CN105085273A - Method for preparing homosalate - Google Patents
Method for preparing homosalate Download PDFInfo
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- CN105085273A CN105085273A CN201510466884.4A CN201510466884A CN105085273A CN 105085273 A CN105085273 A CN 105085273A CN 201510466884 A CN201510466884 A CN 201510466884A CN 105085273 A CN105085273 A CN 105085273A
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
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- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
- C07C29/175—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds with simultaneous reduction of an oxo group
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Abstract
The invention provides a method for preparing homosalate. The method comprises the steps that isophorone serves as raw materials, a hydrogenation reaction is performed under the action of a catalyst, then an epimerization reaction is performed, and 3,3,5-Trimethylcyclohexanol is prepared; a transesterification reaction is performed on the prepared 3,3,5-Trimethylcyclohexanol and methyl salicylate, and finally the homosalate is prepared. The method is easy and convenient to operate, green and environmentally friendly, and the prepared homosalate is high in quality, wherein the cis form content is larger than or equal to 85.0 percent, the trans form content is smaller than or equal to 15 percent, the total content is larger than or equal to 99.0 percent, the single impurity content (GC) is smaller than or equal to 0.1 percent, and the total impurity content (GC) is smaller than or equal to 0.5 percent.
Description
Technical field
The invention belongs to daily-use chemical industry technical field, relate to a kind of preparation method of organic intermediate, the preparation method of the ester that falls apart in particular to the former film of sun-screening agent.
Background technology
The former film of sun-screening agent falls apart ester (HMS), chemistry 3,3,5-trimethylcyclohexyl salicylate by name, and No. CAS is 118-56-9, and English name is Homosalate, and its structural formula is as shown in the formula shown in I:
HMS is water white transparency thick liquid, boiling point 161 ~ 165 DEG C/12mmHg, and relative molecular mass is 262.34, and relative density is 1.049 ~ 1.053g/mL (20 DEG C).
HMS is a kind of ultraviolet (UV) B sun-screening agent, belong to chemical sun, UVB295 ~ 315nm wave band can be absorbed, the consistency of itself and resin is good, not painted, be widely used in the coating such as plastics and nitrocellulose, acrylic resin and urethane such as soft, rigid polyvinyl chloride as photostabilizer, HMS is very little to skin irritation, can add in the cosmetics of super quality, in makeup, the highest addition is 10%, therefore, in recent years, the market requirement of HMS is increasing, is that one has a extensive future, has the product of Development volue.
One of main raw material of synthesis HMS is different Fo Er alcohol (TMC).TMC is the mixture of four kinds of steric isomers, and its structural formula is as shown in the formula shown in II.
Different Fo Er alcohol (TMC), chemical name: 3, 3, 5-cyclonol, English name: 3, 3, 5-Trimethylcyclohexanol, molecular formula: C9H18O, molecular weight: 142.24, CASNo.:116-02-9, it is colourless oil liquid or solid at normal temperatures, there is pure and fresh peppermint fragrance, toxic and pungency, fusing point: 30-32 DEG C, boiling point: 193 ~ 196 DEG C (760mmHg), density: 0.817 ~ 0.860 (25 DEG C, 760mmHg), flash-point: 46 ~ 81 DEG C, specific refractory power: 1.4215 ~ 1.4263 (45 DEG C), vapour pressure 0.173mmHg (25 DEG C), it is water insoluble, be dissolved in alcohols, the organic solvents such as hydro carbons.TMC is that synthesis cyclandelate and former film fall apart the intermediate of ester, the important intermediate of synthesizing new softening agent, lubricant, dintrile, diamines and alcohol.
TMC is prepared with chemical reduction isophorone, such as, at Tetrahedron, 1981,37 (6): 1171 ~ 1179; J.Am.Chem.Soc., 1978,100 (7): 2226 ~ 2227; Tetrahedron1980,36 (13): 1937 ~ 1942; J.Org.Chem., 1980,45 (10): 1946 ~ 1950; Org.React., 2008,71:1 ~ 737; TetrahedronLett., 1995,36 (34): 6051 ~ 6054; Synth.Commun., 1988,18 (1): 89 ~ 96; Bull.KoreanChem.Soc., 2009,30 (7): 1588 ~ 1592; J.Org.Chem., 1986,51 (10): 1769 ~ 1773; Int.J.Cosmet.Sci., 2006, be disclosed in 28 (6): 439-446, these methods have easy to operate, selectivity advantages of higher.But chemical reduction method will use expensive reductive agent, as hydroborate, lithium aluminum hydride, sodium hydride, lithium hydride, trimethyl silane etc., and by producing three a large amount of refuses in last handling process, these methods are made to be difficult to be applied to suitability for industrialized production.
With Ni, Pd, Ru, Cu, Pt etc. for catalyzer, adopt hydrogen or hydrogen transfer reagent to be reductive agent, catalyzer isophorone prepares TMC, such as, in (Catal.Commun., 2008,10 (2): 213 ~ 216; J.Org.Chem., 196025:514 ~ 518; EP1318130; Synlett., 2009, (19): 3143 ~ 3146; PCT2009085826; PrzemyslChemiczny, 2003,82 (8 ~ 9): 1291 ~ 1294; Appl.Catal.B:Environ., 2004,49 (3): 181 ~ 185; PCT2007007646; RSCAdvances, 2013, (26): be disclosed in 10131 ~ 10134, these methods have environmental protection, pollute the advantages such as little, aftertreatment is simple.But method of the prior art or have that pressure is too high or temperature is too high or low conversion rate or produce the shortcoming such as by product or stereoselectivity difference, makes these methods distance suitability for industrialized production also have certain distance, still needs further research.
Synthesis bibliographical information about HMS obtains seldom.US2369084 reports the relevant nature of HMS, but does not provide the synthetic method of HMS.Int.J.Cosmet.Sci., 2006, it is raw material that 28:P439 gives with isophorone, sodium borohydride reduction is utilized to obtain TMC, again with Whitfield's ointment or salicylic acyl chlorides and TMC under an acidic catalyst or basic catalyst effect, and utilize microwave heating, to synthesize the method for HMS, although the productive rate of synthesis TMC is the highest by only 72% up to the productive rate of 99%, HMS.In addition, the solid of adopting the HMS obtained in this way consists of, cis: trans=1:1, but the solid of this composition and on the market available sun-screening agent HMS forms inconsistent.ArhivzaFarmaciju, 1986,36:P161 for raw material, prepare HMS with sodium salicylate and 3,3,5-trimethylcyclohexyl chlorine under phase-transfer catalyst effect, yield only 49 ~ 51%.In addition, document does not provide the steric information of obtained product HMS.
Therefore, need that exploitation is a kind of can to fall apart to the former film of single high-quality the method for ester by easy obtained structure badly.
Summary of the invention
In order to solve the problem, present inventor has performed and study with keen determination, found that: with isophorone as raw material, under catalyst action, carry out hydrogenation reaction, then carry out epimerization reaction, obtained different Fo Er alcohol, obtained different Fo Er alcohol carries out transesterification reaction with wintergreen oil again, and final obtained former film falls apart ester, and the former film obtained according to aforesaid method ester purity of faling apart is high, yield is high, thus completes the present invention.
The object of the present invention is to provide following aspect:
First aspect, the invention provides and a kind ofly prepare former film and to fall apart the method for ester, it is characterized in that, the method comprises the following steps:
Step 1), add isophorone and hydrogenation catalyst in a kettle., pass into hydrogen;
Step 2), epimerization reaction;
Step 3), system cooling step 2 obtained, obtains the different Fo Er alcohol of intermediate;
Step 4), obtained for step 3 different Fo Er alcohol, wintergreen oil and transesterification catalyst are dropped in ester interchange vessel, reacts, obtain former film and to fall apart ester crude product;
Step 5), the ester crude product that fallen apart by former film obtained for step 4 carries out purifying, obtains the former film of product and to fall apart ester.
Second aspect, the present invention also provides a kind of former film that method is obtained according to above-mentioned first aspect to fall apart ester, it is characterized in that, the described former film ester that falls apart is water white transparency thick liquid, refractive index (nd20) is between 1.516-1.519, proportion (20 DEG C, mg/mL) is between 1.049-1.053; Acid number≤1mgKOH/g; %GC content (area normalization method): cis >=85.0%, trans≤15%, total content >=99.0%; Single impurity (GC)≤0.1%, total impurities (GC)≤0.5%.
Embodiment
Below by the present invention is described in detail, the features and advantages of the invention will illustrate along with these and become more clear, clear and definite.
Below in detail the present invention is described in detail.
According to a first aspect of the invention, provide a kind of and prepare former film and to fall apart the method for ester, it is characterized in that, the method comprises the following steps:
Step 1, adds isophorone and hydrogenation catalyst in a kettle., passes into hydrogen.
In the present invention, be first different Fo Er alcohol by isophorone hydrogenating reduction, the present inventor finds, use hydrogen reducing isophorone to prepare different Fo Er alcohol, byproduct of reaction is few, and product yield is high, and isophorone wide material sources, cheap.
In step 1 of the present invention, make spent hydroprocessing catalyst carry out catalysis to its hydrogenation reduction, wherein, described hydrogenation catalyst is skeleton nickel, copper chromite, Rh/C, Rh/Al
2o
3, Pd/C, Pd/Al
2o
3, Ru/C, Ru/Al
2o
3deng, be preferably Ru/C, wherein,
In described Ru/C, based on the gross weight of Ru/C, wherein metal Ru content is 0.5 ~ 50wt% (in butt form), preferably 1 ~ 20wt%, particularly preferably 3 ~ 10wt%, it can be butt form, also can be wet basis form, be preferably wet basis form, more preferably, water ratio is 10 ~ 65%, is preferably 40 ~ 60%;
The present inventor finds, when using above-mentioned hydrogenation catalyst to carry out the hydrogenation reaction of catalysis isophorone, reaction conditions is easy to realize, and easily control, the usage quantity of catalyzer is few, and production cost is low, and convenient post-treatment.
In step 1 of the present invention, the weight ratio of the metallic element (as Ru) in described isophorone and described hydrogenation catalyst except aluminium element is 100000:1 ~ 100:1, preferred 10000:1 ~ 1000:1.
In step 1 of the present invention, optionally, before passing into hydrogen, rare gas element is passed into, as helium, neon, argon gas and/or nitrogen etc., to remove the air in reactor in reactor, thus add security when passing into hydrogen, preferably, make to be full of rare gas element in reactor.
In step 1 of the present invention, when passing into hydrogen, in reactor, hydrogen pressure is 0.5 ~ 10MPa, preferably 0.6 ~ 2.0MPa, is more preferably 0.6 ~ 1.2MPa.
In step 1 of the present invention, when passing into hydrogen, the temperature in reactor is 25 ~ 200 DEG C, preferably 50 ~ 180 DEG C, is more preferably 70 ~ 110 DEG C.
The present inventor finds, under said temperature and pressure condition, isophorone can be reduced sufficiently as different Fo Er alcohol, and products therefrom purity is large, and yield is high.
One of the present invention preferred embodiment in, before passing into hydrogen, first the temperature in reactor is increased to preset temperature, in reactor, hydrogen is passed into again with predetermined pressure, wherein, described preset temperature is above-mentioned temperature when passing into hydrogen in reactor, and described predetermined pressure is above-mentioned hydrogen pressure in reactor when passing into hydrogen.
When the raw material in reactor no longer absorbs hydrogen, stop passing into hydrogen, termination reaction.
Step 2, epimerization reaction.
Because the former film of downstream sunscreen products produced with the cis-structure different Fo Er alcohol ester that falls apart has good sun-proof result, and the former film of transconfiguration falls apart, the sun-proof result of ester is poor, therefore, the industrial different Fo Er alcohol demand to cis-structure is much larger than the different Fo Er alcohol of transconfiguration, but in the different Fo Er alcohol obtained according to the method for step 1 ratio of cis-trans close to 1:1, namely, product close to half will be discarded, this not only causes the reduction of production and productivity, and the huge increasing of production cost can be caused, therefore, the present invention selects to carry out epimerization reaction to the different Fo Er alcohol that step 1 obtains in step 2, make most of convert cis structure in different Fo Er alcohol.
The present inventor finds, the product that step 1 obtains is without the need to shifting out reactor, by means of only conditions such as the temperature and pressures regulated in reactor, continue in reactor, pass into the epimerization reaction that hydrogen can realize different Fo Er alcohol, greatly simplifie production stage, reduce production difficulty and production cost.
When epimerization reaction, in reactor, hydrogen pressure is 1.0 ~ 10MPa, preferably 1.0 ~ 2.5MPa, more preferably 1.0 ~ 1.8MPa.
When epimerization reaction, the temperature in reactor is 130 ~ 250 DEG C, preferably 130 ~ 200 DEG C, more preferably 130 ~ 160 DEG C.
The time of epimerization reaction is 4 ~ 12h, preferably 4 ~ 7h.
The present inventor finds, in aforesaid reaction vessel under hydrogen pressure, reactor temperature and the condition in reaction times, the different Fo Er alcohol that step 1 obtains can realize epimerization, in the product of epimerization, the weight ratio of cis-structure product and transconfiguration is greater than 9:1, even can reach 9.66:1.
Step 3, system step 2 obtained is lowered the temperature, and obtains the different Fo Er alcohol of intermediate.
In step 3 of the present invention, after step 2 epimerization reaction terminates, make reaction system be cooled to 60 ~ 70 DEG C, as 65 DEG C, stop epimerization reaction.
In step 3 of the present invention, after system cooling, the pressure in release reaction still, emptying hydrogen wherein, preferably, reclaims remaining hydrogen in reactor, is transferred to safe place and preserves, and is separated the solid in removing reactor, obtains the different Fo Er alcohol of intermediate.
In the present invention, the method be separated is not particularly limited to, the method for any one solid-liquid separation in prior art can be used, as natural filtration or filtration under diminished pressure etc., be preferably filtration under diminished pressure.
In step 3 of the present invention, described solid is hydrogenation catalyst, and containing product isophorone in filtrate.
Optionally, reclaim hydrogenation catalyst to apply mechanically for lower batch of hydrogenation reaction; The present inventor finds, the hydrogenation catalyst of recovery can recycle more than 35 times.
Preferably, the hydrogenation catalyst of recovery, when applying mechanically, adds appropriate fresh hydrogenation catalyst, and more preferably, hydrogenation catalyst additional amount is the 0.1wt% ~ 5wt% of hydrogenation catalyst charging capacity first, preferred 0.1wt% ~ 0.5wt%.
Step 4, drops into obtained for step 3 different Fo Er alcohol, wintergreen oil and transesterification catalyst in transesterification reactor, reacts, and obtains former film and to fall apart ester crude product.
The present inventor finds, wintergreen oil is the minimum salicylate of molecule, and its structure is simple, sterically hindered little, easily carries out transesterification reaction, and therefore, the present invention selects wintergreen oil and different Fo Er alcohol to react to prepare former film to fall apart ester.
In step 4 of the present invention, described transesterification catalyst is transesterification catalyst, be preferably selected from organic catalyst, organic catalyst or organo-metallic catalyst, be more preferably salt of wormwood, sodium carbonate, calcium oxide, the vitriol oil, aluminum oxide, tosic acid, methylsulfonic acid, tetrabutyl titanate, aluminum isopropylate, di-nbutyltin oxide or di-n-octyl tin oxide etc., more preferably di-nbutyltin oxide (i.e. DOTO).
The present inventor finds, under the effect of above-mentioned transesterification catalyst, the different Fo Er alcohol that step 3 obtains can carry out transesterification reaction with wintergreen oil with appropriate reaction speed, can ensure carrying out fast of transesterification reaction, the speed of transesterification reaction also can be made to remain in controlled scope.
The present invention also finds, use acid or alkali as catalyzer, there is higher catalytic efficiency, but aftertreatment is complicated, inevitably produce a large amount of waste water, contaminate environment, and because of the existence of Determining Micro Acid alkaloid substance in subsequent purification steps, to cause former film fall apart ester decompose, be difficult to obtain the former film of high-quality to fall apart ester, and use di-n-octyl tin oxide as catalyzer, can avoid introducing strong acid or highly basic in reaction system, thus make preparation process more environmental protection, also avoid producing the sewage the like waste that may cause environmental pollution, the former film that simultaneously can obtain high-quality falls apart ester.
Therefore, the present invention preferably uses di-n-octyl tin oxide as catalyzer.
Preferably, the weight ratio of transesterification catalyst and wintergreen oil is the weight of transesterification catalyst: the weight=0.0001:1 ~ 0.1:1 of wintergreen oil, preferred 0.005:1 ~ 0.05:1.The present inventor finds that transesterification reaction speed is excessive, and react wayward, by product increases when the weight ratio of transesterification catalyst and wintergreen oil is greater than 0.1:1; When the weight ratio of transesterification catalyst and wintergreen oil is less than 0.0001:1, speed of reaction is too small, increase consuming time.
In step 4 of the present invention, the different Fo Er alcohol that step 3 obtains and the ratio of the molar weight of wintergreen oil are the molar weight of different Fo Er alcohol: the molar weight=1:1 ~ 10:1 of wintergreen oil, preferred 2:1 ~ 5:1, wherein, the molar weight of different Fo Er alcohol is with the molar amount of its molecule, and the molar weight of wintergreen oil is with the molar amount of its molecule.
In the present invention, different Fo Er alcohol both made solvent, did reaction raw materials again, and therefore, the present invention selects to make different Fo Er alcohol excessive in a large number, preferably, after reaction terminates, was reclaimed by excessive different Fo Er alcohol, applying mechanically for new reaction.
In step 4 of the present invention, reactor used is preferably the reactor with rectifying tower, thus the ester that former for ester exchange offspring film can be fallen apart isolates reaction system by the mode of rectifying, simultaneously, purifying is carried out to ester exchange offspring, makes the former film of product the obtained ester that falls apart have higher purity.
In step 4 of the present invention, the temperature controlling transesterification reaction is 100 ~ 200 DEG C, is preferably 160 ~ 190 DEG C.The present inventor finds, when temperature is 100 ~ 200 DEG C, it is abundant fast that transesterification reaction is carried out, and by product is few.
In step 4 of the present invention, salicylic content in monitoring reaction system, based on the total weight of system, when content salicylic in system is less than 0.5wt%, thinks sufficient reacting, terminated diester permutoid reaction.Be not bound by any theory, the present inventor thinks, in the transesterification reaction that different Fo Er alcohol and wintergreen oil carry out, wintergreen oil is first under catalyst action, Whitfield's ointment and methyl alcohol is hydrolyzed in the condition lower part of heating, wherein, be hydrolyzed the Whitfield's ointment that obtains and different Fo Er alcohol carries out esterification at identical conditions, generate the higher former film of stability and to fall apart ester, after wintergreen oil reacts completely, then no longer produce Whitfield's ointment in system, can sufficient reacting be judged, termination reaction.
In step 4 of the present invention, resultant falls apart except ester except former film, also comprises industry byproduct-methyl alcohol.Preferably, reclaim methyl alcohol to increase economic efficiency.
More preferably, remaining different Fo Er alcohol and transesterification catalyst is reclaimed.
Step 5, the ester crude product that fallen apart by former film obtained for step 4 carries out purifying, obtains the former film of product and to fall apart ester.
In step 4 of the present invention, the former film of preparation fall apart ester process in the former film that is separated fall apart in ester crude product and may be mixed with the raw materials such as different Fo Er alcohol, therefore, need to carry out further purifying to product, preferably use the method for rectifying to carry out purifying in the present invention.
In step 5 of the present invention, when the former film of purifying falls apart ester product, retaining boiling range is the cut of 161 ~ 165 DEG C of parts, and it to fall apart ester for the former film of product; Collect the cut that boiling range is 62 ~ 65 DEG C of parts, it is methyl alcohol; Collect the cut that boiling range is 193 ~ 196 DEG C of parts, it is the different Fo Er alcohol of raw material.
Optionally, the different Fo Er alcohol of recovery is used for applying mechanically.
Optionally, the transesterification catalyst at the end is heated up in a steamer for applying mechanically.
One of the present invention preferred embodiment in, when recovery transesterification catalyst is applied mechanically, need to add appropriate fresh transesterification catalyst, the additional amount of transesterification catalyst is the 1wt% ~ 50wt% of transesterification catalyst charging capacity first, preferred 10wt% ~ 30wt%.
Former film obtained in the step 5 of the present invention ester that falls apart is water white transparency thick liquid, and refractive index (nd20) is 1.516 ~ .519, and proportion (20 DEG C, mg/mL) is 1.049 ~ 1.053; Acid number≤1mgKOH/g; GC content (area normalization method): cis >=85.0%, trans≤15%, total content >=99.0%; Single foreign matter content (GC)≤0.1%, total impurities content (GC)≤0.5%.
According to a second aspect of the invention, a kind of former film that method is obtained according to above-mentioned first aspect is also provided to fall apart ester, it is characterized in that, the described former film ester that falls apart is water white transparency thick liquid, refractive index (nd20) is 1.516 ~ 1.519, proportion (20 DEG C, mg/mL) is 1.049 is 1.053; Acid number≤1mgKOH/g; GC content (area normalization method): cis >=85.0%, trans≤15%, total content >=99.0%; Single foreign matter content (GC)≤0.1%, total impurities content (GC)≤0.5%.
To fall apart according to the former film of preparation provided by the invention the method for ester, there is following beneficial effect:
(1) after isophorone hydrogenation reduction terminates, the stereoselectivity of product different Fo Er alcohol is cis: trans≤1:1, adopt the method for epimerization, the ratio that can obtain cis-isomeride and trans-isomer(ide) is greater than the different Fo Er alcohol of 85:15, and this is that the former film of the follow-up preparation high-quality ester that falls apart provides guarantee;
(2) method of epimerization is adopted, the cis of arbitrary proportion can be obtained: the different Fo Er alcohol of trans >1:1, and epimerization reaction is without the need to using other catalyzer, only need suitably to regulate the temperature in reactor and hydrogen pressure to complete after the completion of reaction, easy and simple to handle, Be very effective;
(3) according to different Fo Er alcohol prepared by method provided by the invention, its purity (cis-trans-isomer sum) >99%, the former film of preparation can be directly used in fall apart ester, without the need to purification process such as extra rectifying, distillations, and only need simple filtration and recyclable hydrogenation catalyst, and the hydrogenation catalyst reclaimed can be used in applying mechanically;
(4) transesterification catalyst that uses of the present invention catalysis TMC and wintergreen oil can carry out transesterify and prepares former film and to fall apart ester, transesterification catalyst wide material sources, easy acquisition, catalytic efficiency is high, can realize being separated of raw material and product and catalyzer through rectifying, and transesterification catalyst is capable of circulation applies mechanically;
(5) technique of the present invention produces without waste water, alleviates environmental protection pressure greatly;
(6) method provided by the invention fundamentally changes the former film of sun-screening agent and to fall apart Lipase absobed complex process, present situation that productive rate is low, solves the difficult problem that its quality faced is not high;
(7) method provided by the invention also has easy, to be easy to control and suitability for industrialized production feature.
Embodiment
embodiment 1
(1) in hydrogenation reaction kettle, 2000kg isophorone and 14.0kgRu/C is added (based on Ru/C gross weight, wherein containing Ru5.1wt%, water ratio 45.4%), close hydrogenation reaction kettle, with air in nitrogen replacement reactor three times, to use in hydrogen exchange reactor nitrogen again three times, hydrogen pressure in still is set in 0.8MPa, opens and stir, be warming up to 80 DEG C and start hydrogenation, to no longer absorbing hydrogen, sampling is GC and is analyzed, and cis is 33.27%, and trans is 66.52%, total content 99.79%, cis: trans=0.5.
(2) epimerization: hydrogen pressure in reactor is risen to 1.4MPa, reactor temperature rises to 140 DEG C, samples after stirring reaction 5h, and cis is 89.89%, and trans is 9.84%, total content 99.73%, cis: trans=9.14.
(3) material in reactor is cooled to 60 DEG C, filtering recovering catalyst Ru/C10.6Kg, applies mechanically for lower batch, obtain different Fo Er alcohol product 2035Kg, yield 98.87%.
(4) in the reactor of band rectifying tower, add the obtained different Fo Er alcohol of 2000kg wintergreen oil, 6000Kg step 3 and 21Kg catalyzer di-nbutyltin oxide (DOTO), open and stir, reactor temperature is risen to 160 DEG C, start clock reaction, sampling analysis after 3h, to reactor, during salicylic acid content <0.5%, terminate reaction, reclaim by-product methyl alcohol 437.5Kg.
(5) reactor temperature is down to 90 DEG C, raw material and product are reclaimed in rectification under vacuum, reclaim different Fo Er alcohol 4331.5Kg altogether, and the former film of product falls apart ester 3200Kg, yield 92.81%.Refractive index (nd20) is 1.516, proportion (20 DEG C, mg/mL) be 1.049 acid numbers≤1mgKOH/g, cis is 90.95%, trans is 8.65%, total content (GC) is 99.60%, single foreign matter content (GC)≤0.1%, and total impurities content (GC) is 0.4%.
embodiment 2
(1) in hydrogenation reaction kettle, 2000kg isophorone is added, embodiment 1 reclaims the fresh Ru/C catalyzer of Ru/C catalyzer 10.6Kg and 2.0Kg (based on Ru/C gross weight, wherein containing Ru5.1%, water ratio 45.4%), close hydrogenation still, with air in nitrogen replacement still three times, to use in hydrogen exchange still nitrogen again three times, hydrogen pressure in still is set in 1.2MPa, open and stir, be warming up to 110 DEG C and start hydrogenation, to no longer absorbing hydrogen, sampling is GC and is analyzed, cis is 10.10%, trans is 89.68%, total content 99.78%, cis: trans=0.11.
(2) epimerization: hydrogen pressure in reactor is risen to 1.6MPa, reactor temperature rises to 150 DEG C, samples after stirring reaction 7h, and cis is 90.35%, and trans is 9.35%, total content 99.70%, cis: trans=9.66.
(3) material in still is cooled to 70 DEG C, filtering recovering catalyst Ru/C13.2Kg, applies mechanically for lower batch, obtain different Fo Er alcohol product 2053.5Kg, yield 99.77%.
(4) add in the reactor of used in embodiment 1 band rectifying tower 2000kg wintergreen oil, embodiment 1 reclaim 4331.5Kg different Fo Er alcohol, add strange Fo Er alcohol 1870Kg and 4.2Kg raw catalyst di-nbutyltin oxide (DOTO), open and stir, reactor temperature is risen to 180 DEG C, start clock reaction, sampling analysis after 3h, to terminating reaction during salicylic acid content <0.5%, reclaim by-product methyl alcohol 445.2Kg.
(5) by still temperature drop to 100 DEG C, raw material and product are reclaimed in rectification under vacuum, reclaim different Fo Er alcohol 4426.3Kg altogether, the former film of product falls apart ester 3310.0Kg, yield 96.0%, refractive index (nd20) is 1.519, proportion (20 DEG C, mg/mL) be 1.053, acid number≤1mgKOH/g, cis is 89.95%, trans is 9.75%, total content (GC) is 99.70%, single foreign matter content (GC)≤0.1%, and total impurities content (GC) is 0.3%.
More than in conjunction with embodiment and exemplary example to invention has been detailed description, but these explanations can not be interpreted as limitation of the present invention.It will be appreciated by those skilled in the art that when not departing from spirit and scope of the invention, can carry out multiple equivalencing, modification or improvement to technical solution of the present invention and embodiment thereof, these all fall within the scope of the present invention.Protection scope of the present invention is as the criterion with claims.
Claims (10)
1. prepare former film to fall apart the method for ester, it is characterized in that, the method comprises the following steps:
Step 1), add isophorone and hydrogenation catalyst in a kettle., pass into hydrogen;
Step 2), epimerization reaction;
Step 3), system cooling step 2 obtained, obtains the different Fo Er alcohol of intermediate;
Step 4), obtained for step 3 different Fo Er alcohol, wintergreen oil and transesterification catalyst are dropped in transesterification reactor, reacts, obtain former film and to fall apart ester crude product;
Step 5), the ester crude product that fallen apart by former film obtained for step 4 carries out purifying, obtains the former film of product and to fall apart ester.
2. method according to claim 1, is characterized in that, in step 1,
Described hydrogenation catalyst is skeleton nickel, copper chromite, Rh/C, Rh/Al
2o
3, Pd/C, Pd/Al
2o
3, Ru/C, Ru/Al
2o
3deng, be preferably Ru/C;
The weight ratio of the metallic element (as Ru) in described isophorone and hydrogenation catalyst except aluminium element is 100000:1 ~ 100:1, preferred 10000:1 ~ 1000:1;
When passing into hydrogen, in reactor, hydrogen pressure is 0.5 ~ 10MPa, preferably 0.6 ~ 2.0MPa, is more preferably 0.6 ~ 1.2MPa;
When passing into hydrogen, the temperature in reactor is 25 ~ 200 DEG C, preferably 50 ~ 180 DEG C, more preferably 70 ~ 110 DEG C.
3. method according to claim 1 and 2, is characterized in that, in step 1,
Described Ru/C can be butt form or wet basis form, and be preferably wet basis form, more preferably, in Ru/C, water ratio is 10 ~ 65%, and preferred water ratio is 40 ~ 60%;
In described Ru/C, based on the gross weight of Ru/C, wherein metal Ru content is 0.5 ~ 50qwt% (in butt form), preferably 1 ~ 20wt%, particularly preferably 3 ~ 10wt%.
4., according to the method one of claims 1 to 3 Suo Shu, it is characterized in that, in step 2,
When epimerization reaction, in reactor, hydrogen pressure is 1.0 ~ 10MPa, preferably 1.0 ~ 2.5MPa, more preferably 1.0 ~ 1.8MPa;
When epimerization reaction, the temperature in reactor is 130 ~ 250 DEG C, preferably 130 ~ 200 DEG C, more preferably 130 ~ 160 DEG C;
The time of epimerization reaction is 4 ~ 12h, preferably 4 ~ 7h.
5., according to the method one of Claims 1 to 4 Suo Shu, it is characterized in that, in step 3,
After step 2 reaction terminates, system is made to be cooled to 60 ~ 70 DEG C,
After system cooling, be separated removing solid wherein, obtain the different Fo Er alcohol of intermediate,
Optionally, reclaim hydrogenation catalyst to apply mechanically for lower batch of hydrogenation reaction;
Preferably, when recovery hydrogenation catalyst is applied mechanically, add appropriate fresh hydrogenation catalyst, more preferably, hydrogenation catalyst additional amount is the 0.1wt% ~ 5wt% of hydrogenation catalyst charging capacity first, preferred 0.1wt% ~ 0.5wt%.
6., according to the method one of Claims 1 to 5 Suo Shu, it is characterized in that, in step 4,
Described transesterification catalyst is organic catalyst, organic catalyst or organo-metallic catalyst, be preferably salt of wormwood, sodium carbonate, calcium oxide, the vitriol oil, aluminum oxide, tosic acid, methylsulfonic acid, tetrabutyl titanate, aluminum isopropylate, di-nbutyltin oxide or di-n-octyl tin oxide etc., be more preferably di-n-octyl tin oxide;
The weight ratio of transesterification catalyst and wintergreen oil is 0.0001:1 ~ 0.1:1, preferred 0.005:1 ~ 0.05:1;
Different Fo Er alcohol is 1:1 ~ 10:1 with the ratio of the molar weight of wintergreen oil, preferred 2:1 ~ 5:1, and wherein, the molar weight of different Fo Er alcohol is with the molar amount of its molecule, and the molar weight of wintergreen oil is with the molar amount of its molecule;
The temperature of reaction of step 4 is 100 ~ 200 DEG C, is preferably 160 ~ 190 DEG C.
7., according to the method one of claim 1 ~ 6 Suo Shu, it is characterized in that, in step 5,
The method of described purifying is rectifying;
Optionally, the different Fo Er alcohol of recovery is applied mechanically;
Optionally, heat up in a steamer end transesterification catalyst to apply mechanically.
8., according to the method one of claim 1 ~ 7 Suo Shu, it is characterized in that, in step 5,
When recovery transesterification catalyst is applied mechanically, add appropriate fresh transesterification catalyst, the additional amount of transesterification catalyst is the 1wt% ~ 50wt% of transesterification catalyst charging capacity first, preferred 10wt% ~ 30wt%.
9., according to the method one of claim 1 ~ 8 Suo Shu, it is characterized in that, in step 5,
The obtained former film ester that falls apart is water white transparency thick liquid, and refractive index (nd20) is 1.516 ~ 1.519, and proportion (20 DEG C, mg/mL) is 1.049 ~ 1.053; Acid number≤1mgKOH/g; GC content (area normalization method): cis >=85.0%, trans≤15%, total content >=99.0%; Single foreign matter content (GC)≤0.1%, total impurities content (GC)≤0.5%.
10. a former film obtained according to the method one of claim 1 ~ 9 Suo Shu falls apart ester, it is characterized in that, the described former film ester that falls apart is water white transparency thick liquid, and refractive index (nd20) is 1.516 ~ 1.519, proportion (20 DEG C, mg/mL) is 1.049 ~ 1.053; Acid number≤1mgKOH/g; GC content (area normalization method): cis >=85.0%, trans≤15%, total content >=99.0%; Single foreign matter content (GC)≤0.1%, total impurities content (GC)≤0.5%.
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