CN105085273A - Method for preparing homosalate - Google Patents

Method for preparing homosalate Download PDF

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CN105085273A
CN105085273A CN 201510466884 CN201510466884A CN105085273A CN 105085273 A CN105085273 A CN 105085273A CN 201510466884 CN201510466884 CN 201510466884 CN 201510466884 A CN201510466884 A CN 201510466884A CN 105085273 A CN105085273 A CN 105085273A
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preferably
step
catalyst
isophorone
homosalate
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CN 201510466884
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CN105085273B (en )
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刘启发
王荣
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安徽圣诺贝化学科技有限公司
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/17Preparation 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
    • C07C29/175Preparation 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
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00Preparation of carboxylic acid esters
    • C07C67/03Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group

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

一种制备原膜散酯的方法 A method for preparing Homosalate

技术领域 FIELD

[0001] 本发明属于日用化工技术领域,涉及一种有机中间体的制备方法,具体而言涉及防晒剂原膜散酯的制备方法。 [0001] The present invention belongs to the technical field of household chemicals, a method for preparing an organic intermediate, particularly relates to a method of preparing sunscreens in Homosalate.

背景技术 Background technique

[0002] 防晒剂原膜散酯(HMS),化学名为3, 3, 5-三甲基环己基水杨酸酯,CAS号为118-56-9,英文名称为Homosalate,其结构式如下式I所示: [0002] Sunscreen Homosalate (HMS), the chemical name is 3, 3, 5-trimethyl-cyclohexyl salicylate, CAS number of 118-56-9, English name for Homosalate, the structural formula of the formula I below:

[0003] [0003]

Figure CN105085273AD00041

[0004] HMS为无色透明粘稠液体,沸点161~165°C /12mmHg,相对分子质量为262. 34,相对密度为1. 049 ~I. 053g/mL(20°C )。 [0004] HMS a colorless transparent viscous liquid, boiling point 161 ~ 165 ° C / 12mmHg, relative molecular mass of 262.34, a relative density of 1. 049 ~ I. 053g / mL (20 ° C).

[0005] HMS是一种紫外线UVB防晒剂,属于化学防晒剂,可以吸收UVB 295~315nm波段, 其与树脂的相容性好,不着色,广泛应用于软质、硬质聚氯乙烯等塑料和硝酸纤维素、丙烯酸树脂及聚氨酯等涂料中作为光稳定剂,HMS对皮肤刺激性很小,可添加到高档化妆品中, 化妆品中最高添加量为10%,因此,近年来,HMS的市场需求越来越大,是一种前景广阔,极具开发价值的产品。 [0005] HMS is an ultraviolet UVB sunscreen agents, chemical sunscreen agents belong, can absorb UVB 295 ~ 315nm band, which has good compatibility with the resin, not colored, and are widely used in soft, rigid PVC and other plastic and cellulose nitrate, acrylic resin, polyurethane, etc., and as a light stabilizer in coatings, HMS little skin irritation, can be added to the high-end cosmetics, cosmetics added in an amount up to 10%, and therefore, in recent years, demand HMS more and more, it is a broad prospect, great value products.

[0006] 合成HMS的主要原料之一为异佛尔醇(TMC)。 One of the main raw material [0006] Synthesis of isophorone HMS alcohol (TMC). TMC为四种立体异构体的混合物,其结构式如下式II所示。 TMC is a mixture of four stereoisomers, which is shown in the following structural formula Formula II.

[0007] [0007]

Figure CN105085273AD00042

[0008] 异佛尔醇(TMC),化学名称:3, 3, 5-三甲基环己醇,英文名: 3, 3, 5-Trimethylcyclohexanol,分子式:C9H180,分子量:142. 24, CAS No. :116-02-9,其在常温下为无色油状液体或固体,具有清新薄荷香气,有毒性及刺激性,熔点:30_32°C,沸点:193 ~196°C (760mmHg),密度:0• 817 ~0• 860(25°C,760mmHg),闪点:46 ~81°C,折射率:1.4215~1.4263(45°C ),蒸汽压0. 173mmHg(25°C ),其不溶于水,溶于醇类、烃类等有机溶剂。 [0008] Isophorone alcohol (the TMC), chemical name: 3, 3, 5-trimethyl-cyclohexanol, English name: 3, 3, 5-Trimethylcyclohexanol, molecular formula: C9H180, molecular weight:. 142 24, CAS No : 116-02-9, which is colorless oily liquids or solids, having a fresh mint aroma, toxic and irritating, mp: 30_32 ° C, boiling point: 193 ~ 196 ° C (760mmHg), density: 0 • 817 ~ 0 • 860 (25 ° C, 760mmHg), flash point: 46 ~ 81 ° C, refractive index: 1.4215 ~ 1.4263 (45 ° C), vapor pressure of 0. 173mmHg (25 ° C), which is insoluble in water, soluble in alcohols, hydrocarbons and other organic solvents. TMC是合成环扁桃酸酯及原膜散酯的中间体,合成新型增塑剂、润滑剂、二腈、二胺和醇的重要中间体。 TMC is an intermediate in the synthesis loop and mandelic esters Homosalate, it is important intermediate in the synthesis of new plasticizers, lubricants, dinitrile, diamine and alcohol.

[0009] 以化学还原异佛尔酮制备TMC,例如在Tetrahedron, 1981,37(6) :1171~1179 ; J.Am.Chem. Soc. ,1978, 100 (7) :2226 ~2227 !Tetrahedron 1980,36(13):1937 ~1942; J. Org. Chem.,1980, 45 (10) : 1946 ~1950 ;0rg. React.,2008, 71:1 ~737 !Tetrahedron Lett.,1995,36 (34):6051 ~6054 ;Synth. Commun.,1988,18(1):89 ~96 ;Bull. Korean Chem.Soc.,2009,30(7):1588 ~1592;J.0rg.Chem.,1986,51 (10):1769 ~1773;Int. J. Cosmet. Sci.,2006, 28(6) :439-446中被公开,这些方法具有操作方便,选择性高等优点。 [0009] In the chemical reduction of isophorone prepared TMC, for example, Tetrahedron, 1981,37 (6): 1171 ~ 1179; J.Am.Chem Soc, 1978, 100 (7):. 2226 ~ 2227 Tetrahedron 1980.! , 36 (13):. 1937 ~ 1942; J. Org Chem, 1980, 45 (10): 1946 ~ 1950; 0rg React, 2008, 71:.. 1 ~ 737 Tetrahedron Lett, 1995,36 (34.!. ): 6051 ~ 6054; Synth Commun, 1988,18 (1):. 89 ~ 96; Bull Korean Chem.Soc, 2009,30 (7):.. 1588 ~ 1592; J.0rg.Chem, 1986,.. (10) 51: 1769 ~ 1773; Int J. Cosmet Sci, 2006, 28 (6):... 439-446 are disclosed in, these methods are easy to operate, selective advantages. 但化学还原法要使用昂贵的还原剂,如硼氢化物、氢化铝锂、氢化钠、氢化锂、三甲基硅烷等,且在后处理过程中将产生大量的三废物,使得这些方法很难应用于工业化生产。 However, chemical reduction of the use of expensive reducing agents, such as boron hydride, lithium aluminum hydride, sodium hydride, lithium hydride, trimethylsilane, and a large amount of waste in the three post-treatment process, so that these methods are difficult to apply industrial production.

[0010] 以Ni、Pd、Ru、Cu、Pt等为催化剂,采用氢气或氢转移试剂为还原剂,催化剂异佛尔酮制备TMC,例如在(Catal. Commun.,2008, 10(2) : 213 ~216 J. Org. Chem.,196025:514 ~ 518 ;EP 1318130 ;Synlett.,2009, (19) :3143 ~3146 ;PCT2009085826;Przemysl Chemiczny,2003,82(8 ~9) :1291 ~1294;Appl.Catal.B:Environ.,2004,49(3):181 ~ 185 ;PCT 2007007646 ;RSC Advances, 2013,(26) : 10131 ~10134 中被公开,这些方法具有绿色环保,污染小、后处理简单等优点。但现有技术中的方法或存在压力太高、或温度太高、 或转化率低、或产生副产物、或立体选择性差等缺憾,使得这些方法距离工业化生产还有一定的距离,仍需进一步研究。 [0010] In Ni, Pd, Ru, Cu, Pt, etc. as a catalyst, using hydrogen gas or hydrogen transfer agent is a reducing agent, the catalyst prepared in the TMC isophorone, for example, (Catal Commun, 2008, 10 (2)..: . 213 ~ 216 J. Org Chem, 196025: 514 ~ 518; EP 1318130; Synlett, 2009, (19):. 3143 ~ 3146; PCT2009085826; Przemysl Chemiczny, 2003,82 (8 ~ 9):. 1291 ~ 1294; Appl.Catal.B: Environ, 2004,49 (3): 181 ~ 185; PCT 2007007646; RSC Advances, 2013, (26):. 10131 ~ 10134 are disclosed, these methods have green, pollution, post-treatment and simple. However, the prior art method or the presence of pressure is too high, or the temperature is too high, or low conversion rate, or by-products, or poor stereoselectivity defects, so that these methods have a certain distance from the industrial production , further research is needed.

[0011] 关于HMS的合成文献报道得很少。 [0011] The synthesis of the literature on HMS very little. US2369084报道了HMS的相关性质,但未给出HMS的合成方法。 US2369084 reported related to the nature of the HMS, HMS synthesis of but did not give. Int. J. Cosmet. Sci.,2006, 28:P439给出了以异佛尔酮为原料,利用硼氢化钠还原制得TMC,再以水杨酸或水杨酸的酰氯与TMC在酸性催化剂或碱性催化剂作用下, 及利用微波加热,以合成HMS的方法,尽管合成TMC的产率高达99%,但HMS的产率最高仅72%。 .. Int J. Cosmet Sci, 2006, 28:. P439 is given to isophorone as starting material, prepared by reducing the TMC sodium borohydride, and then to the acid chloride with salicylic acid or an acidic catalyst TMC or basic catalyst, and the use of microwave heating to HMS synthesized, although the yield of the synthesis of TMC of up to 99%, but the maximum yield of only 72% HMS. 此外,采用这种方法得到的HMS之立体组成为,顺式:反式=1:1,但这一组成与市面上可得的防晒剂HMS的立体组成不一致。 Further, this method obtained a perspective view of a composition of HMS, cis: trans = 1: 1, but with the perspective that the composition of commercially available sunscreen composition HMS inconsistent. Arhiv za Farmaci ju, 1986, 36:P161以水杨酸钠和3, 3, 5-三甲基环己基氯为原料,在相转移催化剂作用下制备HMS,收率仅49~51 %。 Arhiv za Farmaci ju, 1986, 36: P161 sodium salicylate and 3, 3, 5-trimethyl cyclohexyl chloride as starting material, prepared HMS under phase transfer catalyst, yield of only 49 to 51%. 此外,文献没有给出所得到产品HMS的立体信息。 In addition, the document does not give the product HMS stereo information is given.

[0012] 因此,亟需开发一种能够简便制得构向单一的高品质原膜散酯的方法。 [0012] Accordingly, an urgent need to develop a method can be easily made to a single high-quality Homosalate configuration.

发明内容 SUMMARY

[0013] 为了解决上述问题,本发明人进行了锐意研究,结果发现:用异佛尔酮作为原料, 在催化剂作用下进行加氢反应,再进行差向异构化反应,制得异佛尔醇,制得的异佛尔醇再与水杨酸甲酯进行酯交换反应,最终制得原膜散酯,根据上述方法制得的原膜散酯纯度高, 收率高,从而完成了本发明。 [0013] In order to solve the above problems, the present inventors conducted intensive studies, and found that: with isophorone as a starting material in the hydrogenation reaction catalyst, then the epimerization reaction, the product isophorone, alcohol, the resulting alcohol then isophorone transesterification with methyl salicylate, finally obtained Homosalate, high prepared according to the method described above Homosalate purity and high yield, thereby completing the present invention.

[0014] 本发明的目的在于提供以下方面: [0014] The object of the present invention is to provide the following aspects:

[0015] 第一方面,本发明提供一种制备原膜散酯的方法,其特征在于,该方法包括以下步骤: [0015] In a first aspect, the present invention provides a method of preparing Homosalate, characterized in that the method comprises the steps of:

[0016] 步骤1),在反应釜中加入异佛尔酮和加氢催化剂,通入氢气; [0016] Step 1), was added to the kettle isophorone and a hydrogenation catalyst, into hydrogen gas;

[0017] 步骤2),差向异构化反应; [0017] Step 2), the epimerization reaction;

[0018] 步骤3),将步骤2得到的体系降温,得到中间体异佛尔醇; [0018] Step 3), the cooling system obtained in step 2, to give the intermediate alcohol and isophorone;

[0019] 步骤4),将步骤3制得的异佛尔醇、水杨酸甲酯和酯交换催化剂投入酯交换釜中, 进行反应,得到原膜散酯粗产物; [0019] Step 4), prepared in step 3 of isophorone, methyl salicylate and transesterification catalyst is placed into a transesterification reactor, the reaction was carried out to obtain a crude product Homosalate;

[0020] 步骤5),将步骤4制得的原膜散酯粗产物进行纯化,得到产品原膜散酯。 [0020] Step 5), the original film obtained in Step 4 The crude ester was purified bulk, to give the product Homosalate.

[0021] 第二方面,本发明还提供一种根据上述第一方面所述方法制得的原膜散酯,其特征在于,所述原膜散酯为无色透明粘稠液体,折光率(nd20)介于1. 516-1. 519,比重(20°C, mg/mL)介于L 049-1. 053 ;酸值彡lmgKOH/g ; % GC含量(面积归一法):顺式彡85. 0%, 反式彡15%,总含量彡99.0% ;单个杂质(GC)彡0.1%,总杂质(GC)彡0.5%。 [0021] In a second aspect, the present invention also provides a method according to the first aspect of the prepared Homosalate, wherein said Homosalate a colorless transparent viscous liquid, refractive index ( nD20) between 1 516-1519, a specific gravity (20 ° C, mg / mL) interposed L 049-1 053; acid value San lmgKOH / g;% GC content (area normalization method): cis San 85.0%, 15% trans-San, San total content 99.0%; single impurity (GC) San 0.1% total impurities (GC) San 0.5%.

具体实施方式 Detailed ways

[0022] 下面通过对本发明进行详细说明,本发明的特点和优点将随着这些说明而变得更为清楚、明确。 [0022] The present invention will next be described in detail, features and advantages of the present invention will be described as these become more clear and precise.

[0023] 以下详述本发明。 [0023] The following detailed description of the present invention.

[0024] 根据本发明的第一方面,提供一种制备原膜散酯的方法,其特征在于,该方法包括以下步骤: [0024] According to a first aspect of the present invention, there is provided a method of preparing Homosalate, characterized in that the method comprises the steps of:

[0025] 步骤1,在反应釜中加入异佛尔酮和加氢催化剂,通入氢气。 [0025] Step 1, was added isophorone and a hydrogenation catalyst in the reactor, introducing hydrogen.

[0026] 在本发明中,首先将异佛尔酮加氢还原为异佛尔醇,本发明人发现,使用氢气还原异佛尔酮制备异佛尔醇,反应副产物少,产物收率高,且异佛尔酮来源广泛,价格低廉。 [0026] In the present invention, first the hydrogenation of isophorone isophorone alcohol, the present inventors have found that, using hydrogen reduction isophorone prepared isophorone alcohol, fewer reaction by-products, high product yield and isophorone ketone wide source and low prices.

[0027] 在本发明步骤1中,使用加氢催化剂对其加氢还原反应进行催化,其中,所述加氢催化剂为骨架镍、亚铬酸铜、Rh/C、Rh/Al 203、Pd/C、Pd/Al203、Ru/C、RuAl 2O3等,优选为Ru/ C,其中, [0027] In Step 1 of the present invention, hydrogenation catalyst used for the catalytic hydrogenation reaction thereof, wherein the hydrogenation catalyst is Raney nickel, copper chromite, Rh / C, Rh / Al 203, Pd / C, Pd / Al203, Ru / C, RuAl 2O3 and the like, preferably Ru / C, wherein,

[0028] 所述Ru/C中,基于Ru/C的总重量,其中金属Ru含量为0.5~50wt%(以干基形态计),优选1~20wt%,特别优选3~IOwt%,其可以是干基形态,也可以是湿基形态,优选为湿基形态,更优选地,含水率为10~65%,优选为40~60%; [0028] The Ru / C, based on the total weight of the Ru / C, wherein the content of the metal Ru 0.5 ~ 50wt% (on a dry form), preferably 1 ~ 20wt%, particularly preferably 3 ~ IOwt%, it may be is the dry form, may be a form of a wet basis, preferably form a wet group, more preferably a water content of 10 to 65%, preferably from 40 to 60%;

[0029] 本发明人发现,使用上述加氢催化剂来催化异佛尔酮的加氢反应时反应条件易于实现,容易控制,催化剂的使用量少,生产成本低,而且后处理方便。 [0029] The present inventors have found that when the reaction conditions are easily achieved by catalytic hydrogenation of isophorone using the hydrogenation catalyst, easy to control, the use of less catalyst, low production cost, and easy post-treatment.

[0030] 在本发明步骤1中,所述异佛尔酮与所述加氢催化剂中除铝元素外的金属元素(如Ru)的重量比为100000:1 ~100:1,优选10000:1 ~1000:1。 [0030] In Step 1 of the present invention, the isophorone and the hydrogenation catalyst metals (e.g., Ru) is an element other than aluminum, a weight ratio of 100,000: 1 to 100: 1, preferably 10,000: 1 to 1000: 1.

[0031] 在本发明步骤1中,任选地,在通入氢气之前,向反应釜中通入惰性气体,如氦气、 氖气、氩气和/或氮气等,以除去反应釜中的空气,从而增加了通入氢气时安全性,优选地, 使反应釜中充满惰性气体。 [0031] In Step 1 of the present invention, optionally, prior to introducing hydrogen into the reaction vessel an inert gas, such as helium, neon, argon and / or nitrogen, to remove the reactor air, thereby increasing the safety ventilation of hydrogen gas, preferably, the reaction vessel filled with an inert gas.

[0032] 在本发明步骤1中,在通入氢气时,反应釜内氢气压力为0.5~lOMPa,优选0.6~ 2. OMPa,更优选为0• 6 ~I. 2MPa。 [0032] In Step 1 of the present invention, when the hydrogen gas into the inner reactor hydrogen pressure of 0.5 ~ lOMPa, preferably 0.6 ~ 2. OMPa, more preferably 0 • 6 ~ I. 2MPa.

[0033] 在本发明步骤1中,在通入氢气时,反应釜内的温度为25~200°C,优选50~ 180°C,更优选为70~110°C。 [0033] In Step 1 of the present invention, when introducing hydrogen, the temperature in the reactor is 25 ~ 200 ° C, preferably 50 ~ 180 ° C, more preferably 70 ~ 110 ° C.

[0034] 本发明人发现,在上述温度和压力条件下,异佛尔酮能够被充分还原为异佛尔醇, 所得产物纯度大,收率高。 [0034] The present inventors have found that, at the above temperature and pressure conditions, isophorone can be sufficiently reduced to isophorone alcohol, the resulting product was a purity and high yield.

[0035] 在本发明一种优选的实施方式中,在通入氢气前先将反应釜内的温度升高至预定温度,再以预定压力向反应釜内通入氢气,其中,所述预定温度为上述通入氢气时反应釜内的温度,所述预定压力为上述通入氢气时反应釜内氢气压力。 [0035] In a preferred embodiment of the invention, prior to introducing hydrogen first reaction temperature in the autoclave was raised to a predetermined temperature, a predetermined pressure and then introducing hydrogen into the reactor, wherein said predetermined temperature hydrogen pressure within the autoclave when the temperature in the autoclave with hydrogen when the through, the predetermined pressure of hydrogen gas into the via.

[0036]当反应釜内的原料不再吸收氢气时,停止通入氢气,终止反应。 [0036] When the starting material in the reactor is no longer absorbed hydrogen, hydrogen was stopped to terminate the reaction.

[0037] 步骤2,差向异构化反应。 [0037] Step 2, epimerization reaction.

[0038] 由于用顺式结构异佛尔醇生产的下游防晒剂产品原膜散酯具有较好的防晒效果, 而反式结构的原膜散酯的防晒效果差,因此,工业上对顺式结构的异佛尔醇需求量远大于反式结构的异佛尔醇,然而根据步骤1的方法制得的异佛尔醇中顺反式的比例接近1:1, 即,接近一半的产物将被弃去,这不仅导致产量产率的降低,而且会导致生产成本的巨增, 因此,本发明选择在步骤2中对步骤1得到的异佛尔醇进行差向异构化反应,使异佛尔醇中大部分转化顺式结构。 [0038] Since the cis-alcohol production isophorone structure downstream sunscreen products Homosalate has better protection from the sun, the sun protection Homosalate trans configuration difference, therefore, is industrially of cis isophorone alcohol structure is much larger than the demand for alcohol isophorone trans configuration, but close to the ratio of 1 trans isophorone methods cis alcohol obtained in the step 1: 1, i.e., nearly half of the product was is discarded, which not only results in lower production yield, and can lead to a great increase in production cost, therefore, the present invention is selected for the difference of isophorone alcohol obtained in step 1 to step 2 isomerization reaction, iso Dover alcohol is converted mainly cis structure.

[0039] 本发明人发现,步骤1制得的产物无需移出反应釜,仅通过调节反应釜中的温度和压力等条件,继续向反应釜中通入氢气即可实现异佛尔醇的差向异构化反应,极大地简化了生产步骤,降低生产难度和生产成本。 [0039] The present inventors have found that the product of Step 1 was removed from the reaction vessel need not only by adjusting the reactor temperature and pressure, etc., continue to be introduced into the reaction vessel to the hydrogen gas can be realized difference isophorone alcohol isomerization reaction, greatly simplifying the production steps to reduce production cost and difficulty.

[0040] 在差向异构化反应时,反应釜内氢气压力为I. 0~lOMPa,优选I. 0~2. 5MPa,更优选I. 0 ~I. 8MPa。 [0040] when the epimerization reaction, the hydrogen pressure of the autoclave I. 0 ~ lOMPa, preferably I. 0 ~ 2. 5MPa, more preferably I. 0 ~ I. 8MPa.

[0041] 在差向异构化反应时,反应釜内的温度为130~250 °C,优选130~200 °C,更优选130 ~160。 [0041] when the epimerization reaction, the temperature in the reactor is 130 ~ 250 ° C, preferably 130 ~ 200 ° C, more preferably 130 to 160. . .

[0042] 差向异构化反应的时间为4~12h,优选4~7h。 [0042] The difference to the isomerization reaction time is 4 ~ 12h, preferably 4 ~ 7h.

[0043] 本发明人发现,在上述反应釜内氢气压力、反应釜内温度和反应时间的条件下,步骤1制得的异佛尔醇能够实现差向异构化,差向异构化的产物中顺式结构产物与反式结构的重量比大于9:1,甚至可以达到9. 66:1。 [0043] The present inventors have found that, in the above reactor under hydrogen pressure, the reactor temperature and the reaction time of step 1 was isophorone alcohol possible epimerization, the epimerization by weight of the product cis structure and trans structure of the product is greater than 9: 1, even up to 9.66: 1.

[0044] 步骤3,将步骤2得到的体系降温,得到中间体异佛尔醇。 [0044] Step 3, the cooling system obtained in step 2, to give the intermediate alcohol and isophorone.

[0045] 在本发明步骤3中,当步骤2差向异构化反应结束后,使反应体系降温至60~ 70 °C,如65 °C,终止差向异构化反应。 [0045] In the present invention, step 3, when after the epimerization step 2 reaction, the reaction system was cooled to 60 ~ 70 ° C, such as 65 ° C, terminated epimerization reaction.

[0046] 在本发明步骤3中,体系降温后,释放反应釜内的压力,排空其中的氢气,优选地, 回收反应釜中剩余的氢气,转移至安全处保存,分离除去反应釜中的固体,得到中间体异佛尔醇。 [0046] In step 3 of the present invention, the cooling system, releasing the pressure in the reaction vessel, evacuated of hydrogen wherein, preferably, recovering hydrogen remaining in the reaction vessel, transferred to a safe place to save, separating and removing the reaction kettle The solid, to give the intermediate alcohol and isophorone.

[0047] 在本发明中,对分离的方法不做特别限定,可以使用现有技术中任意一种固液分离的方法,如常压过滤或减压过滤等,优选为减压过滤。 [0047] In the present invention, a method for separation is not particularly limited, and any method of the prior art solid-liquid separation such as pressure filtration or filtration under reduced pressure, preferably vacuum filtration.

[0048] 在本发明步骤3中,所述固体为加氢催化剂,而滤液中含有产物异佛尔酮。 [0048] In step 3 of the present invention, the hydrogenation catalyst is a solid, and the filtrate containing the product isophorone.

[0049] 任选地,回收加氢催化剂用于下批加氢反应套用;本发明人发现,回收的加氢催化剂能够循环使用35次以上。 [0049] Optionally, the recovered hydrogenation catalyst for the hydrogenation reaction batch apply; The present inventors have found that the recovery of the hydrogenation catalyst can be recycled more than 35 times.

[0050] 优选地,回收的加氢催化剂在套用时,补加适量的新鲜加氢催化剂,更优选地,加氢催化剂补加量为首次加氢催化剂投料量的〇. Iwt%~5wt%,优选0.1 wt%~0. 5wt%。 [0050] Preferably, the hydrogenation catalyst is recovered when applying, supplemented with a suitable amount of fresh hydrotreating catalyst, more preferably, the hydrogenation catalyst is the amount of additional first feeding amount of a hydrogenation catalyst billion. Iwt% ~ 5wt%, preferably 0.1 wt% ~ 0. 5wt%.

[0051] 步骤4,将步骤3制得的异佛尔醇、水杨酸甲酯和酯交换催化剂投入酯交换反应釜中,进行反应,得到原膜散酯粗产物。 [0051] Step 4, Step 3 was isophorone, methyl salicylate and transesterification catalyst into an ester exchange reactor, reacted to give a crude product Homosalate.

[0052] 本发明人发现,水杨酸甲酯为分子最小的水杨酸酯,其结构简单,空间位阻小,容易进行酯交换反应,因此,本发明选择水杨酸甲酯与异佛尔醇反应制备原膜散酯。 [0052] The present inventors have found that methyl salicylate is salicylate smallest molecules, is simple in structure, steric hindrance, the transesterification reaction easily, therefore, the present invention selects and methyl salicylate isoforskolin Seoul prepared by reacting an alcohol Homosalate.

[0053] 在本发明步骤4中,所述酯交换催化剂为酯交换催化剂,优选选自无机催化剂、有机催化剂或有机金属催化剂,更优选为碳酸钾、碳酸钠、氧化钙、浓硫酸、氧化铝、对甲苯磺酸、甲磺酸、钛酸四丁酯、异丙醇铝、二正丁基氧化锡或二正辛基氧化锡等,进一步优选为二正丁基氧化锡(即D0T0)。 [0053] In step 4 of the present invention, the transesterification catalyst is a transesterification catalyst, preferably a catalyst selected from inorganic, organic catalysts or organometallic catalysts, and more preferably potassium carbonate, sodium carbonate, calcium oxide, sulfuric acid, aluminum , p-toluenesulfonic acid, methanesulfonic acid, tetrabutyl titanate, aluminum isopropoxide, di-n-butyltin oxide or di-n-octyl tin oxide and the like, more preferably di-n-butyltin oxide (i.e. D0T0).

[0054] 本发明人发现,在上述酯交换催化剂的作用下,步骤3制得的异佛尔醇能够与水杨酸甲酯以适当反应速度进行酯交换反应,既能保证酯交换反应的快速进行,也能够使酯交换反应的速度保持在可控的范围内。 [0054] The present inventors have found that, under the action of the above-described transesterification catalyst, obtained in step 3 can be performed isophorone alcohol ester with methyl salicylate in an appropriate reaction rate exchange reaction, can ensure rapid transesterification carried out, it is possible to make the transesterification reaction rate is maintained within a controlled range.

[0055] 本发明还发现,使用酸或者碱作为催化剂,具有较高的催化效率,但后处理复杂, 不可避免地产生大量废水,污染环境,且在后续提纯步骤中因微量酸碱物质的存在,将造成原膜散酯分解,难以获得高品质的原膜散酯,而使用二正辛基氧化锡作为催化剂,能够避免向反应体系中引入强酸或强碱,从而使制备过程更为绿色环保,也避免产生可能会引起环境污染的污水等废弃物,同时能够获得高品质的原膜散酯。 [0055] The present inventors also found that, due to the presence of an acid or a base material in a subsequent trace acid purification step as a catalyst having high catalytic efficiency, but complex, inevitably produce large amounts of waste water, pollution of the environment, and , Homosalate will cause decomposition, it is difficult to obtain a high-quality Homosalate, and di-n-octyl tin oxide as a catalyst, it is possible to avoid the introduction of acid or alkali to the reaction system, so that the manufacturing process greener , but also to avoid sewage and other waste may cause environmental pollution, and possible to obtain high-quality Homosalate.

[0056]因此,本发明优选使用二正辛基氧化锡作为催化剂。 [0056] Accordingly, the present invention is preferably di-n-octyl tin oxide as a catalyst.

[0057] 优选地,酯交换催化剂与水杨酸甲酯的重量比为酯交换催化剂的重量:水杨酸甲酯的重量=0.0001:1~〇. 1:1,优选0.005:1~0.05:1。 [0057] Preferably, the transesterification catalyst and the weight ratio of methyl salicylate by weight of a transesterification catalyst: wt = methyl salicylate 0.0001: 1 to square 1: 1, preferably 0.005: 1 to 0.05: 1. 本发明人发现当酯交换催化剂与水杨酸甲酯的重量比大于〇. 1:1时,酯交换反应速率过大,反应不易控制,副产物增多;当酯交换催化剂与水杨酸甲酯的重量比小于〇. 0001:1时,反应速率过小,耗时增加。 The present inventors found that when a transesterification catalyst to methyl salicylate square weight ratio greater than 1: 1, the transesterification reaction rate is too large, difficult to control the reaction, by-products increased; when the transesterification catalyst and methyl salicylate the weight ratio of less than 0001 square: 1, the reaction rate is too small, time-consuming increased.

[0058] 在本发明步骤4中,步骤3制得的异佛尔醇与水杨酸甲酯的摩尔量之比为异佛尔醇的摩尔量:水杨酸甲酯的摩尔量=1:1~10:1,优选2:1~5:1,其中,异佛尔醇的摩尔量以其分子的摩尔量计,水杨酸甲酯的摩尔量以其分子的摩尔量计。 [0058] In the present invention, in step 4, step 3 was isophorone alcohol molar ratio of methyl salicylate to the amount of isophorone molar amount of alcohol: the molar amount of methyl salicylate = 1: molar amount 1, wherein the molar amount of alcohol in its isophorone molar amount of the molar amount of methyl salicylate in its molecule molecules: 1 to 10: 1, preferably 2: 1 to 5.

[0059] 在本发明中,异佛尔醇既做溶剂,又做反应原料,因此,本发明选择使异佛尔醇大量过量,优选地,当反应结束后,将过量的异佛尔醇回收,用于新反应的套用。 [0059] In the present invention, isophorone both alcohol as solvent, and the reaction raw materials do, therefore, the present invention is selected so that a large excess isophorone alcohol, preferably, when the end of the reaction, the excess alcohol recovered isophorone , apply for a new reaction.

[0060] 在本发明步骤4中,所用反应釜优选为带有精馏塔的反应釜,从而能够将酯交换产物原膜散酯通过精馏的方式分离出反应体系,同时,对酯交换产物进行纯化,使制得的产物原膜散酯具有较高的纯度。 [0060] In the present invention, in step 4, the reaction vessel is preferably used is a reaction kettle with a distillation column, thereby enabling the transesterification product Homosalate reaction system is separated by rectification manner, while the product of the transesterification purification, the product obtained Homosalate having high purity.

[0061] 在本发明步骤4中,控制酯交换反应的温度为100~200°C,优选为160~190°C。 [0061] In step 4 of the present invention, control of the reaction temperature of the transesterification 100 ~ 200 ° C, preferably 160 ~ 190 ° C. 本发明人发现,在温度为100~200°C时,酯交换反应进行的快速充分,且副产物少。 The present inventors have found that, at a temperature of 100 ~ 200 ° C, transesterification reaction was carried out sufficiently quickly, and less by-products.

[0062] 在本发明步骤4中,监控反应体系中水杨酸的含量,基于体系的总重量计,当体系中水杨酸的含量小于〇.5wt%时,认为反应充分,终止酯交换反应。 [0062] In the present invention, in step 4, to monitor the content of salicylic acid in the reaction system, based on the total weight of the system, when the system is less than the salicylic acid 〇.5wt%, the reaction was considered sufficient to terminate the transesterification reaction . 不受任何理论的束缚,本发明人认为,在异佛尔醇与水杨酸甲酯进行的酯交换反应中,水杨酸甲酯首先在催化剂作用下,在加热的条件下部分水解为水杨酸和甲醇,其中,水解得到的水杨酸与异佛尔醇在相同的条件下进行酯化反应,生成了稳定性更高的原膜散酯,当水杨酸甲酯反应完全后,体系中则不再产生水杨酸,即可判断反应充分,终止反应。 Without being bound by any theory, the inventors believe, isophorone ester in an alcohol exchange reaction with methyl salicylate, methyl salicylate in the first catalyst, under heating water partial hydrolysis salicylic acid and methanol, wherein the salicylic acid obtained by hydrolysis with an alcohol isophorone performed under the same conditions as the esterification reaction to produce a higher stability Homosalate, when the complete reaction of methyl salicylate, the system is no longer produce acid, the reaction was judged to be sufficient to terminate the reaction.

[0063]在本发明步骤4中,生成物除原膜散酯外,还包括工业副产品-甲醇。 [0063] In step 4 of the present invention, in addition to product Homosalate, further comprising industrial byproducts - methanol. 优选地,回收甲醇提高经济效益。 Preferably, methanol recovery increase economic efficiency.

[0064] 更优选地,回收剩余的异佛尔醇和酯交换催化剂。 [0064] More preferably, the recovered alcohol and the remaining isophorone transesterification catalyst.

[0065] 步骤5,将步骤4制得的原膜散酯粗产物进行纯化,得到产品原膜散酯。 [0065] Step 5, the original film obtained in Step 4 The crude ester was purified bulk, to give the product Homosalate.

[0066] 在本发明步骤4中,在制备原膜散酯的过程中被分离出来的原膜散酯粗产物中可能会混有异佛尔醇等原料,因此,需要对产物进行进一步的纯化,在本发明中优选使用精馏的方法进行纯化。 [0066] In the present invention, in step 4, it was isolated during the preparation of Homosalate homomenthyl crude product ester may be mixed with the raw material alcohol and isophorone, therefore, the need for further purification of the product was , distillation is preferably used in the present invention a method for purification.

[0067] 在本发明步骤5中,在纯化原膜散酯产品时,保留馏程为161~165°C部分的馏分, 其为产品原膜散酯;收集馏程为62~65°C部分的馏分,其为甲醇;收集馏程为193~196°C 部分的馏分,其为原料异佛尔醇。 [0067] In step 5, the present invention, when the purification Homosalate, reserved a distillation range of 161 ~ 165 ° C partial fraction, which is the product Homosalate; collecting a distillation range section 62 ~ 65 ° C fraction, which is methanol; collecting a distillation range of 193 ~ 196 ° C fraction portion, which is a raw material alcohol and isophorone.

[0068] 任选地,回收的异佛尔醇用于套用。 [0068] Optionally, the recovered isophorone apply for alcohol.

[0069] 任选地,馏底的酯交换催化剂用于套用。 [0069] Optionally, the bottom of the transesterification catalyst was distilled to apply.

[0070] 在本发明一种优选的实施方式中,回收酯交换催化剂进行套用时,需要补加适量的新鲜酯交换催化剂,酯交换催化剂的补加量为首次酯交换催化剂投料量的lwt%~ 50wt %,优选IOwt % ~30wt %。 [0070] In a preferred embodiment of the present invention, the transesterification catalyst recovered when applied, require supplementary amount of fresh transesterification catalyst, an additional amount of the transesterification catalyst for the first time an ester interchange catalyst feeding amount lwt% 50wt%, preferably IOwt% ~ 30wt%.

[0071] 在本发明步骤5中制得的原膜散酯为无色透明粘稠液体,折光率(nd20)为L 516 ~• 519,比重(20°C,mg/mL)为L 049 ~L 053 ;酸值彡lmgKOH/g ;GC 含量(面积归一法):顺式彡85.0%,反式彡15%,总含量彡99.0%;单个杂质含量(GC)彡0• 1%,总杂质含量(GC)彡0. 5%。 [0071] In step 5 of the present invention prepared in Homosalate a colorless transparent viscous liquid, refractive index (nD20) of L 516 ~ • 519, a specific gravity (20 ° C, mg / mL) of L 049 ~ L 053; acid value San lmgKOH / g; GC content (area normalization method): 85.0% San cis, 15% trans-San, San total content 99.0%; individual impurity content (GC) San 0 • 1%, of the total impurity content (GC) San 0.5%.

[0072] 根据本发明的第二方面,还提供一种根据上述第一方面所述方法制得的原膜散酯,其特征在于,所述原膜散酯为无色透明粘稠液体,折光率(nd20)为1. 516~1. 519,比重(20°C,mg/mL)为1. 049 为1. 053;酸值彡lmgKOH/g ;GC含量(面积归一法):顺式彡85. 0%, 反式彡15%,总含量彡99.0%;单个杂质含量(GC)彡0.1%,总杂质含量(GC)彡0.5%。 [0072] According to a second aspect of the present invention there is also provided a method according to the first aspect of the prepared Homosalate, wherein said Homosalate as a colorless transparent viscous liquid. Refractive rate (nD20) of 1.516 to 1 519, a specific gravity (20 ° C, mg / mL) is 1.049 to 1.053; acid San lmgKOH / g; GC content (area normalization method): cis San 85.0%, 15% trans-San, San total content 99.0%; individual impurity content (GC) San 0.1%, the total impurity content (GC) San 0.5%.

[0073] 根据本发明提供的制备原膜散酯的方法,具有以下有益效果: [0073] The method for producing Homosalate present invention provides, has the following advantages:

[0074] (1)异佛尔酮加氢还原反应结束后,产物异佛尔醇的立体选择性为顺式:反式< 1:1,采用差向异构化的方法,可获得顺式异构体与反式异构体的比例大于85:15的异佛尔醇,这为后续制备高品质的原膜散酯提供了保障; After [0074] (1) hydrogenation reaction of isophorone, isophorone stereoselectivity product alcohol is cis: trans <1: 1, the method of epimerization is obtained cis isomer ratio of trans-isomer is greater than 85:15, isophorone alcohol, which follow the preparation of high-quality Homosalate provide a guarantee;

[0075] (2)采用差向异构化的方法,可获得任意比例的顺式:反式>1:1的异佛尔醇,而且差向异构化反应无需使用其它催化剂,仅需在反应结束后适当调节反应釜内的温度和氢气压力即可完成,操作简便,效果显著; [0075] (2) Method of epimerization, in any ratio obtained cis: trans> 1: 1, isobornyl alcohol, and the epimerization reaction without the use of other catalysts, just in after appropriately adjusting the reaction temperature and hydrogen pressure in the reactor to complete, easy to operate, the effect is significant;

[0076] (3)根据本发明提供的方法制备的异佛尔醇,其纯度(顺反异构体之和)>99%,可直接用于制备原膜散酯,无需额外精馏、蒸馏等纯化操作,而且仅需简单过滤即可回收加氢催化剂,且回收的加氢催化剂能够用于套用; [0076] (3) isophorone alcohol prepared according to the process provided by the present invention, having a purity (cis and trans isomers)> 99%, can be directly used to prepare Homosalate, without additional distillation, distillation and other purification operations, but only simple filtration to recover the hydrogenation catalyst, the hydrogenation catalyst can be recovered and used to apply;

[0077] (4)本发明使用的酯交换催化剂能够催化TMC与水杨酸甲酯进行酯交换制备原膜散酯,酯交换催化剂来源广泛,容易获得,催化效率高,经过精馏即可实现原料和产物与催化剂的分离,且酯交换催化剂可循环套用; [0077] (4) an ester exchange catalyst used in the present invention is capable of catalyzing the TMC transesterifying methyl salicylate prepared Homosalate, extensive transesterification catalyst sources, readily available, high catalytic efficiency can be achieved through distillation separate starting material and product and the catalyst, and transesterification catalyst can be recycled applied;

[0078] (5)本发明所述的工艺无废水产生,极大的减轻了环保压力; [0078] (5) The process according to the present invention generates no waste water, greatly reduce the environmental pressure;

[0079] (6)本发明提供的方法从根本上改变了防晒剂原膜散酯合成工艺复杂、产率低的现状,解决了其面临的品质不高的难题; [0079] (6) The method of the present invention provides a fundamentally changed Homosalate sunscreen complex synthesis, low yields status, which faces solve the problem of quality is not high;

[0080] (7)本发明提供的方法还具有简便、易于控制和工业化生产的特点。 [0080] (7) The method of the present invention further provides a simple, easy to control and industrialized production.

[0081] 实施例 [0081] Example

[0082] 实施例1 [0082] Example 1

[0083] (1)在加氢反应釜中加入2000kg异佛尔酮和14. OkgRu/C (基于Ru/C总重量,其中含Ru5. Iwt %,含水率45. 4% ),关闭加氢反应釜,用氮气置换反应釜内空气三次,再用氢气置换反应釜内氮气三次,将釜内氢气压力设定在0. 8MPa,开启搅拌,升温至80°C开始加氢, 至不再吸收氢气为止,取样做GC分析,顺式为33. 27%,反式为66. 52%,总含量99. 79%,顺式:反式=〇• 5。 [0083] (1) In the hydrogenation reaction vessel was added 2000kg isophorone and 14. OkgRu / C (based on Ru / C total weight, which contains Ru5. Iwt%, moisture content 45.4%), hydrogenated Close the reaction vessel was purged with nitrogen three times the air inside the autoclave, the nitrogen was replaced with hydrogen three times within the reactor, the hydrogen pressure in the autoclave set at 0. 8MPa, open stirring, warmed to 80 ° C starts hydrogenated until no absorption Until hydrogen, samples do GC analysis was 33.27% cis, trans was 66.52%, the total content of 99.79%, cis: trans = square • 5.

[0084] (2)差向异构化:将反应釜内氢气压力升至1.4MPa,反应釜内温度升至140°C,搅拌反应5h后取样,顺式为89. 89 %,反式为9. 84 %,总含量99. 73 %,顺式:反式=9. 14。 [0084] (2) epimerization: The hydrogen pressure within the autoclave was raised to 1.4MPa, the reactor temperature was raised to 140 ° C, the reaction was stirred 5h sampled, 89.89% of cis, trans relative 9.84%, the total content of 99.73%, cis: trans = 914.

[0085] (3)将反应釜内物料降温至60°C,过滤回收催化剂Ru/ClO.6Kg,用于下批套用,得异佛尔醇产品2035Kg,收率98. 87%。 [0085] (3) within the autoclave were cooled to 60 ° C, the catalyst was recovered by filtration Ru / ClO.6Kg, apply for the next batch, to obtain an alcohol product isophorone 2035Kg, a yield of 98.87%.

[0086] (4)在带精馏塔的反应釜中加入2000kg水杨酸甲酯、6000Kg步骤3制得的异佛尔醇和21Kg催化剂二正丁基氧化锡(DOTO),开启搅拌,将反应釜内温度升至160°C,开始计时反应,3h后取样分析,至反应釜内水杨酸含量〈0. 5 %时结束反应,回收副产甲醇437. 5Kg。 [0086] (4) added to the reaction kettle with a distillation column, 2000kg methyl salicylate, prepared in step 3 6000Kg isophorone n-butyl alcohol catalyst 21Kg tin oxide (DOTO), open stirring, the reaction the autoclave temperature was raised to 160 ° C, the reaction start timing, sampling and analysis after 3h, the salicylic acid to the reaction kettle <terminate the reaction when 0.5 percent, recovering methanol byproduct 437. 5Kg.

[0087] (5)将反应釜内温度降至90°C,减压精馏回收原料和产品,共回收异佛尔醇4331. 5Kg,产品原膜散酯3200Kg,收率92. 81%。 [0087] (5) The reactor temperature was lowered to within 90 ° C, vacuum distillation recovery of raw materials and products, alcohol co recovered isophorone 4331. 5Kg, Homosalate 3200kg product, a yield of 92.81%. 折光率(nd20)为1. 516,比重(20°C,mg/ mL)为L 049酸值彡lmgKOH/g,顺式为90. 95 %,反式为8. 65 %,总含量(GC)为99. 60 %,单个杂质含量(GC)彡0. 1%,总杂质含量(GC)为0.4%。 Refractive index (nD20) of 1.516, a specific gravity (20 ° C, mg / mL) as an acid value of L 049 San lmgKOH / g, 90.95% of cis, trans was 8.65%, the total content (GC ) was 99.60%, the single impurities (GC) San 0.1%, the total impurity content (GC) 0.4%.

[0088] 实施例2 [0088] Example 2

[0089] (1)在加氢反应釜中加入2000kg异佛尔酮、实施例1回收Ru/C催化剂10. 6Kg 和2. OKg新鲜的Ru/C催化剂(基于Ru/C总重量,其中含Ru5. 1 %,含水率45. 4% ),关闭加氢釜,用氮气置换釜内空气三次,再用氢气置换釜内氮气三次,将釜内氢气压力设定在I. 2MPa,开启搅拌,升温至IKTC开始加氢,至不再吸收氢气为止,取样做GC分析,顺式为10. 10%,反式为89. 68%,总含量99. 78%,顺式:反式=0. 11。 [0089] (1) was added isophorone 2000kg hydrogenation reactor, recovered in Example 1 Ru / C catalyst 10. 6Kg and 2. OKg fresh Ru / C Catalyst (based on the total weight of the Ru / C, which contains Ru5. 1%, water content 45.4%), close hydrogenation reactor, to replace air with nitrogen the autoclave three times, three times with nitrogen and then the autoclave was purged with hydrogen, the hydrogen pressure in the autoclave set at I. 2MPa, open stirring, IKTC warmed to start the hydrogenation to not absorb hydrogen, to do sampling GC analysis was 10.10% cis, trans was 89.68%, the total content of 99.78%, cis: trans = 0. 11.

[0090] (2)差向异构化:将反应釜内氢气压力升至1.6MPa,反应釜内温度升至150°C,搅拌反应7h后取样,顺式为90. 35 %,反式为9. 35 %,总含量99. 70 %,顺式:反式=9. 66。 [0090] (2) epimerization: The hydrogen pressure within the autoclave was raised to 1.6MPa, the reactor temperature was raised to 150 ° C, the reaction was stirred for 7h after sampling, was 90.35% cis, trans relative 9.35%, the total content of 99.70%, cis: trans = 966.

[0091] (3)将釜内物料降温至70°C,过滤回收催化剂Ru/C13. 2Kg,用于下批套用,得异佛尔醇产品2053. 5Kg,收率99. 77%。 [0091] (3) The contents of the autoclave was lowered to 70 ° C, the catalyst was recovered by filtration Ru / C13. 2Kg, apply for the next batch, to obtain an alcohol product isophorone 2053. 5Kg, a yield of 99.77%.

[0092] (4)在实施例1中所使用的带精馏塔的反应釜中加入2000kg水杨酸甲酯、实施例1回收的4331. 5Kg异佛尔醇、补加新异佛尔醇1870Kg和4. 2Kg新催化剂二正丁基氧化锡(DOTO),开启搅拌,将反应釜内温度升至180°C,开始计时反应,3h后取样分析,至水杨酸含量〈0. 5 %时结束反应,回收副产甲醇445. 2Kg。 [0092] (4) was added 2000kg methyl salicylate in an autoclave in Example 1 with the rectification column used in, 4331. 5Kg isophorone alcohol recovered in Example 1 embodiment, additional new isophorone alcohol 4. 2Kg 1870Kg fresh catalyst and di-n-butyltin oxide (DOTO), open stirring, the reaction temperature in the kettle was raised to 180 ° C, the reaction start timing, sampling and analysis after 3h, the salicylic acid to <0.5% when the reaction was completed, the methanol recovered byproduct 445. 2Kg.

[0093] (5)将釜温降至100°C,减压精馏回收原料和产品,共回收异佛尔醇4426. 3Kg,产品原膜散酯3310.0 Kg,收率96. 0%,折光率(nd20)为1. 519,比重(20°C,mg/mL)为1. 053, 酸值< lmgKOH/g,顺式为89. 95 %,反式为9. 75 %,总含量(GC)为99. 70 %,单个杂质含量(GC)彡0. 1 %,总杂质含量(GC)为0. 3 %。 [0093] (5) The pot temperature dropped to 100 ° C, vacuum distillation recovery of raw materials and products, alcohol co recovered isophorone 4426. 3Kg, product Homosalate 3310.0 Kg, a yield of 96.0%, a refractive rate (nD20) of 1.519, a specific gravity (20 ° C, mg / mL) was 1.053, an acid value of <lmgKOH / g, 89.95% of cis, trans was 9.75%, the total content ( GC) was 99.70%, the single impurities (GC) San 0.1%, the total impurity content (GC) of 0.3%.

[0094] 以上结合具体实施方式和范例性实例对本发明进行了详细说明,不过这些说明并不能理解为对本发明的限制。 [0094] with reference to specific exemplary embodiments and examples of the present invention has been described in detail, but these instructions are not construed as limiting the present invention. 本领域技术人员理解,在不偏离本发明精神和范围的情况下, 可以对本发明技术方案及其实施方式进行多种等价替换、修饰或改进,这些均落入本发明的范围内。 Those skilled in the art understand, without departing from the spirit and scope of the present invention may be various equivalents and alternative embodiments of the technical solutions of the present invention, modifications or improvements which fall within the scope of the present invention. 本发明的保护范围以所附权利要求为准。 The scope of the invention is subject to the appended claims.

Claims (10)

1. 一种制备原膜散酯的方法,其特征在于,该方法包括以下步骤: 步骤1),在反应釜中加入异佛尔酮和加氢催化剂,通入氢气; 步骤2),差向异构化反应; 步骤3),将步骤2得到的体系降温,得到中间体异佛尔醇; 步骤4),将步骤3制得的异佛尔醇、水杨酸甲酯和酯交换催化剂投入酯交换反应釜中, 进行反应,得到原膜散酯粗产物; 步骤5),将步骤4制得的原膜散酯粗产物进行纯化,得到产品原膜散酯。 An original method for preparing Homosalate, characterized in that the method comprises the following steps: Step 1), was added to the kettle isophorone and a hydrogenation catalyst, into hydrogen; step 2), the difference isomerization reaction; step 3), the cooling system obtained in step 2, to give the intermediate alcohol, isophorone; step 4), prepared in step 3 isophorone, methyl salicylate and transesterification catalyst is placed into transesterification reaction pot to give the crude product Homosalate; step 5), prepared in step 4 Homosalate crude product was purified to give products Homosalate.
2. 根据权利要求1所述的方法,其特征在于,步骤1中, 所述加氢催化剂为骨架镍、亚铬酸铜、Rh/C、Rh/Al203、Pd/C、Pd/Al 203、Ru/C、RuAl2O3 等,优选为Ru/C ; 所述异佛尔酮与加氢催化剂中除铝元素以外的金属元素(如Ru)的重量比为100000:1 ~100:1,优选10000:1 ~1000:1 ; 在通入氢气时,反应釜内氢气压力为0. 5~lOMPa,优选0. 6~2. OMPa,更优选为0. 6~ I. 2MPa ; 在通入氢气时,反应釜内的温度为25~200 °C,优选50~180 °C,更优选70~110 °C。 2. The method according to claim 1, wherein, in step 1, the hydrogenation catalyst is Raney nickel, copper chromite, Rh / C, Rh / Al203, Pd / C, Pd / Al 203, Ru / C, RuAl2O3 the like, preferably Ru / C; the isophorone with a hydrogenation catalyst in a metal element other than aluminum element (e.g., Ru) weight ratio of 100,000: 1 to 100: 1, preferably 10,000: 1 to 1000: 1; when introducing hydrogen, a hydrogen pressure of the autoclave 0. 5 ~ lOMPa, preferably 0. 6 ~ 2 OMPa, more preferably 0. 6 ~ I. 2MPa; when introducing hydrogen. the temperature in the reactor is 25 ~ 200 ° C, preferably 50 ~ 180 ° C, more preferably 70 ~ 110 ° C.
3. 根据权利要求1或2所述的方法,其特征在于,步骤1中, 所述Ru/C可以是干基形态或湿基形态,优选为湿基形态,更优选地,Ru/C中含水率为10~65 %,优选含水率为40~60 % ; 所述Ru/C中,基于Ru/C的总重量,其中金属Ru含量为0. 5~50qwt % (以干基形态计),优选1~20wt %,特别优选3~IOwt %。 3. The method of claim 1 or claim 2, wherein, in step 1, the Ru / C may be a form of dry or wet form group, preferably form a wet group, more preferably, Ru / C in a water content of 10 to 65%, preferably 40 to 60% water content; the Ru / C, based on the total weight of the Ru / C, wherein the metal content of Ru 0. 5 ~ 50qwt% (dry basis Morphometric) , preferably 1 ~ 20wt%, particularly preferably 3 ~ IOwt%.
4. 根据权利要求1~3之一所述的方法,其特征在于,步骤2中, 在差向异构化反应时,反应釜内氢气压力为1. 〇~l〇MPa,优选I. 0~2. 5MPa,更优选I. 0 ~I. 8MPa ; 在差向异构化反应时,反应釜内的温度为130~250°C,优选130~200°C,更优选130 ~160。 The method according to any one of claims 1 to 3, wherein, in step 2, when the epimerization reaction, the reactor hydrogen pressure of 1 ~ l〇MPa billion, preferably I. 0 . ~ 2 5MPa, more preferably I. 0 ~ I 8MPa;. epimerization at the reaction temperature in the reactor is 130 ~ 250 ° C, preferably 130 ~ 200 ° C, more preferably 130 to 160. . ; 差向异构化反应的时间为4~12h,优选4~7h。 ; Epimerization reaction time is 4 ~ 12h, preferably 4 ~ 7h.
5. 根据权利要求1~4之一所述的方法,其特征在于,步骤3中, 步骤2反应结束后,使体系降温至60~70°C, 体系降温后,分离除去其中的固体,得到中间体异佛尔醇, 任选地,回收加氢催化剂用于下批加氢反应套用; 优选地,回收加氢催化剂套用时,补加适量的新鲜加氢催化剂,更优选地,加氢催化剂补加量为首次加氢催化剂投料量的〇. Iwt%~5wt%,优选0.1 wt%~0. 5wt%。 5. The method of one of claims 1-4, characterized in that, in step 3, step 2. After completion of the reaction, the system cooled to 60 ~ 70 ° C, after cooling the system, wherein the solids separated and removed, to give intermediate isophorone alcohol, optionally, recovering the hydrogenation catalyst for the hydrogenation reaction batch apply; preferably, the hydrogenation catalyst is recovered when applied, additional amount of fresh hydrogenation catalyst, more preferably, the hydrogenation catalyst square additional amount of the first feeding amount of the hydrogenation catalyst. Iwt% ~ 5wt%, preferably 0.1 wt% ~ 0. 5wt%.
6. 根据权利要求1~5之一所述的方法,其特征在于,步骤4中, 所述酯交换催化剂为无机催化剂、有机催化剂或有机金属催化剂,优选为碳酸钾、碳酸钠、氧化钙、浓硫酸、氧化铝、对甲苯磺酸、甲磺酸、钛酸四丁酯、异丙醇铝、二正丁基氧化锡或二正辛基氧化锡等,更优选为二正辛基氧化锡; 酯交换催化剂与水杨酸甲酯的重量比为0.0001:1~〇. 1:1,优选0.005:1~0.05:1 ; 异佛尔醇与水杨酸甲酯的摩尔量之比为1:1~10:1,优选2:1~5:1,其中,异佛尔醇的摩尔量以其分子的摩尔量计,水杨酸甲酯的摩尔量以其分子的摩尔量计; 步骤4的反应温度为100~200°C,优选为160~190°C。 6. The method of one of claims 1-5, characterized in that, in step 4, the transesterification catalyst is an inorganic catalyst, an organic catalyst or an organometallic catalyst, preferably potassium carbonate, sodium carbonate, calcium oxide, concentrated sulfuric acid, aluminum oxide, p-toluenesulfonic acid, methanesulfonic acid, tetrabutyl titanate, aluminum isopropoxide, di-n-butyl-n-octyl tin oxide or tin oxide or the like, more preferably di-n-octyl tin oxide ; weight of methyl salicylate and transesterification catalyst ratio of 0.0001: 1 to square 1: 1, preferably 0.005: 1 to 0.05: 1; isophorone ratio of alcohol to methyl salicylate is a molar amount of : 1 to 10: 1, preferably 2: 1 to 5: 1 molar amount, wherein the molar amount of alcohol in its isophorone molar amount of the molar amount of methyl salicylate in its molecule molecule; step 4 the reaction temperature is 100 ~ 200 ° C, preferably 160 ~ 190 ° C.
7. 根据权利要求1~6之一所述的方法,其特征在于,步骤5中, 所述纯化的方法为精馏; 任选地,回收的异佛尔醇套用; 任选地,馏底酯交换催化剂套用。 7. The method of one of claims 1-6, wherein, in step 5, the purification method is distillation; optionally apply the recovered isophorone alcohol; optionally distilled bottom apply transesterification catalyst.
8. 根据权利要求1~7之一所述的方法,其特征在于,步骤5中, 回收酯交换催化剂进行套用时,补加适量的新鲜酯交换催化剂,酯交换催化剂的补加量为首次酯交换催化剂投料量的Iwt%~50wt%,优选IOwt%~30wt%。 8. The method according to one of claims 1 to 7, wherein, in step 5, when a transesterification catalyst recovered apply, supplemented with a suitable amount of fresh transesterification catalyst, an additional amount of the transesterification catalyst for the first ester exchange catalyst feeding amount Iwt% ~ 50wt%, preferably IOwt% ~ 30wt%.
9. 根据权利要求1~8之一所述的方法,其特征在于,步骤5中, 制得的原膜散酯为无色透明粘稠液体,折光率(nd20)为1. 516~1. 519,比重(20°C, mg/mL)为L 049~L 053 ;酸值彡lmgKOH/g ;GC含量(面积归一法):顺式彡85. 0%,反式彡15%,总含量彡99.0% ;单个杂质含量(GC)彡0.1%,总杂质含量(GC)彡0.5%。 9. The method according to any one of claims 1 to 8, wherein, in step 5, resulting Homosalate a colorless transparent viscous liquid, refractive index (nD20) of 1.516 to 1. 519, a specific gravity (20 ° C, mg / mL) of L 049 ~ L 053; acid value San lmgKOH / g; GC content (area normalization method): 85.0% San cis, 15% trans-San, total San content 99.0%; individual impurity content (GC) San 0.1%, the total impurity content (GC) San 0.5%.
10. -种根据权利要求1~9之一所述的方法制得的原膜散酯,其特征在于,所述原膜散酯为无色透明粘稠液体,折光率(nd20)为1. 516~1. 519,比重(20°C,mg/mL)为1. 049~ 1.053 ;酸值< lmgKOH/g ;GC含量(面积归一法):顺式彡85.0%,反式< 15%,总含量彡99. 0 % ;单个杂质含量(GC)彡0• 1 %,总杂质含量(GC)彡0• 5 %。 10. - Homosalate seed obtained according to the method according to any one of claims 1 to 9, wherein said Homosalate a colorless transparent viscous liquid, refractive index (nD20) 1. 516 ~ 1,519, a specific gravity (20 ° C, mg / mL) was 1.049 ~ 1.053; acid <lmgKOH / g; GC content (area normalization method): 85.0% San cis, trans <15% , San total content of 99.0%; individual impurity content (GC) San 0 • 1%, the total impurity content (GC) San 0 • 5%.
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