CN100348558C - Production of phenylethylene compound - Google Patents
Production of phenylethylene compound Download PDFInfo
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- CN100348558C CN100348558C CNB2005100678561A CN200510067856A CN100348558C CN 100348558 C CN100348558 C CN 100348558C CN B2005100678561 A CNB2005100678561 A CN B2005100678561A CN 200510067856 A CN200510067856 A CN 200510067856A CN 100348558 C CN100348558 C CN 100348558C
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Abstract
The present invention relates to novel technology of a styrene compound, which uses alpha-phenylethanol or beta-phenylethanol compounds as raw material to generate dehydration reaction under the action of catalyst to prepare the styrene compound. The dehydration reaction has the process that reaction raw materials of the alpha-phenylethanol or the beta-phenylethanol compounds (parts), the catalyst and inhibitive substance solution which are uniformly mixed in advance are dripped with the alpha-phenylethanol or the beta-phenylethanol compounds, and a product of the styrene compound can be continuously steamed out by reducing pressure when the dehydration reaction is generated. The dehydration reaction which is carried out by the method can greatly reduce the reaction temperature and enhances the reaction rate.
Description
Technical field
The present invention relates to a kind of novel process of producing styrene compound.This distyryl compound comprises vinylbenzene and have various substituent styrene derivativess on phenyl ring.
Background technology
Styrene compound is the important monomer of synthetic polystyrene resin, and the various different substituents on the phenyl ring can give the polystyrene resin that makes various character, thereby adapts to various purposes.For example be used for synthetic ion-exchange resin, the ion exchange resin that obtains has favorable mechanical performance and resistance toheat, can be used to prepare high purity water in fuel-burning power plant, Nuclear power plants, nuclear-propelled submarine, semi-conductor industry, pharmacy and sugar-refining industry.In addition, styrene compound can also be used to prepare various functional high molecule materials such as photosensitive resin, tackiness agent, polymeric membrane, is applicable to many fields.
At present one of method of synthesizing styrene compounds be utilize α-or the bata-phenethyl alcohol compounds under the high temperature reduced pressure, dewater.Among JP49086332 and the US3917223 parachloroacetophenone is mixed hot altogether with aluminum isopropylate, at first make parachloroacetophenone be reduced to 1-(rubigan) ethanol, at high temperature decompression dehydration obtains chloro-styrene again, in this method this two-step reaction is once carried out in same reactor,, in dehydration reaction, do not add catalyzer though reaction process is simplified, cause dewatering efficiency poor, temperature of reaction is higher, and the reaction times increases, and reaction yield is not high.Will be under the sal enixum effect among EP355983, US5041614, US5345074 and the US5151546 to acetoxyl group phenyl methyl methyl alcohol, about 240 ℃, under the 150mmHg condition, in thin-film evaporator, carry out the dehydration reaction preparation to acetoxy-styrene in continuous or semi-continuous mode.This method is with all dehydration reaction raw materials, comprise acetoxyl group phenyl methyl methyl alcohol and sal enixum and stopper mixing back are dripped in the reactor under certain temperature, pressure, because sal enixum is a solid and be liquid to acetoxyl group phenyl methyl alcohol, the difficulty that the solid-liquid mixing is fed in raw material is bigger, may cause mixing inhomogeneous, the carrying out of influence reaction.Use thin-film evaporator as reactor in this reaction in addition, separating effect is relatively poor, product and reaction raw materials can not be separated fully, causes the rate of recovery of reaction product lower.
The present invention is directed to above problem and adopt a kind of new reaction process, with α-or the bata-phenethyl alcohol compounds be that raw material prepares styrene compound through dehydration reaction.In the present invention with catalyzer, stopper and partial reaction raw material α-or after the bata-phenethyl alcohol compounds places the reactor uniform mixing, to wherein dripping α-or bata-phenethyl alcohol compounds, such reactive mode helps the uniform mixing of reaction raw materials and catalyzer, make dehydration reaction under lower temperature, to carry out, need not to be heated to above fully the carrying out of just can guaranteeing to react of the melt temperature of catalyzer.Under reduced pressure, constantly steam the product of generation in the reaction process.The use of catalyzer makes dewatering efficiency improve, and with catalyzer place still and partial reaction raw material in advance uniform mixing can overcome solid-liquid and mix the reinforced difficulty of bringing, simultaneously make that also temperature of reaction has substantial degradation, these all help simplifying the operation course, and reduce the energy consumption in the production process.Adopt and produce the styrene compound productive rate in such a way and can reach more than 95%.
Summary of the invention
The present invention be with α-or the bata-phenethyl alcohol compounds be raw material, through high temperature decompression dehydration prepared in reaction styrene compound.Methyl phenyl carbinol (a) and bata-phenethyl alcohol (b) compounds dehydration reaction are as follows:
Position or contraposition can be H between wherein R was positioned at, or halogen, for example fluorine, chlorine, bromine and iodine; Or the alkyl of straight or branched, for example methyl, ethyl, propyl group, butyl, sec.-propyl, the tertiary butyl, amyl group, hexyl etc.; Or straight or branched alkoxyl group, for example methoxyl group, oxyethyl group, propoxy-, butoxy, isopropoxy, tert.-butoxy etc.; Or ester group, for example ethoxycarbonyl, propyl ester base, butyl ester base etc.
Reaction raw materials α-or the bata-phenethyl alcohol compounds join in two batches in the reactor, first is the 10-80% of total amount, preferred 20-40% joins in the reactor when reaction is initial, is used to realize the uniform mixing with catalyzer and stopper; Second batch is remaining reaction raw materials, joins in the mode that drips and carries out dehydration reaction in the reactor.
Dewatering agent can be mineral acid, for example vitriol oil, concentrated hydrochloric acid, strong phosphoric acid, phosphorous acid etc. in this reaction; Or organic acid, for example tosic acid, methylsulphonic acid etc.; Or inorganic oxide, for example aluminum oxide, titanium dioxide, silica gel etc.; Or acidic ion exchange resin; Or hydrosulfate, for example sal enixum, aluminium hydrogen sulfate etc.; And the mixture of above-mentioned various dewatering agents.Preferably sulfuric acid hydrogen potassium, tosic acid etc.The consumption of dewatering agent is that reaction raw materials α-or the 0.1-1 of bata-phenethyl alcohol compounds weight doubly, and preferred 0.3-0.5 doubly.
Because styrene compound is easy to polymerization, therefore in reaction, must add stopper.The stopper that uses in the reaction can be 2,2,6,6-tetramethyl--4-hydroxyl oxidize pyridine (TMP), p-ten.-butylcatechol (TBC), Resorcinol, tetrachlorobenzene quinone, t-butyl catechol, thiodiphenylamine, d-tert-butyl-p-cresol etc., preferred p-ten.-butylcatechol.The stopper consumption is reaction raw materials α-or the 0.001-10% of bata-phenethyl alcohol compounds weight, preferred 0.1-1%.
Usually do not use solvent in this dehydration reaction.Temperature of reaction 100-250 ℃, preferred 120-200 ℃.Reactions vary fixes on raw material α-or more than the melt temperature of bata-phenethyl alcohol compounds and dewatering agent, as long as can guarantee each reaction raw materials uniform mixing.Reaction pressure 0.1-760mmHg, preferred 50-760mmHg.Constantly isolate the water of product styrene compound and generation in the reaction process.
Reaction is carried out in continuous or semi-continuous mode, and reaction unit comprises reactor, rectifier unit and condensing works.Earlier with partial reaction raw material α-or bata-phenethyl alcohol compounds and dewatering agent, stopper in reactor, mix and be heated to certain temperature.In reactor, drip remaining reaction raw materials α-or bata-phenethyl alcohol compounds then.α-or the bata-phenethyl alcohol compounds dehydration reaction takes place rapidly under the effect of catalyzer in reactor, steam simultaneously unreacting material α-or bata-phenethyl alcohol compounds, product styrene compound and water byproduct under the heating reduced pressure simultaneously from reactor, this mixture enters rectifier unit from the bottom or the middle part of rectifying tower.Because the boiling point of styrene compound is usually less than α-or the boiling point of bata-phenethyl alcohol compounds, by regulating the stage number of rectifying tower, can make unreacting material α-or the condensation of bata-phenethyl alcohol compounds after come back in the reactor and to continue reaction, product styrene compound and water byproduct then steam from the rectifying tower top, behind condensing works, collect and obtain the styrene compound crude product, can obtain pure styrene compound through behind the vacuum fractionation again.
To specify the present invention among the following embodiment, but scope of the present invention is not limited to therewith.
Embodiment
Embodiment 1
To synthesizing of chloro-styrene
In reactor, add 600g rubigan carbinol methine, and then add 6gTMP and 650g sal enixum, mix.Pressure in the reactor is reduced to 680-690mmHg, and temperature rises to 120 ℃.Speed with 50g/hr drips 1000g rubigan carbinol methine in reactor.Slowly temperature of reaction kettle is risen to 160 ℃ after beginning to receive product in the condensation receiving trap, the rate of addition of rubigan carbinol methine is brought up to 100g/h.Reacted again after dropwising 30 minutes, and temperature of reaction kettle was elevated to 190 ℃ then, to there not being stopped reaction behind the overhead product.Rectifying behind the adding 32g TMP finally obtains to chloro-styrene 1348g productive rate 95.3% in the emulsified soln that collection obtains.
Embodiment 2-6
With the method for embodiment 1, synthetic with conditions such as differing temps, pressure, input speed, dewatering agent consumptions to chloro-styrene, the results are shown in table 1.Temperature in the table and input speed are meant temperature and the input speed that begins in the condensing works to collect behind the product.
Table 1
| Embodiment | Rubigan carbinol methine total amount g (the ratio % that preloads) | Sal enixum consumption g | Temperature ℃ | Pressure mm Hg | Input speed g/h | Productive rate % |
| 2 | 1600(25) | 800 | 120 | 680 | 100 | 85.8 |
| 3 | 1600(30) | 800 | 200 | 700 | 150 | 90.4 |
| 4 | 1600(15) | 500 | 160 | 650 | 100 | 92.5 |
| 5 | 1600(15) | 600 | 150 | 540 | 200 | 93.7 |
| 6 | 1600(50) | 800 | 160 | 650 | 150 | 91.0 |
Embodiment 7
To synthesizing of acetoxy-styrene
In reactor, add 720g to acetoxy-methyl methyl alcohol, and then add 7g TMP and 600g sal enixum, mix.Pressure in the reactor is reduced to about 200mmHg, and temperature rises to 120 ℃.Speed with 55g/hr drips 1080g to acetoxy-methyl methyl alcohol in reactor.After beginning to receive product in the condensation receiving trap, slowly temperature of reaction kettle is risen to 150 ℃, the rate of addition of acetoxy-methyl methyl alcohol is brought up to 150g/h.Reacted again after dropwising 30 minutes, and temperature of reaction kettle was elevated to 180 ℃ then, to there not being stopped reaction behind the overhead product.Rectifying behind the adding 40gTMP finally obtains to acetoxy-styrene 1563g productive rate 96.5% in the emulsified soln that collection obtains.
Embodiment 8-14
With the method for embodiment 7, synthetic with conditions such as differing temps, pressure, input speed, dewatering agent consumptions to acetoxy-styrene, the results are shown in table 2.Temperature in the table and input speed are meant temperature and the input speed that begins in the condensing works to collect behind the product.
Table 2
| Embodiment | Rubigan carbinol methine total amount g (the ratio % that preloads) | Sal enixum consumption g | Temperature ℃ | Pressure mm Hg | Input speed g/h | Productive rate % |
| 8 | 1800(25) | 600 | 160 | 500 | 150 | 95.2 |
| 9 | 1800(50) | 900 | 180 | 650 | 100 | 92.4 |
| 10 | 1800(30) | 700 | 130 | 100 | 200 | 92.9 |
| 11 | 1800(30) | 300 | 160 | 100 | 200 | 90.7 |
| 12 | 1800(10) | 500 | 160 | 600 | 150 | 93.0 |
| 13 | 2700(30) | 800 | 180 | 200 | 250 | 96.1 |
| 14 | 2700(40) | 1500 | 150 | 300 | 300 | 94.3 |
Embodiment 15
Cinnamic synthetic to tert.-butoxy
In reactor, add 750g to the tert.-butoxy carbinol methine, and then add 8gTMP and 700g sal enixum, mix.Pressure in the reactor is reduced to about 500mmHg, and temperature rises to 130 ℃.Speed with 60g/hr drips 1190g to the tert.-butoxy carbinol methine in reactor.After beginning to receive product in the condensation receiving trap, slowly temperature of reaction kettle is risen to 180 ℃, the rate of addition of tert.-butoxy carbinol methine is brought up to 190g/h.Reacted again after dropwising 30 minutes, and temperature of reaction kettle was elevated to 190 ℃ then, to there not being stopped reaction behind the overhead product.Rectifying behind the adding 55gTMP finally obtains tert.-butoxy vinylbenzene 1655g, productive rate 94.0% in the emulsified soln that collection obtains.
Embodiment 16-20
With the method for embodiment 15, synthetic with conditions such as differing temps, pressure, input speed, dewatering agent consumptions to tert.-butoxy vinylbenzene, the results are shown in table 3.Temperature in the table and input speed are meant temperature and the input speed that begins to collect product afterreaction still in the condensing works.
Table 3
| Embodiment | Rubigan carbinol methine total amount g (the ratio % that preloads) | Sal enixum consumption g | Temperature ℃ | Pressure mmHg | Input speed g/h | Productive rate % |
| 16 | 1552(20) | 460 | 150 | 300 | 160 | 95.2 |
| 17 | 1940(40) | 900 | 160 | 500 | 200 | 93.9 |
| 18 | 1940(40) | 750 | 180 | 100 | 200 | 96.1 |
| 19 | 1940(30) | 750 | 180 | 100 | 300 | 95.3 |
| 20 | 1552(10) | 400 | 160 | 500 | 160 | 91.6 |
Claims (5)
- One kind utilize α-or the bata-phenethyl alcohol compounds method that dehydration reaction is produced styrene compound takes place under catalyst action, it is characterized in that:Described α-or the bata-phenethyl alcohol compounds beOr
Position or contraposition were alkyl, straight or branched alkoxyl group or the ester group of H, halogen, straight or branched between R base wherein was positioned at; Described reaction is carried out as follows:(1) with the α of 10%-80%-or bata-phenethyl alcohol compounds, dewatering agent and stopper uniform mixing in advance in reactor;(2) temperature of reaction kettle is risen to behind the preset temperature to wherein dripping residue reaction raw materials α-or bata-phenethyl alcohol compounds;(3) under reduced pressure product is steamed from the rectifying tower top by the condensing works collection in the reaction process, unreacting material then condensation is got back to continuation reaction in the reactor. - 2. the method for production styrene compound as claimed in claim 1 is characterized in that: described dewatering agent is selected from mineral acid, organic acid, inorganic oxide, acidic ion exchange resin or hydrosulfate, and the mixture of above-mentioned various dewatering agents.
- 3. the method for production styrene compound as claimed in claim 1 is characterized in that: the consumption of described dewatering agent is that α-or the 0.1-1 of bata-phenethyl alcohol compounds weight doubly.
- 4. the method for production styrene compound as claimed in claim 1 is characterized in that: described reaction is carried out under 100-250 ℃.
- 5. the method for production styrene compound as claimed in claim 1 is characterized in that: the pressure of described dehydration reaction is 0.1-760mmHg.
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| CNB2005100678561A CN100348558C (en) | 2005-04-29 | 2005-04-29 | Production of phenylethylene compound |
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| CNB2005100678561A CN100348558C (en) | 2005-04-29 | 2005-04-29 | Production of phenylethylene compound |
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| CN100348558C true CN100348558C (en) | 2007-11-14 |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103922902B (en) * | 2013-01-11 | 2016-12-28 | 南京科技职业学院 | To the methoxybenzene ethanol synthesis technique to methoxy styrene |
| CN103936553A (en) * | 2013-01-18 | 2014-07-23 | 南京化工职业技术学院 | Process for synthesizing chlorostyrene by chlorophenethyl alcohol |
| KR102093540B1 (en) * | 2017-08-11 | 2020-03-25 | 주식회사 엘지화학 | Production method of halo-substituted styrene monomer |
| CN111689827B (en) * | 2019-03-14 | 2023-01-03 | 中国石化工程建设有限公司 | Device and method for preparing styrene |
| CN110776389B (en) * | 2019-11-29 | 2022-08-05 | 万华化学集团股份有限公司 | Compound catalyst and method for preparing styrene |
| RU2721773C1 (en) * | 2019-12-31 | 2020-05-22 | Общество С Ограниченной Ответственностью "Научно-Производственное Объединение "Еврохим" | Method of producing styrene |
| CN111087303A (en) * | 2019-12-31 | 2020-05-01 | 浙江工业大学 | Synthesis method of p-acetoxystyrene |
Citations (8)
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|---|---|---|---|---|
| CN86103091A (en) * | 1986-05-09 | 1987-11-18 | 中国科学院化学研究所 | Synthetic process of vinyl pyridine at atmomspheric pressure |
| JPS6317833A (en) * | 1986-07-11 | 1988-01-25 | Mitsui Toatsu Chem Inc | Dehydration of methylphenylcarbinol |
| CN1043694A (en) * | 1988-12-26 | 1990-07-11 | 三井石油化学工业株式会社 | The preparation method of propylene |
| CN1300272A (en) * | 1998-05-11 | 2001-06-20 | 国际壳牌研究有限公司 | Process for the preparation of styrenes |
| CN1310698A (en) * | 1998-07-20 | 2001-08-29 | 国际壳牌研究有限公司 | Process for the preparation of styrene and propylene oxide |
| WO2004020369A1 (en) * | 2002-08-27 | 2004-03-11 | Shell Internationale Research Maatschappij B.V. | Process for the preparation of styrene or substituted styrene |
| WO2004085351A1 (en) * | 2003-03-26 | 2004-10-07 | Sumitomo Chemical Company, Limited | METHOD FOR PRODUCING α-METHYLSTYRENE |
| US6849771B2 (en) * | 2002-08-06 | 2005-02-01 | Shell Oil Company | Process |
-
2005
- 2005-04-29 CN CNB2005100678561A patent/CN100348558C/en not_active Expired - Fee Related
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86103091A (en) * | 1986-05-09 | 1987-11-18 | 中国科学院化学研究所 | Synthetic process of vinyl pyridine at atmomspheric pressure |
| JPS6317833A (en) * | 1986-07-11 | 1988-01-25 | Mitsui Toatsu Chem Inc | Dehydration of methylphenylcarbinol |
| CN1043694A (en) * | 1988-12-26 | 1990-07-11 | 三井石油化学工业株式会社 | The preparation method of propylene |
| CN1300272A (en) * | 1998-05-11 | 2001-06-20 | 国际壳牌研究有限公司 | Process for the preparation of styrenes |
| CN1310698A (en) * | 1998-07-20 | 2001-08-29 | 国际壳牌研究有限公司 | Process for the preparation of styrene and propylene oxide |
| US6849771B2 (en) * | 2002-08-06 | 2005-02-01 | Shell Oil Company | Process |
| WO2004020369A1 (en) * | 2002-08-27 | 2004-03-11 | Shell Internationale Research Maatschappij B.V. | Process for the preparation of styrene or substituted styrene |
| WO2004085351A1 (en) * | 2003-03-26 | 2004-10-07 | Sumitomo Chemical Company, Limited | METHOD FOR PRODUCING α-METHYLSTYRENE |
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