CN102453006A - Method for preparing epoxy chloropropane - Google Patents
Method for preparing epoxy chloropropane Download PDFInfo
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- CN102453006A CN102453006A CN2010105229447A CN201010522944A CN102453006A CN 102453006 A CN102453006 A CN 102453006A CN 2010105229447 A CN2010105229447 A CN 2010105229447A CN 201010522944 A CN201010522944 A CN 201010522944A CN 102453006 A CN102453006 A CN 102453006A
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- epoxy chloropropane
- reaction
- catalyzer
- catalyst
- quaternary ammonium
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Abstract
The invention discloses a method for preparing epoxy chloropropane. The method comprises the following step of: oxidizing chloropropene by using a phosphotungstic acid quaternary ammonium salt, a phosphoric acid quaternary ammonium salt and hydrogen peroxide under a solvent-free condition to generate the epoxy chloropropane.
Description
Technical field
The present invention relates to the preparation of epoxy chloropropane, specifically a kind of method that is used for preparing epichlorohydrin by chloropropene epoxidation.
Background technology
Epoxy chloropropane (ECH) is a kind of important Organic Chemicals and midbody, is widely used in the production of epoxy resin, chlorohydrin rubber.The operational path of epoxy chloropropane has two kinds: chlorohydrination and allyl acetate method.Chlorohydrination propylene high-temperature chlorination before this generates propenyl chloride (Allyl Chloride), and propenyl chloride generates 1 with the chlorine water solution reaction again, 3-two chloro-2-propyl alcohol, and cyclization generates epoxy chloropropane under the alkaline solution effect.The monovalent epoxy chloropropane generates will follow monovalent CaCl
2Get into water, this technology environmental pollution is very serious.The allyl acetate method is to generate allyl acetate to propylene oxidation in acetic acid earlier, and hydrolysis gets vinyl carbinol, and vinyl carbinol and chlorine reaction get 1, the 3-dichlorohydrine.Cyclization generates epoxy chloropropane under the alkaline solution effect.The monovalent epoxy chloropropane generates will follow 0.5 normal CaCl
2Get into water.Therefore allyl acetate technology also has pollution to environment.The pollution that is difficult to effect a radical cure is the common difficulty that existing two kinds of working methods exist.The process for cleanly preparing of exploitation epoxy chloropropane has become the inevitable requirement of era development.The technological line that the direct epoxidation of propenyl chloride is produced epoxy chloropropane should be the developing direction of following epoxy chloropropane production technology, and key problem in technology wherein is successfully to develop the direct epoxidised technology of the free of contamination propenyl chloride of no burn into.
With H
2O
2Be oxygen source, phospho heteropoly tungstate is a catalyzer, and catalyzed oxidation propenyl chloride system epoxy chloropropane is a kind of operational path of green.Venturello etc. have reported with [(C
8H
17)
3NCH
3]
3[PO
4[W (O) (O
2)
2]
4] be homogeneous catalyst, H
2O
2Chloro propylene epoxidation reaction for oxygen source.The 2.5h that in benzene/water two-phase system, refluxes, the yield of epoxy chloropropane is 85%.(J.Org.Chem., 1988,53:1553～1557) Sun Yu etc. has reported with [π-C
5H
5NC
16H
33]
3[PW
4O
16] be catalyzer, be solvent with toluene and tributyl phosphate, the hydrogen peroxide that uses the molecular oxygen oxidation anthrahydroquinone to generate is oxygen source, reacts 1.5h under 75 ℃ of conditions, the yield of epoxy chloropropane is 80.5%.(J.Mol.Catal.A-Chem.; 2001; 166:219～224) in the catalystsystem of Venturello, catalyzer is made up of methyl trioctylphosphine quaternary ammonium salt and peroxide phospho-wolframic acid heteropolyanion, and reaction finishes rear catalyst and can't from reaction system, separate out; And catalyst levels is big, therefore how to solve this homogeneous catalyst separation, whether practical reclaim and recycle problem be this system key.
Calendar year 2001 Xi Zuwei etc. has developed a kind of novel catalystsystem-reaction-controlled phase transfer catalysis system.(Science, 2001,292:1139～1141) in water oil two-phase system, the phosphorus heteropoly tungstic acid salt catalyst is insoluble to oil phase, but at H
2O
2Effect is dissolving gradually down, catalyzed alkene and H under the homogeneous phase condition
2O
2Epoxidation reaction.When reaction finishes H
2O
2After being exhausted, catalyzer becomes soluble again, from reaction system, separates out, and reaches the purpose of recycling.This type catalyst stability is good, and has the advantage of homogeneous catalyst and heterogeneous catalyst concurrently, and this separation that is difficult to for homogeneous catalyst provides effective way.
Li Jian etc. are applied to the phospho heteropoly tungstate reaction control phase transfer catalyst in the reaction of propenyl chloride oxidation system epoxy chloropropane, with (about 30%) H commonly used
2O
2The aqueous solution is green oxygen source, is solvent with the ethylene dichloride, and the phosphorus heteropoly tungstic acid salt catalyst has very high activity.The productive rate of epoxy chloropropane can reach 88.3%, and catalyzer is recyclable.(Journal of Molecular Catalysis, 2006,20:395-398)
Yang Hongyun etc. are with H
2O
2Be oxygenant, in chloroform solvent, studied reaction control phase transfer catalyst { [C
16H
33(CH
3)
3(70%)+C
18H
37(CH
3)
3(30%)] N} [PW
4O
16] catalysis chloro propylene epoxidation system epichlorohydrin reaction.(petrochemical complex, 2008,37 (11): 1172) suitable condition of chloro propylene epoxidation reaction is: with the chloroform solvent, K
2HPO
4Consumption (with respect to the total reactant quality mark) 0.04%, 50 ℃ of temperature of reaction, reaction times 4h, m (propenyl chloride): m (H
2O
2)=5.0, m (catalyzer): m (H
2O
2)=1.0.Under this reaction conditions, H
2O
2Transformation efficiency is 96.4%, and the selectivity of epoxy chloropropane and yield are respectively 89.4% and 86.2%.
Li Jian etc. are to H
2O
2The aqueous solution is that chlorine monoxide propylene production epoxy chloropropane has carried out preliminary study under the oxygen source condition of no solvent.Result of study is illustrated in reaction control phase transfer catalyst [C under the condition of no solvent
16H
33N (CH
3)
3]
3PW
4O
16Very high catalytic activity and the stability of reaction performance at propenyl chloride oxidation system epoxy chloropropane.The yield of 65 ℃ of reaction 2h epoxy chloropropane reaches 88.7%, and the yield of twice back of catalyst recirculation epoxy chloropropane still can reach 85.0%.(Res.Chem.Intermed.，2007，33：523)
In sum, the phosphorus heteropoly tungstic acid salt catalyst is to H
2O
2For the preparing epichlorohydrin by chloropropene epoxidation of oxygen source has good active, reaction control phase transfer catalyst can recycle, but activity of such catalysts reduces along with the increase of reaction times gradually.For example Yang Hong cloud etc. adopts and adds KH
2PO
4Under the condition for additive, catalyzer can circulating reaction 5 times, but the yield of epoxy chloropropane drops to 82% of 4 secondary responses by 86.2% of fresh reactant.Li Jian etc. adopt and add NaHCO
3Or NaH
2PO
4Be additive, catalyzer can recycle 3 times under solvent and the solvent-free condition having.The yield of epoxy chloropropane also drops to 85% of 2 secondary responses by 88.7% of fresh reactant.
The object of the invention is to overcome the problem that catalyst activity that above-mentioned epoxy systems exists reduces, and provides a kind of propenyl chloride to produce the new process of epoxy chloropropane.This method catalyzer is easy to reclaim and recycle, and activity of such catalysts do not reduce, and has reduced production cost, and environment is not polluted.
Summary of the invention
The present invention provides a kind of propenyl chloride to produce the novel method of epoxy chloropropane.This method catalyzer is easy to reclaim and recycle, and activity of such catalysts do not reduce, and has reduced production cost, and environment is not polluted.
The method that the present invention provides a kind of propenyl chloride to produce epoxy chloropropane, this method are by catalyzer, and oxygenant and additive are formed, and wherein additive is the phosphoric acid quaternary ammonium salt, and its molecule is to be [(C
nH
2n+1) N (CH
3)
3]
3PO
4, wherein n=4-18 is preferably n=10-16.
Catalyst molecule formula used in the present invention is [(C
nH
2n+1) N (CH
3)
3]
3PW
4O
16, wherein n=10-18 is preferably n=12-18.
The consumption of additive of the present invention is 0.002-0.2 a times of catalyst levels.
Oxygenant used in the present invention is an aqueous hydrogen peroxide solution.
The temperature of reaction that the present invention is fit to typically is about 45～80 ℃.Preferably, this reaction is carried out about 50～70 ℃.
The mol ratio of catalyzer of the present invention and ydrogen peroxide 50 is 1: 50-1: 400; The mol ratio of propenyl chloride and ydrogen peroxide 50 is 1.5: 1-8: 1.
The invention has the advantages that:
1, the ydrogen peroxide 50 with green is an oxygen source;
2, catalyst stability is high;
3, catalyzer is easy to reclaim and recycle;
4, simple to operate, product is easily separated, environmentally safe.
Embodiment
The oxidizing reaction of all propenyl chlorides is all carried out in having churned mechanically 500mL glass reaction still.The yield of epoxy chloropropane is that benchmark calculates with the ydrogen peroxide 50, and the selectivity of epoxy chloropropane is that benchmark calculates with the propenyl chloride.
Embodiment 1
With 200g purity is 98% propenyl chloride (ALC), 12g catalyzer [(C
16H
33) N (CH
3)
3]
3PW
4O
16With 2g additive [(C
16H
33) N (CH
3)
3]
3PO
4Put in the 500mL glass reaction still, be warmed up to 65 ℃, under stirring condition, pump into the H of 68g 50% lentamente
2O
2, add the back and under this temperature, continue reaction 3h, with the frozen water cooling, liquid-solid separation, solid catalyst is used for secondary response down, and liquid is told oil phase, carries out yield and selectivity that gas chromatographic analysis obtains epoxy chloropropane.The step that the recovery catalyzer reacts is the same, carries out 10 secondary response results altogether and sees table 1.
Table 1
| Reaction times | Epoxy chloropropane yield (%) | Epoxy chloropropane selectivity (%) |
| 1 | 87.6 | 96.5 |
| 2 | 86.9 | 95.9 |
| 3 | 88.0 | 96.0 |
| 4 | 87.5 | 96.2 |
| 5 | 87.9 | 95.8 |
| 6 | 87.2 | 96.1 |
| 7 | 86.8 | 96.0 |
| 8 | 87.3 | 97.0 |
| 9 | 88.0 | 96.8 |
| 10 | 87.9 | 96.5 |
Visible by table 1, additive [(C
16H
33) N (CH
3)
3]
3PO
4Adding, can improve the stability of catalyzer, catalyst recirculation uses the yield of 9 (react 10 times) epoxy chloropropane to remain on about 87%, the selectivity of epoxy chloropropane remains on about 96%, all less than reduction.
Embodiment 2
With 200g purity is 98% propenyl chloride (ALC), 8g catalyzer [(C
12H
25) N (CH
3)
3]
3PW
4O
16With 1g additive [(C
12H
25) N (CH
3)
3]
3PO
4Put in the 500mL glass reaction still, be warmed up to 55 ℃, under stirring condition, pump into the H of 70g 30% lentamente
2O
2, add the back and under this temperature, continue reaction 3h, with the frozen water cooling, liquid-solid separation, solid catalyst is used for secondary response down, and liquid is told oil phase, carries out yield and selectivity that gas chromatographic analysis obtains epoxy chloropropane.The step that the recovery catalyzer reacts is the same, carries out 8 secondary response results altogether and sees table 2.
Table 2
| Reaction times | Epoxy chloropropane yield (%) | Epoxy chloropropane selectivity (%) |
| 1 | 84.6 | 94.5 |
| 2 | 83.9 | 94.9 |
| 3 | 85.0 | 94.0 |
| 4 | 84.5 | 94.2 |
| 5 | 84.9 | 93.8 |
| 6 | 85.2 | 94.1 |
| 7 | 83.8 | 94.0 |
| 8 | 84.3 | 95.0 |
The visible catalyst recirculation of table 2 uses the yield and the selectivity of 7 (reacting 8 times) epoxy chloropropane to remain on respectively about 84% and 94%, does not reduce, and the stability of catalyzer is able to keep.
Embodiment 3
With 300g purity is 98% propenyl chloride (ALC), 10g catalyzer [(C
18H
37) N (CH
3)
3]
3PW
4O
16With 0.5g additive [(C
18H
37) N (CH
3)
3]
3PO
4Put in the 500mL glass reaction still, be warmed up to 48 ℃, under stirring condition, pump into the H of 50g 50% lentamente
2O
2, add the back and under this temperature, continue reaction 4h, with the frozen water cooling, liquid-solid separation, solid catalyst is used for secondary response down, and liquid is told oil phase, carries out yield and selectivity that gas chromatographic analysis obtains epoxy chloropropane.The step that the recovery catalyzer reacts is the same, carries out 15 secondary response results altogether and sees table 3.
Table 3
| Reaction times | Epoxy chloropropane yield (%) | Epoxy chloropropane selectivity (%) |
| 1 | 83.2 | 94.5 |
| 2 | 83.0 | 94.6 |
| 3 | 83.5 | 95.0 |
| 4 | 84.0 | 94.2 |
| 5 | 82.9 | 94.8 |
| 6 | 83.0 | 95.0 |
| 7 | 83.4 | 94.9 |
| 8 | 82.8 | 94.3 |
| 9 | 83.2 | 94.3 |
| 10 | 83.1 | 94.5 |
| 11 | 82.8 | 95.1 |
| 12 | 84.0 | 94.3 |
| 13 | 83.5 | 94.2 |
| 14 | 83.8 | 94.3 |
| 15 | 83.5 | 95.0 |
The visible catalyst recirculation of table 3 uses the yield and the selectivity of 14 (reacting 15 times) epoxy chloropropane to remain on about 83% and 94%, explains that catalyzer has very high stability under this reaction conditions.
Claims (7)
1. the method for an epoxy chloropropane; It is characterized in that: in the presence of additive phosphoric acid quaternary ammonium salt; Relatively the excessive propenyl chloride of oxygenant is that oxygenant react direct generation epoxy chloropropane under reflux state with the ydrogen peroxide 50 under the effect of catalyzer quaternary ammonium salt phosphor-tungstic heteropoly acid.
2. method according to claim 1 is characterized in that: the molecular formula of additive phosphoric acid quaternary ammonium salt is [(C
nH
2n+1) N (CH
3)
3]
3PO
4, n=4-18.
3. method according to claim 1 and 2 is characterized in that: the consumption of additive is 0.002-0.2 a times of catalyst levels.
4. method according to claim 1 is characterized in that: the mol ratio of catalyzer and ydrogen peroxide 50 is 1: 50-1: 400.
5. method according to claim 1 is characterized in that: the mol ratio of propenyl chloride and ydrogen peroxide 50 is 1.5-8: 1.
6. method according to claim 1 is characterized in that: temperature of reaction is 45 ℃-80 ℃.
7. method according to claim 1 is characterized in that: employed catalyst molecule formula is [(C
nH
2n+1) N (CH
3)
3]
3PW
4O
16, n=10-18 wherein.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105229447A CN102453006B (en) | 2010-10-27 | 2010-10-27 | Method for preparing epoxy chloropropane |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105229447A CN102453006B (en) | 2010-10-27 | 2010-10-27 | Method for preparing epoxy chloropropane |
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|---|---|
| CN102453006A true CN102453006A (en) | 2012-05-16 |
| CN102453006B CN102453006B (en) | 2013-12-11 |
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ID=46036734
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102875492A (en) * | 2012-09-06 | 2013-01-16 | 大连工业大学 | Method for compounding epoxy fatty acid ester with unsaturated fatty acid ester |
| CN108329283A (en) * | 2018-04-10 | 2018-07-27 | 江苏扬农化工集团有限公司 | A kind of recovery method of chloro propylene epoxidation water layer catalyst-solvent |
| CN110479374A (en) * | 2019-09-20 | 2019-11-22 | 济南大学 | A kind of phosphorus heteropoly tungstic acid salt catalyst and preparation method thereof for synthesizing epoxy chloropropane |
| CN110479370A (en) * | 2019-09-20 | 2019-11-22 | 济南大学 | A kind of catalyst and preparation method thereof for chloro propylene epoxidation |
| WO2020082863A1 (en) * | 2018-10-23 | 2020-04-30 | 江苏扬农化工集团有限公司 | Method for preparing key intermediate of epoxy resin |
| CN116143727A (en) * | 2023-02-09 | 2023-05-23 | 浙江皇马科技股份有限公司 | Refining method of methyl epoxy chloropropane |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1900071A (en) * | 2005-07-21 | 2007-01-24 | 中国科学院大连化学物理研究所 | Process for preparing epoxy chloropropane |
| CN101045717A (en) * | 2006-03-27 | 2007-10-03 | 中国石油化工股份有限公司 | Method of directly catalytic epoxidation |
-
2010
- 2010-10-27 CN CN2010105229447A patent/CN102453006B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1900071A (en) * | 2005-07-21 | 2007-01-24 | 中国科学院大连化学物理研究所 | Process for preparing epoxy chloropropane |
| CN101045717A (en) * | 2006-03-27 | 2007-10-03 | 中国石油化工股份有限公司 | Method of directly catalytic epoxidation |
Non-Patent Citations (2)
| Title |
|---|
| 《Science》 20010511 Xi Zuwei,et al. "Reaction-Controlled Phase-Transfer Catalysis for Propylene Epoxidation to Propylene Oxide" 1139-1141 1-7 第292卷, * |
| XI ZUWEI,ET AL.: ""Reaction-Controlled Phase-Transfer Catalysis for Propylene Epoxidation to Propylene Oxide"", 《SCIENCE》, vol. 292, 11 May 2001 (2001-05-11), pages 1139 - 1141 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102875492A (en) * | 2012-09-06 | 2013-01-16 | 大连工业大学 | Method for compounding epoxy fatty acid ester with unsaturated fatty acid ester |
| CN108329283A (en) * | 2018-04-10 | 2018-07-27 | 江苏扬农化工集团有限公司 | A kind of recovery method of chloro propylene epoxidation water layer catalyst-solvent |
| WO2020082863A1 (en) * | 2018-10-23 | 2020-04-30 | 江苏扬农化工集团有限公司 | Method for preparing key intermediate of epoxy resin |
| CN110479374A (en) * | 2019-09-20 | 2019-11-22 | 济南大学 | A kind of phosphorus heteropoly tungstic acid salt catalyst and preparation method thereof for synthesizing epoxy chloropropane |
| CN110479370A (en) * | 2019-09-20 | 2019-11-22 | 济南大学 | A kind of catalyst and preparation method thereof for chloro propylene epoxidation |
| CN116143727A (en) * | 2023-02-09 | 2023-05-23 | 浙江皇马科技股份有限公司 | Refining method of methyl epoxy chloropropane |
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