mol/mol)，1--5
CH
2=CHCl (CH
2=CClCH
3)/solvent (mol/mol), 0.1--10 catalyzer cuprous chloride proportioning are low excessively to reduce speed of response, has prolonged the reaction times, also is unfavorable for reaction conversion ratio and optionally raising simultaneously.Can not have a direct impact though catalyzer cuprous chloride proportioning is too high, can increase preparation cost, be unfavorable for recycle and reuse simultaneously yet reaction.Tetracol phenixin must guarantee in higher level the proportioning of vinylchlorid or 2-propenyl chloride, at least should be greater than 1, and the dimer that the too small meeting of proportioning generates reaction increases, and influences reaction preference.The too high meeting of proportioning makes the reduction production capacity, and also making raw material reclaim load simultaneously increases.The proportioning of solvent is crossed the low dispersiveness of cuprous chloride in reaction system that can directly cause and is reduced, and influences reactive activity.The too high unit production capacity that both had been unfavorable for of solvent burden ratio also is unfavorable for the transformation efficiency that reacts.
Of the present invention 1,1,1,3,3-pentachloropropane and 1,1,1,3, the preparation method of 3-pentachloro-butane, 50--150 ℃ of its telomerization temperature range; Reaction pressure scope: 0.1Mpa--1.5Mpa.Cross low temperature of reaction, speed of response is reduced, too high temperature of reaction can make reaction preference reduce, and produces some unknown higher-boiling compounds, simultaneously working pressure is increased.Reaction pressure is relevant with temperature of reaction, and temperature high pressure more is high more, and temperature low pressure more is low more.The temperature that reaction is selected is preferably at 110-130 ℃.
When the recovery of reaction raw materials tetracol phenixin, vinylchlorid or 2-propenyl chloride, solvent, because the boiling point of vinylchlorid or 2-propenyl chloride is lower, distillation should be adopted normal pressure or pressure to be no more than the air distillation of 0.1Mpa and import a solvent absorbing device and absorb tail gas.After steaming the vinylchlorid or 2-propenyl chloride of the overwhelming majority, should use underpressure distillation instead fully to steam tetracol phenixin, solvent as far as possible.The temperature that absorbs operation is low more in theory good more.But cross low temperature and can increase equipment and process cost.The absorption of the inventive method operates in-and 30--40 ℃ temperature range carries out, preferably carries out in-10-0 ℃ scope.Absorption strength is low more to be beneficial to absorptions such as vinylchlorid more.But absorption strength is crossed the low increase that can face expense equally, and the absorption of the inventive method operates in the 20%--1% scope to be carried out, and is preferably in the 10%--5% scope and carries out.
Claims (5)
1,1,1,1,3,3-pentachloropropane and 1,1,1,3, the improvement preparation method of 3-pentachloro-butane, it is characterized in that its processing step: (a) raw material vinylchlorid or 2-propenyl chloride and tetracol phenixin carry out the liquid phase telomerization in a reaction system of being made up of catalyzer and reaction solvent; (b) steam unreacted raw material vinylchlorid or 2-propenyl chloride tetracol phenixin and solvent completely after reaction finishes, and import an absorption tower, absorb with absorption agent and reclaim lower boiling vinylchlorid or 2-propenyl chloride; (c) reclaim the solid catalyzer with solid separation method commonly used such as filtration, sedimentation; D) distill filtrate with the underpressure distillation mode and make 1,1,1,3,3-pentachloropropane and 1,1,1,3,3-pentachloro-butane; (e) catalyzer of Hui Shouing and raw material tetracol phenixin, vinylchlorid or 2-propenyl chloride and absorption liquid can be recycled.
2, by claim 1 described 1,1,1,3,3-pentachloropropane and 1,1,1,3, the preparation method of 3-pentachloro-butane is characterized in that the catalyzer of liquid phase telomerization system adopts cuprous chloride (CuCl), and reaction solvent is that moment of dipole is greater than 3.5 debye, specific inductivity is at 40--55 scope dipolar aprotic solvent, and dipolar aprotic solvent is that one or more mixture of nitrile, acid amides, nitro-paraffin, alkyl sulfoxide, alkyl sulfone, sulfuric acid diester, sultones, carbonic diester, carbonic acid lactone is formed.
3, by the mixed solvent of the described reaction solvent of claim 2 with one or more compositions in one or more and methyl-sulphoxide in acetonitrile, Nitromethane 99Min., the dimethyl formamide, tetramethylene sulfone, methyl-sulfate, sulfuric acid glycol ester, methylcarbonate, the ethylene carbonate ester.
4, described 1,1,1,3 by claim 1,3-pentachloropropane and 1,1,1,3, the preparation method of 3-pentachloro-butane, the absorption agent that it is characterized in that processing step (b) is CCl
4, the solvent that adopts of reaction or both mixtures, the absorption pattern that absorbs classics such as adopting bubbling, spray or packing tower spray carries out, absorption operating temperature range :-30 ℃--40 ℃; Absorb working pressure :-0.1Mpa-0.1Mpa.
5, described 1,1,1,3 by claim 1,3-pentachloropropane and 1,1,1,3, the preparation method of 3-pentachloro-butane is characterized in that the telomerization mole ratio range in the processing step (a):
CH
2＝CHCl(CH
2＝CClCH
3)/CuCl(mol/mol)，????0.001--0.10
CH
2＝CHCl(CH
2＝CClCH
3)/CCl
4(mol/mol)，????1--5
CH
2=CHCl (CH
2=CClCH
3)/solvent (mol/mol), 0.1-10,
Range of reaction temperature: 50--150 ℃; Reaction pressure scope: 0.1Mpa--1.5Mpa.
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|---|---|---|---|
| CN 200310106388 CN1239448C (en) | 2003-11-24 | 2003-11-24 | Improved 1,1,1,3,3-pentachloropropane and 1,1,1,3,3-pentachlorinbutane preparation method |
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|---|---|---|---|
| CN 200310106388 CN1239448C (en) | 2003-11-24 | 2003-11-24 | Improved 1,1,1,3,3-pentachloropropane and 1,1,1,3,3-pentachlorinbutane preparation method |
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| CN1239448C CN1239448C (en) | 2006-02-01 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100427442C (en) * | 2005-12-19 | 2008-10-22 | 浙江蓝天环保高科技股份有限公司 | Improved preparing process for 1,1,1,3,3-pentachloro propane |
| CN111659322A (en) * | 2019-03-06 | 2020-09-15 | 浙江佳汇新材料有限公司 | Device and process for preparing 1,1,1, 3-tetrachloropropane |
| CN114349594A (en) * | 2021-12-16 | 2022-04-15 | 西安近代化学研究所 | Method and reactor for preparing polyhalogenated hydrocarbon |
| CN114634396A (en) * | 2021-12-29 | 2022-06-17 | 山东东岳化工有限公司 | Pentachloropropane and preparation method thereof |
-
2003
- 2003-11-24 CN CN 200310106388 patent/CN1239448C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100427442C (en) * | 2005-12-19 | 2008-10-22 | 浙江蓝天环保高科技股份有限公司 | Improved preparing process for 1,1,1,3,3-pentachloro propane |
| CN111659322A (en) * | 2019-03-06 | 2020-09-15 | 浙江佳汇新材料有限公司 | Device and process for preparing 1,1,1, 3-tetrachloropropane |
| CN114349594A (en) * | 2021-12-16 | 2022-04-15 | 西安近代化学研究所 | Method and reactor for preparing polyhalogenated hydrocarbon |
| CN114349594B (en) * | 2021-12-16 | 2024-02-20 | 西安近代化学研究所 | Method and reactor for preparing polyhalogenated hydrocarbon |
| CN114634396A (en) * | 2021-12-29 | 2022-06-17 | 山东东岳化工有限公司 | Pentachloropropane and preparation method thereof |
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