CN110483287A - A kind of production method of the fluffy Lipase absobed fragrance of high-content ring lattice - Google Patents

A kind of production method of the fluffy Lipase absobed fragrance of high-content ring lattice Download PDF

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Publication number
CN110483287A
CN110483287A CN201910828326.6A CN201910828326A CN110483287A CN 110483287 A CN110483287 A CN 110483287A CN 201910828326 A CN201910828326 A CN 201910828326A CN 110483287 A CN110483287 A CN 110483287A
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reaction
added
kettle
fluffy
fragrance
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王天义
徐基平
徐基龙
汪洋
吴旭
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ANHUI HYEA AROMAS Co Ltd
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ANHUI HYEA AROMAS Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/28—Molybdenum
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/09—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid esters or lactones
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/31—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of functional groups containing oxygen only in singly bound form
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B9/00—Essential oils; Perfumes
    • C11B9/0026—Essential oils; Perfumes compounds containing an alicyclic ring not condensed with another ring
    • C11B9/0034—Essential oils; Perfumes compounds containing an alicyclic ring not condensed with another ring the ring containing six carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated

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Abstract

The invention discloses a kind of production methods of the fluffy Lipase absobed fragrance of high-content ring lattice; it include: (1) using dichloroethanes as solvent; under the conditions of nitrogen protection; using solid catalyst; ethyl diazoacetate and cyclohexanol are starting material; cyclohexyloxy ethyl ester is obtained through O-H intercalation reaction, is then saponified, is acidified to obtain cyclohexyloxy；(2) using solid acid as catalyst, cyclohexyloxy and allyl alcohol carry out esterification, obtain the fluffy ester fragrance product of ring lattice；The present invention produces the fluffy ester fragrance of high-content ring lattice after O-H intercalation reaction, saponification, acidification, esterification, substantially reduces the reaction time using cyclohexanol and ethyl diazoacetate as starting material, and process flow is relatively brief, and raw material is easy to get, and total recovery improves.

Description

A kind of production method of the fluffy Lipase absobed fragrance of high-content ring lattice
Technical field
The invention belongs to technical field of spice production, and in particular to a kind of producer of the fluffy Lipase absobed fragrance of high-content ring lattice Method.
Background technique
The fluffy ester of ring lattice, CAS 68901-15-5, chemical name cyclohexyloxy allyl acetate are a kind of important ring lattice Fluffy esters synthetic perfume, colourless liquid, with strong lattice it is fluffy as green fragrant fragrance be widely used in and with fruity note In daily chemical essence formula, it is mainly used for fragrance for detergents, in synthetic detergent composition, dosage 0.1%, it can also be used to fragrant The flavoring of the various products such as water, cosmetics, air freshener.
The fluffy ester production method of traditional ring lattice is to prepare cyclohexyloxy, yield by Williamson reaction first 80% or so, catalyst is then made with sulfuric acid, perchloric acid, p-methyl benzenesulfonic acid etc., obtains ring lattice through esterification with propenyl Fluffy ester；This intermediate of synthesizing cyclohexane 1 ethoxyacetic acid just becomes the key for preparing cyclohexyloxy allyl acetate, synthesizing cyclohexane 1 oxygen Guanidine-acetic acid is firstly the need of cyclohexyloxy sodium is prepared, and report mainly has 3 kinds of methods at present: first is that using metallic sodium as reaction reagent, Dehydrogenation is reacted with cyclohexanol and prepares hexamethylene sodium alkoxide, then prepares hexamethylene oxygen as solvent and chloroacetate reaction dechlorination sodium in dimethylbenzene Guanidine-acetic acid, reaction require to carry out under anhydrous system, and technology difficulty is big, high using metallic sodium risk, are difficult to realize industrialization Production；Second is that using sodium hydride as reaction reagent, in the case where tetrahydrofuran is as solvent and after cyclohexanol reaction production sodium alkoxide, then Cyclohexyloxy sodium is generated with chloroacetate reaction under dimethyl sulphoxide solution, then acidification prepares hexamethylene oxygen under strongly acidic conditions Guanidine-acetic acid, reaction use sodium hydride, require reaction system extremely stringent, it is desirable that reaction system is anhydrous, low temperature, using a large amount of Organic solvent, and have hydrogen generation, severe reaction conditions, trivial operations, cost of material is high, and it is raw to be unsuitable for industrially scalable It produces；Third is that sodium chloroacetate and cyclohexanol reaction generate cyclohexyloxy sodium, then acidified using NaOH as catalysts After obtain cyclohexyloxy, low using the route reaction yield, the reaction time is long, and post-processing difficulty is big, is unsuitable for industry Metaplasia produces.In addition acid catalyst sulfuric acid used in step of esterification etc. is cheap as traditional esterifications catalyst, catalysis Effect is preferably used till today, but its severe corrosion to equipment, and acid-bearing wastewater pollutes environment.
Summary of the invention
The purpose of the present invention is to provide a kind of production method of the fluffy Lipase absobed fragrance of high-content ring lattice, instead of Williamson reaction, uses ethyl diazoacetate and cyclohexanol for starting material, passes through under solid acid catalyst catalytic action O-H insertion, saponification, acidification and esterification produce the fluffy Lipase absobed fragrance of ring lattice, substantially reduce reaction time, Essential Safety Level is improved.
The purpose of the present invention can be achieved through the following technical solutions:
A kind of production method of the fluffy Lipase absobed fragrance of ring lattice, specifically includes the following steps:
(1) dichloroethanes is added into ingredients pot, ethyl diazoacetate is then added, turn on agitator is configured to 30% Ethyl diazoacetate is driven into spare in head tank；
(2) it first passes through reaction kettle hand hole and solid rhodium series catalysts is added, hexamethylene alcohol and solvent is then added into reaction kettle Dichloroethanes opens reaction kettle stirring, is continually fed into nitrogen；
(3) open reaction kettle steam valve, begin to warm up, kettle temperature risen to 60-80 DEG C, from head tank by be added dropwise pump to The dichloroethane solution of 30% ethyl diazoacetate is added dropwise in reaction kettle, time for adding control continues after 4-8h, completion of dropwise addition Insulation reaction 2-4h, the content of sampling gas chromatographic detection ethyl diazoacetate is 0.5% hereinafter, reaction was completed, by reaction kettle Temperature is reduced to room temperature；Solid catalyst recoil is washed till in reaction kettle by automatic backwashing filter and carries out the anti-of lower batch It answers, the reaction solution of liquid phase is transferred in the distillation still of still distillation tower；
(4) distillation still steam valve is opened, kettle temperature is risen to 57-60 DEG C, normal pressure recycles dichloroethanes, until tower top does not discharge Or when tower top temperature decline, terminate recycling dichloroethanes, the dichloroethanes of recycling is applied, and low vacuum, vacuum distillation are opened Excessive cyclohexanol is recycled, the cyclohexanol of recycling is applied；
(5) distillation still bottom reaction solution is transferred in agitated kettle, 10% sodium hydroxide solution of addition, turn on agitator, It is heated to 60 DEG C, after saponification 3-5h, reaction was completed, and kettle temperature is reduced to room temperature, and 15% hydrochloric acid is added and is acidified, to tune Reaction solution pH=2.5-3.0 is saved, 2h is stood, layering separates water layer to Sewage Disposal and handled, and saturation chlorination is added in oil reservoir Sodium solution washs 3 times, separates water layer and is driven into head tank and applied, separates oil reservoir and obtain cyclohexyloxy, be transferred to In a cyclohexyloxy high position；
(6) allyl alcohol and water entrainer hexamethylene is added into the reaction kettle of the esterification with tower respectively, solid is added by hand hole Acid catalyst and polymerization inhibitor, then the cyclohexyloxy that step (5) obtains is transferred in reaction kettle of the esterification, open esterification Kettle temperature is risen to 60-65 DEG C, reacts 2-4h, separate hexamethylene and water in time from the tower top of reaction kettle of the esterification, passed through by kettle steam valve When the content of gas chromatographic detection cyclohexyloxy is below 0.5%, reaction was completed, will be consolidated by backwashing automatic filter The recoil of body acid is washed till the operation that lower batch is carried out in reaction kettle of the esterification, and the reaction solution of liquid phase is transferred in washing kettle；
(7) 10% sodium hydroxide solution is added into washing kettle, turn on agitator is washed, and stratification separates water Layer is sent into Sewage Disposal and is handled；Then clear water is added to the oil reservoir separated and carries out washing 3 times, separate water layer and be sent into sewage Treating stations are handled, and the oil reservoir separated is transferred in the rectifying still of autoclave rectifying column；
(8) rectifying still steam valve is opened, rectifying still is heated up, opens low vacuum, excessive allyl is collected in vacuum distillation Alcohol, the allyl alcohol recycled of recycling are then turned on high vacuum, and the fluffy ester fragrance product of ring lattice is collected in vacuum distillation.
Further, solid rhodium series catalysts described in step (2) are Rh2(OAc)4, the quality amount of addition is diazoacetic acid second The 1%-5% of ester quality is preferably added the 1.5%-2% that quality is ethyl diazoacetate quality.
Further, the inventory molar ratio of the ethyl diazoacetate and cyclohexanol of the dropwise addition is 1:1-1:5, preferably Molar ratio is 1:1.5-1:2.
Further, the automatic back flush filtration of solid rhodium series catalysts and solid acid catalyst takes following manner to handle: Reaction dissolvent is squeezed into dehydrating kettle automatic backwashing filter from solvent head tank with chemical industry dnockout pumps, and temporary by reaction solution The nitrogen inlet of slot is passed through nitrogen, in solid rhodium series catalysts or solid acid catalyst pressurized backwash to kettle, will carry out down criticizing It is applied when secondary operation.
Further, cy500 stainless steel ripple packing is filled in the still distillation tower.
Further, the condition of the vacuum distillation recycling cyclohexanol are as follows: 71-74 DEG C of temperature, vacuum pressure 3333Pa.
Further, the solid acid catalyst is Yb-MoO3/Al2O3-ZrO2, the addition quality amount of solid acid catalyst For the 1%-10% of cyclohexyloxy quality, it is preferably added the 1.5%-2.5% that quality is cyclohexyloxy quality.
Further, the molar ratio of cyclohexyloxy and allyl alcohol is 1:1-5:1 in the esterification, is preferably rubbed You are than being 1:1.5-1:1.8.
Further, solid acid catalyst Yb-MoO described in step (6)3/Al2O3-ZrO2, wherein element Yb:Mo:Al:Zr Mass ratio be 0.5-0.7:4.5-5.8:3.0-3.5:5.4-8.2.
Further, the polymerization inhibitor is the compound polymerization inhibitor of N, N-diethylhydroxylamine and tert-butyl catechol, and compounding proportion is 2:1-1:2 (wt%), additional amount are the 0.1%-1% of allyl alcohol mass ratio, and the amount of being preferably added is allyl alcohol mass ratio 0.1%-0.25%.
Further, cy700 stainless steel ripple packing is filled in the autoclave rectifying column.
Further, the condition of the vacuum distillation recycling allyl alcohol are as follows: 37-40 DEG C of temperature, vacuum pressure 6667Pa, The condition of the fluffy ester of ring lattice is collected in vacuum distillation are as follows: and 108-111 DEG C of temperature, vacuum pressure 1333Pa.
Further, the allyl alcohol content in the fluffy ester fragrance product of the ring lattice of collection controls below 0.1%.
Beneficial effects of the present invention:
The present invention provides a kind of production methods of the fluffy Lipase absobed fragrance of ring lattice, react instead of Williamson, use Ethyl diazoacetate and cyclohexanol are starting material, after O-H intercalation reaction, saponification and acidification obtain cyclohexyloxy, then After solid acid catalysis and allyl alcohol condensation, the production fluffy Lipase absobed fragrance of ring lattice substantially reduces the reaction time, improves essence Safety, and produce the allyl alcohol content in the obtained fluffy ester of ring lattice and control 0.1% hereinafter, avoiding allyl alcohol too high levels institute Caused deferred irritation problem in final cosmetics.
In addition solid acid catalyst Yb-MoO3/Al2O3-ZrO2It is set with being easy to separate with liquid-phase reaction system, not corrode Advantage standby, post-processing is simple overcomes the problem of existing liquid acid is to equipment corrosion and acid-bearing wastewater pollution environment, Er Qiexuan Selecting property is high, can carry out at a lower temperature, save energy consumption, reduce the generation of side reaction, can greatly improve production efficiency, The fluffy ester content of ring lattice of preparation is up to 99% or more, soft with the strong fluffy fragrance of lattice and fruity fragrance, aroma of pure.
Specific embodiment
The technical scheme in the embodiments of the invention will be clearly and completely described below, it is clear that described implementation Example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is common Technical staff's all other embodiment obtained without creative efforts belongs to the model that the present invention protects It encloses.
Embodiment 1
Acid catalyst the preparation method comprises the following steps:
The eight hydration zirconyl chloride solutions that 100ml mass concentration is 26% are prepared, sequentially add 10g hydroxide while stirring Aluminium, 11g ammonium molybdate add 1.56g Yb (NO after stirring 15min is completely dissolved3)3·5H2O will be above-mentioned after stirring and dissolving The ammonium hydroxide that solution is prepared together with 8mol/L is added in the ammonia spirit of 300ml pH=9.00 simultaneously, and process is added dropwise and keeps solution PH be maintained between 8.95-9.10, after completion of dropwise addition, continue stir 30min, be aged at room temperature for 24 hours, filter, using go from Sub- water washing solid is existed and (is detected using the silver nitrate solution of 0.1mol/L) without chloride ion into cleaning solution, is done at 105 DEG C Dry 8h is finally putting into atmosphere protection batch-type furnace (nitrogen protection) and roasts 2h at 800 DEG C, and taking-up is cooled to room temperature and obtains acid Catalyst Yb-MoO3/Al2O3-ZrO2。
Embodiment 2
A kind of production method of the fluffy Lipase absobed fragrance of ring lattice, specifically includes the following steps:
(1) then the metered dichloroethanes 260L into 500L ingredients pot is added metering ethyl diazoacetate 120L, opens Blender is opened, 30% ethyl diazoacetate is configured to, is driven into spare in head tank；
(2) it first passes through 1000L reaction kettle hand hole and solid rhodium series catalysts 2kg is added, hexamethylene is then added into reaction kettle Alcohol 135L and solvent dichloroethanes 200L opens reaction kettle stirring, is continually fed into nitrogen；
(3) reaction kettle steam valve is opened, begins to warm up, kettle temperature is risen to 65 DEG C, is pumped from head tank by being added dropwise to anti- The dichloroethane solution 380L that 30% ethyl diazoacetate is added dropwise in kettle is answered, time for adding control continues after 5h, completion of dropwise addition Insulation reaction 4h samples the content of gas chromatographic detection ethyl diazoacetate 0.5% hereinafter, reaction was completed, will react kettle temperature Degree is reduced to room temperature；Solid catalyst recoil is washed till in reaction kettle by automatic backwashing filter and carries out the anti-of lower batch It answers, the reaction solution of liquid phase is transferred in the 1000L distillation still of still distillation tower；
(4) open distillation still steam valve, kettle temperature risen to 57 DEG C, normal pressure recycles dichloroethanes, until tower top do not discharge or When tower top temperature declines, terminate recycling dichloroethanes, the dichloroethanes of recycling is transferred to dichloroethanes head tank and is applied, opened Low vacuum is opened, at 72 DEG C of temperature, under the conditions of vacuum pressure is 3333Pa, excessive cyclohexanol, the ring of recycling are recycled in vacuum distillation Hexanol, which is transferred in cyclohexanol head tank, apply when next batch operation；
(5) distillation still bottom reaction solution is transferred in 1000L agitated kettle, configured 10% sodium hydroxide solution is added 200L, turn on agitator are heated to 60 DEG C, and after saponification 4h, reaction was completed, and kettle temperature is reduced to room temperature, 15% salt is added Acid is acidified, and until adjusting reaction solution pH=2.5-3.0, stands 2h, layering separates at water layer to Sewage Disposal Reason, oil reservoir are added saturated sodium chloride solution and wash 3 times, and saturated sodium chloride solution 50L is added every time, and preceding washing twice separates water layer It is driven into head tank and is applied, divide water water layer to be transferred to Sewage Disposal for the last time and handled.The oil reservoir separated obtains To cyclohexyloxy 135kg, it is transferred in cyclohexyloxy head tank；
(6) allyl alcohol 100L and water entrainer hexamethylene 200L is added into the 500L reaction kettle of the esterification with tower respectively, passes through Solid acid catalyst 3kg, polymerization inhibitor 0.2kg is added in hand hole, then the cyclohexyloxy that step (5) obtains is transferred to esterification instead It answers in kettle, opens reaction kettle of the esterification steam valve, kettle temperature is risen to 65 DEG C, reacts 4h, tower top and time-division from reaction kettle of the esterification Hexamethylene and water out, when the content through gas chromatographic detection cyclohexyloxy is below 0.5%, reaction was completed, passes through recoil It washes automatic filter and solid acid recoil is washed till to the operation for carrying out lower batch in reaction kettle of the esterification, the reaction solution of liquid phase is transferred to In 500L washing kettle；
(7) 10% sodium hydroxide solution 60L is added into washing kettle, turn on agitator is washed, and stratification separates Water layer is sent into Sewage Disposal and is handled.Then clear water is added to the oil reservoir separated and carries out washing 3 times, each clear water additional amount For 100L, separates water layer feeding Sewage Disposal and handled, the oil reservoir separated is transferred to the 500L rectifying still of autoclave rectifying column In；
(8) rectifying still steam valve is opened, rectifying still is heated up, opens low vacuum, at 40 DEG C of temperature, vacuum pressure is Under the conditions of 6667Pa, excessive allyl alcohol is collected in vacuum distillation, and the allyl alcohol of recycling is transferred to circulating sleeve in allyl alcohol head tank With, be then turned on high vacuum, under the conditions of 108-111 DEG C of temperature, vacuum pressure 1333Pa, vacuum distillation collect the fluffy ester of ring lattice, obtain To the fluffy ester fragrance product 150kg of ring lattice.
Product testing GC condition are as follows: chromatographic column HP-5 (30m x 0.32mm x 0.25um)；Detector FID, temperature 250 ℃；Sample introduction: sample volume about 0.2ul, split ratio 1:100,250 DEG C of injector temperature；Carrier gas: N2, flow velocity 20L/min are pressed before column 34.47kPa；Chromatograph oven temperature: for linear temperature program from 80 DEG C -220 DEG C, rate is 10 DEG C/min, retains 20min.
Detect the obtained fluffy Lipase absobed fragrance of ring lattice have strong lattice it is fluffy as green fragrant fragrance, and with fruity note, It is 99.40% through gas chromatographic analysis product assay, allyl alcohol content 0.02%, (20 DEG C) of refraction index of detection are 1.4632, (25 DEG C) of relative density are 1.0151.
Embodiment 3
A kind of production method of the fluffy Lipase absobed fragrance of ring lattice, specifically includes the following steps:
(1) then metering ethyl diazoacetate 66kg is added in the metered dichloroethanes 154kg into 250L ingredients pot, Turn on agitator is configured to 30% ethyl diazoacetate, is driven into spare in head tank；
(2) it first passes through 500L reaction kettle hand hole and solid rhodium series catalysts 1kg is added, cyclohexanol is then added into reaction kettle 95kg and solvent dichloroethanes 100kg opens reaction kettle stirring, is continually fed into nitrogen；
(3) reaction kettle steam valve is opened, begins to warm up, kettle temperature is risen to 60 DEG C, is pumped from head tank by being added dropwise to anti- The dichloroethane solution 220kg for 30% ethyl diazoacetate for answering a dropping step in kettle (1) spare, time for adding are controlled in 8h, The subsequent continuous insulation reaction 4h of completion of dropwise addition samples the content of gas chromatographic detection ethyl diazoacetate 0.5% hereinafter, terminating anti- It answers, temperature of reaction kettle is reduced to room temperature.By automatic backwashing filter by solid catalyst recoil be washed till in reaction kettle into The reaction of the lower batch of row, the reaction solution of liquid phase is transferred in the 500L distillation still of still distillation tower；
(4) open distillation still steam valve, kettle temperature risen to 60 DEG C, normal pressure recycles dichloroethanes, until tower top do not discharge or When tower top temperature declines, terminate recycling dichloroethanes, the dichloroethanes of recycling is transferred to dichloroethanes head tank and is applied, opened Low vacuum is opened, at 74 DEG C of temperature, under the conditions of vacuum pressure is 3333Pa, excessive cyclohexanol, the ring of recycling are recycled in vacuum distillation Hexanol, which is transferred in cyclohexanol head tank, apply when next batch operation；
(5) distillation still bottom reaction solution is transferred in 500L agitated kettle, configured 10% sodium hydroxide solution is added 100kg, turn on agitator are heated to 60 DEG C, and after saponification 5h, reaction was completed, and kettle temperature is reduced to room temperature, 15% salt is added Acid is acidified, and until adjusting reaction solution pH=2.5-3.0, stands 2h, layering separates at water layer to Sewage Disposal Reason, oil reservoir are added saturated sodium chloride solution and wash 3 times, and saturated sodium chloride solution 30kg is added every time, and preceding washing twice separates water Layer, which is driven into head tank, to be applied, and is divided water water layer to be transferred to Sewage Disposal for the last time and is handled；The oil reservoir separated Cyclohexyloxy 67kg is obtained, is transferred in cyclohexyloxy head tank；
(6) allyl alcohol 42kg and water entrainer hexamethylene 78kg is added into the 250L reaction kettle of the esterification with tower respectively, passes through Solid acid catalyst 1.5kg and polymerization inhibitor 0.1kg is added in hand hole, then the cyclohexyloxy that step (5) obtains is transferred to ester Change in reaction kettle, open reaction kettle of the esterification steam valve, kettle temperature is risen to 65 DEG C, reacts 2h, from the tower top of reaction kettle of the esterification and When separate hexamethylene and water, when the content through gas chromatographic detection cyclohexyloxy is below 0.5%, reaction was completed, passes through Solid acid recoil is washed till the operation that lower batch is carried out in reaction kettle of the esterification by backwash automatic filter, and the reaction solution of liquid phase is turned It moves on in 250L washing kettle；
(7) 10% sodium hydroxide solution 30kg is added into washing kettle, turn on agitator is washed, stratification, point Water-yielding stratum is sent into Sewage Disposal and is handled.Then clear water is added to the oil reservoir separated and carries out washing 3 times, clear water is added every time 30kg separates water layer feeding Sewage Disposal and is handled, and the oil reservoir separated is transferred in the 250L rectifying still of autoclave rectifying column；
(8) rectifying still steam valve is opened, rectifying still is heated up, opens low vacuum, at 38 DEG C of temperature, vacuum pressure is Under the conditions of 6667Pa, excessive allyl alcohol is collected in vacuum distillation, and the allyl alcohol of recycling is transferred to circulating sleeve in allyl alcohol head tank With, be then turned on high vacuum, under the conditions of 102-105 DEG C of temperature, vacuum pressure 1333Pa, vacuum distillation collect the fluffy ester of ring lattice, obtain To the fluffy ester fragrance product 75kg of ring lattice.
Product testing GC condition are as follows: chromatographic column HP-5 (30m x 0.32mm x 0.25um)；Detector FID, temperature 250 ℃；Sample introduction: sample volume about 0.2ul, split ratio 1:100,250 DEG C of injector temperature；Carrier gas: N2, flow velocity 20L/min are pressed before column 34.47kPa；Chromatograph oven temperature: for linear temperature program from 80 DEG C -220 DEG C, rate is 10 DEG C/min, retains 20min.
Detect the obtained fluffy Lipase absobed fragrance of ring lattice have strong lattice it is fluffy as green fragrant fragrance, and with fruity note, It is 99.31% through gas chromatographic analysis product assay, allyl alcohol content 0.02%, (20 DEG C) of refraction index of detection are 1.4628, (25 DEG C) of relative density are 1.0152.
It is anti-instead of Williamson the present invention provides a kind of synthetic method of cyclohexyloxy allyl acetate fragrance It answers, using ethyl diazoacetate and cyclohexanol in catalyst Rh2(OAc)4O-H intercalation reaction is carried out under catalytic action has synthesized ring Hexyloxy ethyl acetate, be saponified, be acidified after obtain cyclohexyloxy, then with allyl alcohol be condensed production the fluffy ester of ring lattice, greatly The reaction time is shortened greatly, process flow is relatively brief, and essential safety level improves；Solid catalyst uses automatic backwash Filtering technique realizes the separation of solid and liquid of solid acid catalyst, has and is easy to separate with liquid-phase reaction system, does not corrode equipment, rear place Simple advantage is managed, overcomes the problem of existing liquid acid is to equipment corrosion and acid-bearing wastewater pollution environment, and selectivity is high, It can carry out at a lower temperature, save energy consumption, reduce the generation of side reaction, production efficiency can be greatly improved, produced To the fluffy ester content of ring lattice reach 99% or more, and contained allyl alcohol content is controlled 0.1% hereinafter, avoiding allyl alcohol content Irritation problem deferred in final cosmetics caused by excessively high, product have the strong fluffy fragrance of lattice and fruity fragrant Gas, aroma of pure are soft.
The above content is just an example and description of the concept of the present invention, affiliated those skilled in the art It makes various modifications or additions to the described embodiments or is substituted in a similar manner, without departing from invention Design or beyond the scope defined by this claim, be within the scope of protection of the invention.

Claims (10)

1. a kind of production method of the fluffy Lipase absobed fragrance of high-content ring lattice, it is characterised in that: specifically includes the following steps:
(1) dichloroethanes is added into ingredients pot, ethyl diazoacetate is then added, turn on agitator is configured to 30% diazonium Ethyl acetate is driven into spare in head tank；
(2) it first passes through reaction kettle hand hole and solid rhodium series catalysts is added, hexamethylene alcohol and solvent dichloro is then added into reaction kettle Ethane opens reaction kettle stirring, is continually fed into nitrogen；
(3) reaction kettle steam valve is opened, begins to warm up, kettle temperature is risen to 60-80 DEG C, from head tank by the way that pump is added dropwise to reaction The dichloroethane solution of 30% ethyl diazoacetate is added dropwise in kettle, time for adding control is in 4-8h, the subsequent continuation of insurance temperature of completion of dropwise addition 2-4h is reacted, the content of sampling gas chromatographic detection ethyl diazoacetate is 0.5% hereinafter, reaction was completed, by temperature of reaction kettle It is reduced to room temperature；Solid catalyst recoil is washed till to the reaction that lower batch is carried out in reaction kettle by automatic backwashing filter, The reaction solution of liquid phase is transferred in the distillation still of still distillation tower；
(4) distillation still steam valve is opened, kettle temperature is risen to 57-60 DEG C, normal pressure recycles dichloroethanes, until tower top does not discharge or tower When the temperature drops, terminating recycling dichloroethanes, the dichloroethanes of recycling is applied on top, opens low vacuum, vacuum distillation recycling The cyclohexanol of excessive cyclohexanol, recycling is applied；
(5) distillation still bottom reaction solution is transferred in agitated kettle, 10% sodium hydroxide solution, turn on agitator, heating is added To 60 DEG C, after saponification 3-5h, reaction was completed, and kettle temperature is reduced to room temperature, and 15% hydrochloric acid is added and is acidified, to adjusting instead Liquid pH=2.5-3.0 is answered, 2h is stood, layering separates water layer to Sewage Disposal and handled, and it is molten that saturated sodium-chloride is added in oil reservoir Liquid washs 3 times, separates water layer and is driven into head tank and applied, obtains oil reservoir cyclohexyloxy, be transferred to cyclohexyloxy In acetic acid head tank；
(6) allyl alcohol and water entrainer hexamethylene is added into the reaction kettle of the esterification with tower respectively, solid acid is added by hand hole and is urged Agent and polymerization inhibitor, then the cyclohexyloxy that step (5) obtains is transferred in reaction kettle of the esterification, it opens reaction kettle of the esterification and steams Kettle temperature is risen to 60-65 DEG C, reacts 2-4h, hexamethylene and water are separated in time from the tower top of reaction kettle of the esterification, through gas phase by steam valve door When chromatography detects the content of cyclohexyloxy below 0.5%, reaction was completed, by backwashing automatic filter for solid acid Recoil is washed till the operation that lower batch is carried out in reaction kettle of the esterification, and the reaction solution of liquid phase is transferred in washing kettle；
(7) 10% sodium hydroxide solution is added into washing kettle, turn on agitator is washed, stratification, is separated water layer and is sent Enter Sewage Disposal to be handled；Then clear water is added to the oil reservoir separated and carries out washing 3 times, separate water layer and be sent into sewage treatment Station is handled, and the oil reservoir separated is transferred in the rectifying still of autoclave rectifying column；
(8) rectifying still steam valve is opened, rectifying still is heated up, opens low vacuum, excessive allyl alcohol is collected in vacuum distillation, is returned The allyl alcohol recycled of receipts, is then turned on high vacuum, and the fluffy ester fragrance product of ring lattice is collected in vacuum distillation.
2. a kind of production method of the fluffy Lipase absobed fragrance of high-content ring lattice according to claim 1, it is characterised in that: step (2) the solid rhodium series catalysts described in are Rh2(OAc)4, the quality that solid rhodium series catalysts are added is ethyl diazoacetate quality 1%-5%, be preferably added quality be ethyl diazoacetate quality 1.5%-2%.
3. a kind of production method of solid acid catalyst synthesis fluffy ester fragrance of ring lattice according to claim 1, feature exist In: the inventory molar ratio of the cyclohexanol and ethyl diazoacetate is 1:1-5:1, and preferred molar ratio is 1.5:1-2:1.
4. a kind of production method of the fluffy Lipase absobed fragrance of high-content ring lattice according to claim 1, it is characterised in that: step (6) solid acid catalyst described in is Yb-MoO3/Al2O3-ZrO2, wherein the mass ratio of element Yb:Mo:Al:Zr is 0.5- 0.7:4.5-5.8:3.0-3.5:5.4-8.2；The addition quality of solid acid catalyst is the 1%- of cyclohexyloxy quality 10%, it is preferably added the 1.5%-2.5% that quality is cyclohexyloxy quality.
5. a kind of production method of solid acid catalyst synthesis fluffy ester fragrance of ring lattice according to claim 1, feature exist In: the molar ratio of cyclohexyloxy described in step (6) and allyl alcohol is 1:1-5:1, and preferred molar ratio is 1:1.5-1: 1.8。
6. a kind of production method of solid acid catalyst synthesis fluffy ester fragrance of ring lattice according to claim 1, feature exist In: polymerization inhibitor described in step (6) is the compound polymerization inhibitor of N, N-diethylhydroxylamine and tert-butyl catechol, N, N-diethylhydroxylamine and tert-butyl Catechol compounding proportion is 2:1-1:2, and the additional amount of polymerization inhibitor is the 0.1%-1% of allyl alcohol mass ratio, is preferably added Amount is the 0.1%-0.25% of allyl alcohol mass ratio.
7. a kind of production method of solid acid catalyst synthesis fluffy ester fragrance of ring lattice according to claim 1, feature exist In: the condition of vacuum distillation recycling cyclohexanol are as follows: 71-74 DEG C of temperature, vacuum pressure 3333Pa.Vacuum distillation recycling allyl alcohol Condition are as follows: 37-40 DEG C of temperature, vacuum pressure 6667Pa, vacuum distillation collect the fluffy ester of ring lattice condition are as follows: temperature 108- 111 DEG C, vacuum pressure 1333Pa.
8. a kind of production method of the fluffy Lipase absobed fragrance of high-content ring lattice according to claim 1, it is characterised in that: solid The automatic back flush filtration of rhodium series catalysts and solid acid catalyst takes following manner to handle: beating from solvent head tank chemical industry Material pump squeezes into reaction dissolvent to dehydrating kettle automatic backwashing filter, and is passed through nitrogen by the nitrogen inlet of reaction solution temporary tank Gas apply when lower batch operation by solid rhodium series catalysts or solid acid catalyst pressurized backwash to kettle.
9. a kind of production method of the fluffy Lipase absobed fragrance of high-content ring lattice according to claim 1, it is characterised in that: step (8) in, the control of allyl alcohol content is below 0.1% in the fluffy ester fragrance product of the ring lattice.
10. a kind of production method of the fluffy Lipase absobed fragrance of high-content ring lattice according to claim 1, it is characterised in that: institute Cy500 stainless steel ripple packing is filled in the still distillation tower stated, and fills cy700 stainless steel ripple in the autoclave rectifying column Filler.
CN201910828326.6A 2019-09-03 2019-09-03 A kind of production method of the fluffy Lipase absobed fragrance of high-content ring lattice Withdrawn CN110483287A (en)

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