WO2019034006A1 - Procédé de production d'écoulement en ligne entièrement continu pour la préparation directe de peroxyde organique à partir d'alcool ou d'alcane - Google Patents

Procédé de production d'écoulement en ligne entièrement continu pour la préparation directe de peroxyde organique à partir d'alcool ou d'alcane Download PDF

Info

Publication number
WO2019034006A1
WO2019034006A1 PCT/CN2018/100115 CN2018100115W WO2019034006A1 WO 2019034006 A1 WO2019034006 A1 WO 2019034006A1 CN 2018100115 W CN2018100115 W CN 2018100115W WO 2019034006 A1 WO2019034006 A1 WO 2019034006A1
Authority
WO
WIPO (PCT)
Prior art keywords
continuous flow
process according
production process
still
full continuous
Prior art date
Application number
PCT/CN2018/100115
Other languages
English (en)
Chinese (zh)
Inventor
马兵
潘帅
舒鑫琳
Original Assignee
上海惠和化德生物科技有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from CN201810900615.8A external-priority patent/CN109553560A/zh
Application filed by 上海惠和化德生物科技有限公司 filed Critical 上海惠和化德生物科技有限公司
Priority to JP2020516679A priority Critical patent/JP6925079B2/ja
Priority to EP18846139.6A priority patent/EP3666754B1/fr
Publication of WO2019034006A1 publication Critical patent/WO2019034006A1/fr
Priority to US16/787,029 priority patent/US10919849B2/en

Links

Images

Classifications

    • 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
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C407/00—Preparation of peroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C409/00—Peroxy compounds
    • C07C409/38—Peroxy compounds the —O—O— group being bound between a >C=O group and a carbon atom, not further substituted by oxygen atoms, i.e. esters of peroxy acids

Definitions

  • the invention relates to the field of chemistry, in particular to an in-line full continuous flow production process for directly preparing an organic peroxide from an alcohol or an alkane, wherein the organic peroxide is a flammable and explosive compound.
  • the organic peroxide refers to an organic compound containing a -O-O-peroxy functional group formed by replacing a hydrogen atom in hydrogen peroxide with an organic group such as an alkyl group, an acyl group or an aromatic group.
  • the characteristic is that when the heat exceeds a certain temperature, it will decompose to generate oxygenated free radicals, which is unstable and easy to decompose.
  • the organic peroxide produced by the chemical industry is mainly used as a polymerization initiator and catalyst for synthetic resins. In the field of polymer materials, organic peroxides are used as initiators for radical polymerization, initiators for grafting reactions, crosslinkers for rubber and plastics, curing agents for unsaturated polyesters, and in the preparation of spun grade polypropylene.
  • Organic peroxides are sources of free radicals for use in the following: 1 free radical polymerization and copolymerization initiators of vinyl and diene monomers; 2 vulcanizing agents for thermosetting resins; 3 crosslinkers of elastomers and polyethylene .
  • organic peroxides are used as photoinitiators and sensitizers in the film industry for photosensitive polymer materials, photosensitive resins, etc., and are also commonly used in the production of epoxy resins;
  • organic peroxides are also used in bleaching agents, decolorizing agents, bactericides, cleaning agents, etc. for the sterilization of medical devices and foods, textiles, paper, and the like.
  • Peroxycarboxylic acid esters and peroxycarbonates are important organic peroxides, such as tert-butyl peroxy-2-octanyl carbonate, cumene peroxy neodecanoate and neodecanoic acid-1. 1,3,3-tetramethylbutyl ester.
  • Peroxycarboxylic acid esters and peroxycarbonates are low temperature initiators for free radical polymerization and are widely used in polyethylene (LDPE), polyvinyl chloride (PVC), polystyrene (PS), and styrene copolymers (eg, Production areas such as ABS), polymethacrylate (PMMA) and polyvinyl acetate (PVAc).
  • Peroxy ketals are mainly used as crosslinking agents for unsaturated polyesters, as initiators for rubber and plastics.
  • the demand for peroxycarboxylic acid esters, peroxycarbonates and peroxyketals is increasing in domestic and foreign markets, so the continuous production process of developing organic peroxides has practical significance and great prospects.
  • Organic peroxides are very reactive compounds that are easily decomposed into highly reactive free radicals and oxygen, which can release a large amount of heat or even cause an explosion.
  • SADT self-accelerating decomposition temperature
  • the exothermic rate of the organic peroxide decomposition reaction is unbalanced with the environmental heat dissipation rate, that is, the heat of the system is Accumulating, at this time, organic peroxides can cause dangerous self-accelerating decomposition reactions and explosions or fires in adverse environments by thermal decomposition. Contact with incompatible materials and increased mechanical stress can result in decomposition at or below SADT.
  • the organic peroxide decomposes under the action of temperature due to the presence of an oxygen-oxygen bond which can be opened in the energy range ⁇ H of about 84 to 184 kJ/mol, depending on the organic peroxide. nature. That is to say, the energy required for the decomposition of different organic peroxides to open the oxygen-oxygen bond is different depending on the respective properties. Therefore, different organic peroxides have large differences in self-decomposition acceleration temperature and thermal stability.
  • peroxy carboxylic acid ester peroxide peroxyphenyl phthalate has a self-decomposition acceleration temperature (SADT) of 10 ° C, a 10-hour half-life corresponding to a temperature of 38 ° C; peroxypivalic acid
  • SADT self-decomposition acceleration temperature
  • TBPV tert-butyl ester
  • SADT self-decomposition acceleration temperature
  • SADT self-decomposition acceleration temperature
  • SADT self-decomposition acceleration temperature
  • tert-butyl peroxy neodecanoate is 15 ° C, 10
  • the half-life of the hour corresponds to a temperature of 46 ° C
  • the peroxycarbonate peroxide peroxide 2-ethylhexyl carbonate tert-butyl ester (TBEC) self-decomposition acceleration temperature (SADT) is 60 ° C
  • the 10-hour half-life corresponds to the temperature 100 ° C
  • the first step is an oxidation reaction.
  • the alcohol or alkane reacts with an oxidant to synthesize an alkyl peroxide R(OOH) n and a dialkyl peroxide ROOR.
  • impurities such as dialkyl peroxide ROOR and water are removed.
  • the oxidation reaction product alkyl peroxide R(OOH) n is obtained , and the reaction formula is as follows:
  • the second step is a condensation reaction in which an alkyl peroxide R(OOH) n is reacted with a base and an acyl compound to synthesize a peroxycarboxylate or a peroxycarbonate.
  • the reaction formula is as follows:
  • the alkyl peroxide R(OOH) n is reacted with an acid and an alcohol or a ketone to synthesize a peroxy ketal.
  • the reaction formula is as follows:
  • R is selected from saturated or unsaturated C 1 -C 12 alkyl, unsubstituted or substituted aryl, unsubstituted or substituted heterocyclic aryl, unsubstituted or substituted saturated heterocycloalkyl, unsubstituted Or a partially saturated heterocycloalkyl group, an unsubstituted or substituted cycloalkyl group.
  • R 1 is selected from a saturated or unsaturated C 1 -C 20 alkyl group, an unsubstituted or substituted aryl group, an unsubstituted or substituted heterocyclic aryl group.
  • R 2 is selected from a saturated or unsaturated C 1 -C 20 alkyl group, an unsubstituted or substituted aryl group, an unsubstituted or substituted heterocyclic aryl group, an unsubstituted or substituted saturated heterocycloalkyl group, an unsubstituted or Substituting partially saturated heterocycloalkyl, unsubstituted or substituted cycloalkyl.
  • R 3 is selected from saturated or unsaturated C 1 -C 12 alkyl, unsubstituted or substituted aryl, unsubstituted or substituted heterocyclic aryl, unsubstituted or substituted saturated heterocycloalkyl, unsubstituted or Substituting partially saturated heterocycloalkyl, unsubstituted or substituted cycloalkyl.
  • R 4 or R 4 ' is selected from a saturated or unsaturated C 1 -C 12 alkyl group, an unsubstituted or substituted aryl group, an unsubstituted or substituted heterocyclic aryl group, an unsubstituted or substituted saturated heterocycloalkyl group. Unsubstituted or substituted partially saturated heterocycloalkyl, unsubstituted or substituted cycloalkyl.
  • the improvement of the industrial production process of chemical products mainly refers to the improvement of the process.
  • the process refers to a method and a process for processing or reacting raw materials by using various equipments to obtain a final product, and is a process of obtaining a product by adjusting chemical, physical, or physical processes by adjusting technical parameters such as temperature, pressure, and material ratio. That is, the production process refers to the process of realizing a chemical reaction or a physical process on an industrial scale.
  • a process can contain one reaction or multiple reactions.
  • the reaction involved in the preparation of the chemical product and the corresponding reaction route are determined by the reaction mechanism, but for the same reaction route, it can be achieved by different production processes.
  • Production process optimization and improvement may achieve the following effects: first, improve production efficiency, increase production capacity, reduce production costs; second, improve process safety; third, improve product quality; fourth, reduce “three wastes” emissions.
  • the oxidation reaction and the condensation reaction correspond to an oxidation process and a condensation process, respectively.
  • the oxidation reaction and the condensation reaction are both oil-water two-phase reaction, the reaction efficiency is low, and a large amount of water exists in the reaction system.
  • the oxidant used in the first oxidation reaction is a liquid oxidant (for example: hydrogen peroxide) or a gaseous oxidant (for example, oxygen).
  • the two problems caused by the oxidation reaction are: 1) due to the oxidation process, the oxidant cannot be completely converted, and Inevitably, dialkyl peroxides are formed, and dialkyl peroxides and oxidants which are not completely reacted become impurities in the oxidation process, and these impurities must be removed to carry out the next condensation reaction.
  • peroxide impurities dialkyl peroxide and hydrogen peroxide directly affect the quality of the final product (peroxycarboxylic acid ester, peroxycarbonate, peroxyketal).
  • the target product is tert-butyl peroxy neodecanoate
  • the tert-butyl peroxy neodecanoate has a SADT of 15 ° C
  • the half-life of 10 h corresponds to a temperature of 46 ° C
  • the second process of preparing peroxy neodecanoate is prepared.
  • the SADT of tert-butyl hydroperoxide is 80 ° C, and the half-life of 10 h corresponds to a temperature of 121 ° C.
  • the SADT and half-life of different concentrations of hydrogen peroxide are different.
  • the half-life of hydrogen peroxide in fresh water at normal temperature is 8 hours. In 20 days, it can be seen that the SADT and the half-life of the three are very different, and the mixture of the three cannot meet the single use requirement.
  • the initiator is usually a free radical initiator such as azobisisobutyronitrile (SADT is 50 ° C, 10 h half-life) Decomposition temperature is 65 ° C), dicumyl hydroperoxide (SADT is 75 ° C, 10 h half-life decomposition temperature is 117 ° C), etc., if not removed into the final product will also affect product quality and performance, and second, water and other impurities will Influencing the reaction rate, which in turn affects the production efficiency.
  • SADT azobisisobutyronitrile
  • Decomposition temperature is 65 ° C
  • water and other impurities will Influencing the reaction rate, which in turn affects the production efficiency.
  • the product obtained after the oxidation process is a mixture containing alkyl peroxides, impurities, and a large amount of water, in order to ensure the condensation process.
  • a purification process is required to remove impurities and a large amount of water from the mixture to prepare an alkyl peroxide which meets the standards of commercial industrial products (for example, commercially available t-butyl hydroperoxide is as follows: di-tert-butyl peroxide) ⁇ 0.08%, tert-butanol ⁇ 0.5%, other organic matter ⁇ 0.4%).
  • the purification process may be gas-liquid separation, acid-base method, vacuum distillation or distillation, flash separation, etc., the purification process usually adopts a batch process, and the Chinese patent CN106588734 mentions the purification step of cumene hydroperoxide. Including gas-liquid separation, flash separation and concentration, Chinese patent CN102617432 mentions the synthesis of t-butyl hydroperoxide, which is allowed to stand still to obtain the upper organic phase, and the alkali solution is added to the organic phase at a reaction temperature of 10 to 50 ° C.
  • the existing condensation process only obtains crude peroxycarboxylate, peroxycarbonate or peroxyketal, contains water, alkyl peroxide, salt, etc., and needs to be post-treated to obtain the city.
  • Standard products such as commercially available tert-butyl peroxy neodecanoate are required as follows: chloride ion content ⁇ 0.05%, tert-butyl hydroperoxide content ⁇ 0.1%)
  • the post-treatment process may be separation, alkali washing, Washing, vacuum distillation or distillation, flash separation, drying, etc.
  • Chinese patent CN102558399 mentioned that the post-treatment method of peroxy neodecanoate tert-butyl ester is to stand for 20-40 min after the end of the reaction, and the mother liquor is separated and the reaction is carried out.
  • the product is washed to a pH of 5-7, and a solvent of a solvent-type peroxy neodecanoate is obtained by adding an alkane solvent and stirring at 0 ° C for 20-30 min.
  • the post-treatment time is greater than 40 min; the Chinese patent CN102336694 mentions 1,1-
  • the post-treatment method of bis(tert-butylperoxy)cyclohexane is the alkali washing of the reaction mother liquid and washing with water to obtain a neutral reaction liquid, and the colorless liquid is obtained by distillation under reduced pressure to obtain the product 1,1-di(tert-butyl group).
  • Oxidation of cyclohexane refer to existing post-treatment processes 1-2 hours.
  • the existing post-treatment process takes a long time and has low efficiency.
  • separate equipment such as a rectification tower is required, and different post-treatment processes of peroxy carboxylic acid ester, peroxycarbonate or peroxy ketal are also different, and the existing production process is also There is no universal equipment and process that can purify a variety of different peroxycarboxylic acid esters, peroxycarbonates or peroxyketals.
  • the prior art process for producing peroxycarboxylic acid esters, peroxycarbonates or peroxyketals in accordance with commercially available standards needs to be divided into four steps, the first step being an oxidation process, the products of which are comprising alkyl peroxides and impurities.
  • the second step is a purification process, in addition to impurities and a large amount of water, to obtain an alkyl peroxide (ie, an intermediate product) that meets the requirements of a commercially available industrial product, and stores it for use;
  • the crude product of the target product peroxycarboxylic acid ester, peroxycarbonate or peroxyketal
  • the fourth step of the post-treatment process removes impurities and water to obtain peroxidation in accordance with the requirements of commercially available industrial products. Carboxylic acid ester, peroxycarbonate or peroxyketal.
  • alkyl peroxides are flammable and explosive dangerous materials, so there is a great safety risk in the process of accumulation, storage and purification of such compounds, and since the alkyl peroxides are flammable and explosive Temperatures are extremely sensitive and require cold chain storage and transportation, which greatly increases the cost of use and production.
  • the accumulation, storage and purification of alkyl peroxides are not possible, and the oxidation process and the condensation process cannot be seamlessly coupled to realize the direct continuous preparation of peroxycarboxylic acid esters, peroxycarbonates and peroxidation from alcohols or alkanes.
  • alkyl peroxide is of the formula R(OOH) n , wherein R is selected from a saturated or unsaturated C 1 -C 12 alkyl group, an unsubstituted or substituted aryl group, an unsubstituted or substituted hetero Cycloaryl, unsubstituted or substituted saturated heterocycloalkyl, unsubstituted or substituted partially saturated heterocycloalkyl, unsubstituted or substituted cycloalkyl.
  • R is selected from a saturated or unsaturated C 3 -C 8 alkyl group, an unsubstituted or substituted aryl group, an unsubstituted or substituted heterocyclic aryl group, an unsubstituted or substituted saturated heterocycloalkyl group, Substituting or substituting partially saturated heterocycloalkyl, unsubstituted or substituted cycloalkyl.
  • R is selected from the group consisting of t-butyl, tert-amyl, cumyl, 1,4-diisopropylphenyl, 2,4,4-trimethyl-2-pentyl, 2,5-dimethyl Base group.
  • alkyl peroxide is selected from the group consisting of:
  • the most important characteristics of the batch process are two points. One is that there is “stay” or “interruption” in the process, and the second is that the production of the products is spaced apart, that is, the product has a batch and only one fixed quantity of product can be obtained in one batch. That is, for each batch of production, a fixed amount of the raw materials is reacted in the order of the reaction steps, resulting in a limited fixed amount of product (product); then a fixed amount of the raw material is put, and the same step is followed. The batch reacted to produce a limited fixed product.
  • each step in one reactor there are two ways to achieve a batch process: 1) using multiple reactors (eg, flasks, reactors, etc.), each step in one reactor; 2) using a reactor (eg, flask, reaction) In the reactor, etc., each step of the reaction is sequentially completed in the reactor, and a plurality of raw materials need to be sequentially added according to the progress of the reaction, that is, after each step of the reaction, there is a “stay”, waiting for further addition of the raw materials of the subsequent reaction. .
  • Some literatures also refer to mode 2) as continuous, which is also intermittent in nature, because there is "stay” in the process, waiting for feeding, or adjusting to the appropriate temperature for the next reaction (for example, heating, cooling) Or keep warm).
  • the first step oxidation process Whether using oxygen auto-oxidation method or hydrogen peroxide oxidation method, the batch process reactor has a large liquid holding capacity, and a single reaction requires a large amount of pure oxygen or hydrogen peroxide, so the batch process has great safety hazards.
  • the third step of the condensation process is mostly exothermic, and the reactor needs to have good heat transfer performance to ensure that the reaction does not fly. Once the temperature is too high, the product will decompose and the yield will decrease.
  • the existing batch process mainly controls the reaction temperature by controlling the addition rate of the oxidant (slow drop or slow aeration) in combination with the corresponding heat transfer device, so that the operation time is greatly prolonged and the production efficiency is lowered; A large amount of peroxide exists for a long time, and the process safety hazard is very large, and the process safety problem is not fundamentally solved. That is, intermittent process safety, product yield and quality stability are in urgent need of improvement.
  • the amplification effect refers to the results obtained by using small equipment for chemical process (ie, small-scale) experiments (such as laboratory scale), and the results obtained under the same operating conditions with large-scale production devices (such as industrial scale). There are often big differences. The effect of these differences is called the amplification effect.
  • the reason is mainly that the temperature, concentration, and material residence time distribution in small-scale experimental equipment are different from those in large-scale equipment. That is to say, under the same operating conditions, the results of small-scale experiments cannot be completely repeated on the industrial scale; if the results of the same or similar results as the small-scale experiments are obtained on the industrial scale, it is necessary to optimize the adjustment and change the process parameters and Operating conditions.
  • the amplification effect is a difficult and urgent problem to be solved.
  • Local production means that the manufacturer places the equipment in the nearest or same location for the end consumer (or downstream user), thus greatly reducing the number of products from the manufacturer to the end consumer (or downstream users).
  • Intermediate links such as warehousing, logistics, etc., save a lot of costs.
  • local production still cannot avoid the storage and transportation of a small number of products, for example, from one workshop of the factory to another, taking products from the production equipment of synthetic products and transporting them to downstream production equipment.
  • On-line manufacturing as a kind of on-site production, refers to the production and use of products at the same time, seamlessly connecting with downstream processes, and synchronous production methods, so that the products are ready for use (produce- To-use), ready-to-use flexible manufacturing.
  • the so-called ready-to-use that is, the output is the use, the production and use of the product at the same time; with the production, it is always ready to produce, no need to wait, on-demand production of zero inventory; plug-and-production production equipment, is Immediately after the production device is started, the product is obtained and produced on demand. After the demand is met, the vehicle can be stopped.
  • the production time of online production can be shortened to more than ten minutes or even minutes, which can be seamlessly connected with the production equipment and production process of downstream users, which fundamentally avoids the storage and transportation of products, saves costs and improves production.
  • the safety also increases production efficiency.
  • the production time refers to the time required from the entry of the raw material into the reactor to the output of the commercially available product, including the reaction time and the post-treatment time, which is also referred to as the residence time in the continuous flow process.
  • the organic peroxide integrated full continuous flow process and reactor of the invention can be directly and seamlessly connected to the process and reactor of the downstream end user, realizes ready-to-use use, and may even realize that the whole process has not been macroscopically
  • the integrated continuous flow process can be directly connected with the polymerizer in the field of polymer materials, the vulcanizer of the film industry, etc., forming a continuous and continuous production and use of organic peroxides, subverting existing production-storage-transport-storage-use. Production mode, realize the new production mode of production and use, organic peroxide online production, ready-to-use, on-demand production, zero inventory and no logistics.
  • tert-butyl 2-ethylhexyl carbonate as a crosslinking agent is the most critical core material for EVA film in solar modules.
  • the integrated continuous flow reactor of the present invention can be seamlessly coupled with an EVA film vulcanizer.
  • the tert-butyl peroxy 2-ethylhexyl carbonate meets the commercially available standard and is directly connected to the batching kettle of the vulcanizer after being discharged from the integrated continuous flow reactor, and then vacuum laminating into the vulcanizer to obtain an EVA film, and finally cutting the package.
  • Real production is the use, without the accumulation and storage of tert-butyl 2-ethylhexyl carbonate, on the one hand greatly improving the safety of the overall process, on the other hand further reducing the production costs and greatly improving the production efficiency .
  • Organic peroxides are very reactive compounds that are easily decomposed into highly reactive free radicals and oxygen. During this process, a large amount of heat is released and even an explosion is caused. Therefore, organic peroxides are extremely sensitive to temperature and must be stored and transported at low temperatures. .
  • the existing process involves the accumulation, purification, storage and transportation of a large number of oxidation reaction products (alkyl peroxides) and products (peroxycarboxylic acid esters, peroxycarbonates or peroxyketals), both of which are flammable. Explosive organic peroxides, so one-third of the cost of existing organic peroxides is used for cold chain storage and transportation of intermediate products and products. On-line production is produced on demand when the product is needed.
  • Chinese patent CN101479239 describes a method for continuously preparing an organic peroxide using a plate heat exchanger having high heat exchange capacity, which is continuously prepared at a given temperature by introducing different reactants at different positions (plates) of the plate heat exchanger. Selected peroxide.
  • the temperature is given to a temperature above which the organic peroxide becomes thermally sensitive. This indicates that the reaction temperature is lower than the corresponding organic peroxide SDAT, and the final preferred reaction temperature ranges from 5 to 60 °C.
  • the yield is close to the higher temperature, but lower than the corresponding organic peroxide SADT.
  • the synthesis reaction time is in the range of 1 second to 45 seconds in the laboratory scale, and up to 2 minutes to 3 minutes on the industrial scale.
  • the reaction time refers to the time required for the reaction material to enter the reactor until the end of the reaction to obtain the crude product of the target product, excluding the time of the post-treatment.
  • the continuous preparation method has certain advantages in production efficiency and safety.
  • the industrial scale reaction time is 2 to 180 times of the laboratory scale, and there is a large
  • the amplification effect of determining greatly increases the difficulty of industrialization.
  • This large-scale and uncertain amplification effect will bring many disadvantages to the industrial application of the process. For example, when industrialization is amplified, only multiple steps of amplification can be adopted, and in order to achieve consistency with the laboratory scale.
  • each process of amplification must be re-adjusted to optimize process conditions and parameters, which will greatly consume manpower and material resources and project development time; even if multiple step-by-step amplification is used, the magnification effect may be too large, which may eventually lead to amplification. Afterwards, the results of the laboratory scale cannot be achieved; at the same time, the large-scale uncertain amplification effect will affect the stability and reliability of the process, resulting in unstable product quality and difficult to control; in addition, it will bring potential safety to the production process. risk.
  • the production time takes 3 to 18 hours, the reaction time is long, the production efficiency is low, and it is impossible to achieve on-line production, that is, ready to use.
  • the existing processes all have different degrees of amplification effects, resulting in a large amount of manpower and material resources and a lot of uncertainty when industrialization is amplified; the process reliability after amplification also has problems, resulting in unstable product quality, difficult to control; and production
  • the process lacks flexibility and has potential safety risks; due to the low reaction temperature, the total reaction time is too long and the yield is not high, which reduces the production efficiency, which increases the difficulty of industrialization.
  • the inability to achieve mass production limits its application. Therefore, it is necessary to find a fully continuous flow production process of an organic peroxide which is simple, safe, efficient, and capable of on-line production, is easy to mass-produce, and has no amplification effect.
  • the technical problem to be solved by the present invention is to provide an in-line continuous continuous flow production process for directly preparing an organic peroxide from an alcohol or an alkane, wherein the organic peroxide is a peroxycarboxylic acid ester.
  • peroxycarbonate or peroxyketal the production process directly from the safe starting materials (alcohols or alkanes) to produce high-risk organic peroxides, macroscopically non-hazardous alkyl peroxides (ie intermediate products)
  • safe starting materials alcohols or alkanes
  • macroscopically non-hazardous alkyl peroxides ie intermediate products
  • Flexible manufacturing the process is simple, safe and efficient, and there is no amplification effect.
  • the obtained organic peroxide product has high yield and content, and is easy to mass produce. Low production cost and improve the safety of an organic peroxide and downstream production of products.
  • aryl refers to an all-carbon monocyclic or fused polycyclic group of 5 to 12 carbon atoms having a fully conjugated pi-electron system.
  • aromatic rings are: benzene rings, naphthalene rings, and anthracene rings. The aromatic ring may be unsubstituted or substituted.
  • the substituent of the aromatic ring is selected from the group consisting of halogen, nitro, amino, cyano, hydroxy, C 1 -C 6 alkyl, C 1 -C 6 alkoxy, halogenated C 1 -C 6 alkyl, halogenated C 1 -C 6 alkoxy, C 3 -C 6 cycloalkyl, halogenated C 3 -C 6 cycloalkyl.
  • heterocyclic aryl refers to an unsaturated carbocyclic ring of 5 to 12 ring atoms in which one or more carbon atoms are replaced by a hetero atom such as N, O, S or the like.
  • the heteroaryl ring may be a single ring or a double ring, that is, fused by two rings.
  • Specific heterocyclic aryl groups may be: pyridyl, pyrimidinyl, pyrazinyl, isoxazolyl, isothiazolyl, pyrazolyl, thiazolyl, oxazolyl and imidazolyl, and the like.
  • the heterocyclic aryl group can be unsubstituted or substituted.
  • the substituent of the heterocyclic aryl group is selected from the group consisting of halogen, nitro, amino, cyano, hydroxy, C 1 -C 6 alkyl, C 1 -C 6 alkoxy, halogenated C 1 -C 6 alkyl, halogenated C 1 -C 6 alkoxy, C 3 -C 6 cycloalkyl, halogenated C 3 -C 6 cycloalkyl.
  • heterocycloalkyl refers to a monocyclic or fused ring radical having from 5 to 12 ring atoms in the ring wherein one or both ring atoms are selected from N, O or S(O) m ( Wherein m is a hetero atom of 0 to 2 integers, and the remaining ring atoms are C. These rings may contain one or more double bonds, but these rings do not have a fully conjugated pi-electron system.
  • the unsubstituted heterocycloalkyl group may be a pyrrolidinyl group, a piperidinyl group, a piperazinyl group, a morpholino group, a thiomorpholino group, a homopiperazinyl group or the like.
  • the heterocyclic ring can be unsubstituted or substituted.
  • the substituent of the heterocyclic ring is selected from the group consisting of halogen, nitro, amino, cyano, hydroxy, C 1 -C 6 alkyl, C 1 -C 6 alkoxy, halogenated C 1 -C 6 alkyl, halogenated C 1 -C 6 alkoxy, C 3 -C 6 cycloalkyl, halogenated C 3 -C 6 cycloalkyl.
  • cycloalkyl refers to a saturated monocyclic carbocyclic ring having from 3 to 12 carbon atoms unless a different number of atoms are indicated.
  • the cycloalkyl group includes a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group and the like.
  • a cycloalkyl group can be unsubstituted or substituted.
  • the cycloalkyl group can also be optionally substituted on any available carbon with one or more substituents selected from the group consisting of alkoxy, halogen, haloalkyl such as perfluoroalkyl.
  • alkyl as used in this patent includes both straight chain alkyl and branched alkyl groups.
  • a single alkyl group such as "propyl”
  • a single branched-chain alkyl group such as "isopropyl”
  • C1-6 alkyl includes C1-4 alkyl, C1-3 alkyl, methyl, ethyl, n-propyl, isopropyl and t-butyl.
  • alkoxy refers to an -O-alkyl group wherein alkyl is as defined above.
  • alkoxy as used in this patent include, but are not limited to, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy and tert-butoxy.
  • Alkoxy also includes substituted alkoxy groups. The alkoxy group may be optionally substituted by one or more halogen atoms.
  • the continuous process refers to the connection between the production steps of the production system in the production process, and the continuous operation is ensured as a whole, but the waiting is allowed in each step.
  • continuous flow production process continuous-flow process
  • the raw materials are continuously produced continuously, and the materials in the process (that is, the reaction mixture containing raw materials, intermediates, products, solvents, etc.) are continuously flowing without interruption, and there is no waiting, that is, the products are continuously produced. Come out, it is a kind of "pipeline" type of chemical production process.
  • the state parameters such as composition and temperature of the material at any position in the reactor do not change with time, which is a steady state process, and thus the production process and product quality are stable.
  • the process can be referred to as a semi-continuous process; and only all steps are continuous
  • the material is continuously flowing throughout the process, that is, continuous addition of raw materials, continuous product, can be called continuous flow process (or full process continuous process).
  • the present invention innovatively provides an in-line full continuous flow production process for directly preparing an organic peroxide from an alcohol or an alkane, starting from a very safe material alcohol or alkane.
  • the reaction raw materials are successively successively subjected to two processes of oxidative condensation and post-treatment to prepare an organic peroxide, and the production process is carried out in a plug-and-production integrated continuous flow reactor in which the integrated continuous flow reactor is The feed inlet, the oxidant and the condensing agent are continuously added to the feed port, and the target product organic peroxide is continuously obtained at the outlet of the integrated continuous flow reactor, and the production process has no amplification effect, and the organic
  • the peroxide is selected from the group consisting of a peroxycarboxylic acid ester, a peroxycarbonate, a peroxyketal, the reaction substrate is an alcohol or an alkane, and the condensing agent is in the production of a peroxycarboxylic acid ester or a peroxycarbon
  • the invention thoroughly improves the prior art process for producing organic peroxide by integrating the reaction process and the advantages of the plug-and-production integrated continuous flow reactor, and can realize the online continuous continuous flow production of the organic peroxide, which will oxidize
  • the condensation process and the post-treatment process are effectively integrated into one process, which not only directly produces a highly dangerous organic peroxide from a safe starting material (alcohol or alkane), but also macroscopically non-hazardous alkyl peroxide (middle)
  • the process of accumulation, purification and residence of the product avoids the steps of purification, storage and transportation of the alkyl peroxide, realizes the ready-to-use use of the organic peroxide, and overcomes the amplification effect problem, and at the same time realizes On-line manufacturing, production and use of products at the same time, seamlessly coupled with downstream processes and equipment, synchronized production methods, so that the product is ready-to-use, useless Ready-to-use flexible manufacturing.
  • the production process of the invention has the following formula:
  • a 1 is an alcohol or an alkane
  • a 2 is selected from the group consisting of an acid chloride, a chloroformate, an alcohol, a ketone
  • the oxidizing agent is selected from hydrogen peroxide and oxygen
  • C is selected from the group consisting of a peroxycarboxylic acid ester, a peroxycarbonate, and a peroxyketal.
  • R is selected from saturated or unsaturated C 1 -C 12 alkyl, unsubstituted or substituted aryl, unsubstituted or substituted heterocyclic aryl, unsubstituted or substituted saturated heterocycloalkyl, unsubstituted or substituted Partially saturated heterocycloalkyl, unsubstituted or substituted cycloalkyl;
  • R 1 is selected from a saturated or unsaturated C 1 -C 20 alkyl group, an unsubstituted or substituted aryl group, an unsubstituted or substituted heterocyclic aryl group;
  • R 2 is selected from a saturated or unsaturated C 1 -C 20 alkyl group, an unsubstituted or substituted aryl group, an unsubstituted or substituted heterocyclic aryl group, an unsubstituted or substituted saturated heterocycloalkyl group, an unsubstituted or Substituting a partially saturated heterocycloalkyl group, an unsubstituted or substituted cycloalkyl group;
  • R 3 is selected from saturated or unsaturated C 1 -C 12 alkyl, unsubstituted or substituted aryl, unsubstituted or substituted heterocyclic aryl, unsubstituted or substituted saturated heterocycloalkyl, unsubstituted or Substituting a partially saturated heterocycloalkyl group, an unsubstituted or substituted cycloalkyl group;
  • R 4 or R 4 ' is selected from a saturated or unsaturated C 1 -C 12 alkyl group, an unsubstituted or substituted aryl group, an unsubstituted or substituted heterocyclic aryl group, an unsubstituted or substituted saturated heterocycloalkyl group. , unsubstituted or substituted partially saturated heterocycloalkyl, unsubstituted or substituted cycloalkyl;
  • R is selected from a saturated or unsaturated C3-C8 alkyl group, an unsubstituted or substituted aryl group, an unsubstituted or substituted heterocyclic aryl group, an unsubstituted or substituted saturated heterocyclic ring, an unsubstituted or substituted partially saturated hetero Ring, unsubstituted or substituted cycloalkyl;
  • R 1 is selected from a saturated or unsaturated C 1 -C 18 alkyl group, an unsubstituted or substituted aryl group, an unsubstituted or substituted heterocyclic aryl group;
  • R 2 is selected from a saturated or unsaturated C 1 -C 18 alkyl group, an unsubstituted or substituted aryl group, an unsubstituted or substituted heterocyclic aryl group, an unsubstituted or substituted saturated heterocyclic ring, an unsubstituted or substituted partially saturated Heterocyclic, unsubstituted or substituted cycloalkyl;
  • R 3 is selected from a saturated or unsaturated C 3 -C 8 alkyl group, an unsubstituted or substituted aryl group, an unsubstituted or substituted heterocyclic aryl group, an unsubstituted or substituted saturated heterocyclic ring, an unsubstituted or substituted moiety. a saturated heterocyclic ring, an unsubstituted or substituted cycloalkyl group;
  • R 4 or R 4 ' is selected from a saturated or unsaturated C 3 -C 8 alkyl group, an unsubstituted or substituted aryl group, an unsubstituted or substituted heterocyclic aryl group, an unsubstituted or substituted saturated heterocyclic ring, Substituting or substituting a partially saturated heterocyclic ring, an unsubstituted or substituted cycloalkyl group;
  • R is selected from the group consisting of t-butyl, tert-amyl, cumyl, 1,4-diisopropylphenyl, 2,4,4-trimethyl-2-pentyl, 2,5-dimethylhexyl, 1,3-diisopropylphenyl;
  • R 1 is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, isopentyl, n-pentyl, isoheptyl, octyl, isooctyl, 2,2 - dimethylheptyl, decyl, undecyl, phenyl, 2-methylphenyl, 4-methylphenyl, 4-chlorophenyl, 2,4-dichlorophenyl, naphthyl;
  • R 2 is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, 2-ethylhexyl, isotridecyl, heptadecyl, cyclohexyl, 4-tert-butylcyclohexyl, Benzyl, phenoxyethyl;
  • R 3 is selected from the group consisting of t-butyl, tert-amyl, 2,5-dimethylhexyl, 1,4-diisopropylphenyl, 1,3-diisopropylphenyl;
  • R 4 or R 4 ' is selected from the group consisting of methyl and ethyl;
  • R 4 is selected from -(CH 2 ) 5 -, -CH 2 -C(CH 3 ) 2 -CH 2 -CH(CH 3 )-CH 2 -;
  • R(OH) n is selected from the group consisting of tert-butanol, tert-amyl alcohol, 2,4,4-trimethyl-2-pentanol, 2,5-dimethyl-2,5-dihydroxyhexane, dihydroxy-1 , 4-diisopropylbenzene, dihydroxy-1,3-diisopropylbenzene;
  • R(H) n is selected from the group consisting of cumene, 1,4-diisopropylbenzene, and 1,3-diisopropylbenzene;
  • R 1 COCl is selected from the group consisting of acetyl chloride, propionyl chloride, butyryl chloride, isobutyryl chloride, valeryl chloride, 2-methylbutyryl chloride, pivaloyl chloride, 2-methylpentanoyl chloride, 2-ethylbutyryl chloride, 2-ethyl Hexanoyl chloride, decanoyl chloride, 2,4,4-trimethylpentanoyl chloride, 3,5,5-trimethylhexanoyl chloride, neodecanoyl chloride, decanoyl chloride, lauroyl chloride, benzoyl chloride, 2-methylbyl Acid chloride, 4-methylbenzoyl chloride, 4-chlorobenzoyl chloride, 2,4-dichlorobenzoyl chloride, naphthoyl chloride;
  • R 2 OCOCl is selected from the group consisting of methyl chloroformate, ethyl chloroformate, n-propyl chloroformate, isopropyl chloroformate, n-butyl chloroformate, sec-butyl chloroformate, 2-ethylhexyl chloroformate, chloroformic acid.
  • R 3 (OH) n is selected from the group consisting of tert-butanol, tert-amyl alcohol, 2,4,4-trimethyl-2-pentanol, 2,5-dimethyl-2,5-dihydroxyhexane, dihydroxy- 1,4-diisopropylbenzene, dihydroxy-1,3-diisopropylbenzene;
  • R 4 R 4' (CO) is selected from methyl ethyl ketone; R 4 (CO) is selected from cyclohexanone, 3,3,5-trimethylcyclohexanone.
  • organic peroxide is selected from the group consisting of:
  • the process of accumulating, purifying and waiting for the alkyl peroxide (intermediate product) which is macroscopically non-hazardous in the production process of the invention realizes the reaction substrate with alcohol or alkane as the starting substrate, and continuously produces the organic peroxide.
  • Peroxycarboxylic acid esters, peroxycarbonates, peroxy ketals innovative online production of organic peroxides, ready to use, breaking through the limitations of existing processes.
  • the alkyl peroxide is of the formula R(OOH) n , wherein R is selected from a saturated or unsaturated C 1 -C 12 alkyl group, an unsubstituted or substituted aryl group, an unsubstituted or substituted heterocyclic aryl group.
  • R is selected from a saturated or unsaturated C 1 -C 12 alkyl group, an unsubstituted or substituted aryl group, an unsubstituted or substituted heterocyclic aryl group.
  • R is selected from a saturated or unsaturated C 3 -C 8 alkyl group, an unsubstituted or substituted aryl group, an unsubstituted or substituted heterocyclic aryl group, an unsubstituted or substituted saturated heterocyclic ring, an unsubstituted or Substituting partially saturated heterocyclic, unsubstituted or substituted cycloalkyl.
  • R is selected from the group consisting of t-butyl, tert-amyl, cumyl, 1,4-diisopropylphenyl, 2,4,4-trimethyl-2-pentyl, 2,5-dimethyl Base group.
  • alkyl peroxide is selected from the group consisting of:
  • the target product organic peroxide obtained by the process of the invention is a product conforming to the standard of commercial industrial products, and further, the chloride ion content of the target product organic peroxide is ⁇ 0.05wt%, and other organic peroxide impurities The content is ⁇ 0.1% by weight, and the other organic peroxide impurities are selected from any one or any of H 2 O 2 , alkane peroxide, and dialkyl hydrocarbon peroxide.
  • the production time of the process of the present invention is ⁇ 15 min, preferably the production time is ⁇ 10 min; more preferably, the production time is 3 to 13 min; more preferably, the production time is 4 to 11 min; More preferably, the production time is 5 to 10 minutes.
  • the production time refers to the time required from the reaction raw materials (reaction substrate, oxidizing agent and condensing agent) to enter the integrated continuous flow reactor to produce a target product which meets the commercially available standard, including the oxidative condensation process. Time and time of the post-processing process.
  • the yield of the organic peroxide is ⁇ 64%; preferably, the yield of the organic peroxide is ⁇ 75%; more preferably, the yield of the organic peroxide is ⁇ 81%.
  • the content of the organic peroxide is ⁇ 77%; preferably, the content of the organic peroxide is ⁇ 85%; and the content of the organic peroxide is ⁇ 97%.
  • the temperature of the oxidative condensation process is 0 to 200 ° C, preferably 0 to 180 ° C, more preferably 0 to 160 ° C, still more preferably 0 to 140 ° C, still more preferably 5 to 130 ° C.
  • the post-treatment temperature is 0 to 60 ° C, preferably 0 to 50 ° C, more preferably 0 to 40 ° C, still more preferably 0 to 30 ° C, still more preferably 5 to 30 ° C.
  • the base is selected from the group consisting of water-soluble metal hydroxides, water-soluble quaternary ammonium hydroxides, water-soluble tertiary amines, water-soluble metal carbonates or water-soluble metal phosphates, preferably alkali metal hydroxides, alkaline earth metals
  • the hydroxide or water-soluble metal carbonate is more preferably sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate or lithium hydroxide.
  • the alkali liquid has a mass concentration of 5% to 45%, preferably 15% to 35%, more preferably 20% to 30%.
  • the acid is selected from all known organic and inorganic acids, preferably sulfuric acid, phosphoric acid or trifluoroacetic acid.
  • the acid solution has a mass concentration of 50% to 90%, preferably 60% to 80%, more preferably 70% to 80%.
  • the oxidizing agent is selected from the group consisting of hydrogen peroxide and oxygen.
  • reaction substrate is selected from the group consisting of t-butanol, tert-amyl alcohol, cumene, 1,4-diisopropylbenzene, p-mentane, decane, tetrahydronaphthalene, 2,4,4-trimethyl Base-2-pentanol, 1,3-diisopropylbenzene, dihydroxy-1,4-diisopropylbenzene, dihydroxy-1,3-diisopropylbenzene.
  • the acyl compound in the condensing agent is selected from the group consisting of acetyl chloride, propionyl chloride, butyryl chloride, isobutyryl chloride, valeryl chloride, 2-methylbutyryl chloride, pivaloyl chloride, 2-methylpentanoyl chloride, 2-B Butyryl chloride, 2-ethylhexanoyl chloride, decanoyl chloride, 2,4,4-trimethylpentanoyl chloride, 3,5,5-trimethylhexanoyl chloride, neodecanoyl chloride, decanoyl chloride, lauroyl chloride, benzoyl Acid chloride, 2-methylbenzoyl chloride, 4-methylbenzoyl chloride, 4-chlorobenzoyl chloride, 2,4-dichlorobenzoyl chloride, naphthoyl chloride, methyl chloroformate, ethyl chloroformate, chlorine N-propyl format
  • the molar ratio of the acid to the reaction substrate is from 0.3:1 to 1.5:1, preferably from 0.4:1 to 1.2:1, more preferably from 0.5:1 to 1:1.
  • the molar ratio of the oxidizing agent to the reaction substrate is from 0.8:1 to 2.2:1, preferably from 0.9:1 to 2.1:1, more preferably from 1:1 to 2:1, still more preferably from 1.3:1 to 1.8:1.
  • the molar ratio of the base to the reaction substrate is from 0.7:1 to 2:1, preferably from 0.9:1 to 1.8:1, more preferably from 1:1 to 1.6:1, still more preferably from 1:1 to 1.4:1.
  • the molar ratio of the acyl compound to the reaction substrate is from 0.5:1 to 1.2:1, preferably from 0.6:1 to 1.1:1, more preferably from 0.7:1 to 1:1.
  • the molar ratio of the condensation raw material to the reaction substrate is from 0.5:1 to 1.2:1, preferably from 0.6:1 to 1.1:1, more preferably from 0.7:1 to 1:1.
  • reaction substrate has a flow rate of 0.2 to 10 L/h, preferably 0.5 to 8 L/h, more preferably 1 to 6 L/h.
  • the acid flow rate is 0.2 to 5 L/h, preferably 0.4 to 4 L/h, more preferably 0.5 to 3 L/h.
  • the lye flow rate is 0.2 to 12 L/h, preferably 0.3 to 9 L/h, more preferably 0.5 to 8 L/h.
  • the flow rate of the acyl compound or the condensation raw material is 0.2 to 8 L/h, preferably 0.3 to 6 L/h, more preferably 0.5 to 4 L/h.
  • the target product of the online full continuous flow production process is t-butyl peroxy neodecanoate
  • the reaction substrate is t-butanol
  • the acyl compound is neodecanoyl chloride
  • the oxidant is hydrogen peroxide, wherein , preferred:
  • the hydrogen peroxide has a mass concentration of 30% to 50%
  • the production time of the production process is ⁇ 10 min, preferably, the production time is 3-9 min; more preferably, the production time is 4-8 min; more preferably, the production time is 5-7 min. .
  • the yield of the tert-butyl peroxy neodecanoate is ⁇ 68%; preferably, the yield of t-butyl peroxy neodecanoate is ⁇ 81%.
  • the content of the tert-butyl peroxy neodecanoate is ⁇ 87%; preferably, the content of t-butyl peroxy neodecanoate is ⁇ 91%.
  • the target product has a chloride ion content of 0.03 to 0.05% by weight in tert-butyl peroxy neodecanoate, a content of other organic peroxide impurities of 0.05 to 0.08% by weight, and the other organic peroxide impurity is H 2 . O 2 and di-tert-butyl peroxide.
  • the temperature of the oxidative condensation process is from 0 to 160 ° C, preferably from 20 to 130 ° C, more preferably from 40 to 120 ° C, still more preferably from 60 to 100 ° C, still more preferably from 70 to 90 ° C.
  • the post-treatment temperature is 0 to 50 ° C, preferably 0 to 40 ° C, more preferably 5 to 30 ° C, still more preferably 5 to 20 ° C.
  • the t-butanol flow rate is from 1 to 8 L/h, preferably from 1.5 to 6 L/h, more preferably from 2 to 4 L/h.
  • the acid flow rate is 0.4 to 5 L/h, preferably 0.5 to 4 L/h, more preferably 1 to 3 L/h, still more preferably 1.5 to 2.5 L/h.
  • the lye flow rate is 0.4 to 9 L/h, preferably 0.8 to 7 L/h, more preferably 1 to 6 L/h, still more preferably 1.2 to 5 L/h, still more preferably 1.5 to 3 L/h.
  • the neodecanoyl chloride flow rate is 0.4 to 7 L/h, preferably 0.8 to 6 L/h, more preferably 1 to 5 L/h, still more preferably 1.5 to 4 L/h, still more preferably 2 to 3 L/h.
  • the molar ratio of the acid to tert-butanol is from 0.3:1 to 1.3:1, preferably from 0.4:1 to 1.2:1, more preferably from 0.5:1 to 1:1, still more preferably from 0.5:1 to 0.8:1.
  • the molar ratio of the hydrogen peroxide to the tert-butanol is from 0.8:1 to 1.5:1, preferably from 0.9:1 to 1.4:1, more preferably from 1:1 to 1.3:1, still more preferably from 1.05:1 to 1.2:1.
  • the molar ratio of the base to tert-butanol is from 0.9:1 to 1.6:1, preferably from 1:1 to 1.4:1, more preferably from 1.2:1 to 1.3:1.
  • the molar ratio of the neodecanoyl chloride to tert-butanol is from 0.5:1 to 1.1:1, preferably from 0.6:1 to 1:1, more preferably from 0.7:1 to 0.9:1.
  • the base is selected from the group consisting of water-soluble metal hydroxides, water-soluble quaternary ammonium hydroxides, water-soluble tertiary amines, water-soluble metal carbonates or water-soluble metal phosphates, preferably alkali metal hydroxides, alkaline earth metal hydroxides Or a water-soluble metal carbonate, more preferably sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate or lithium hydroxide.
  • the acid is selected from all known organic and inorganic acids, preferably sulfuric acid, phosphoric acid or trifluoroacetic acid.
  • the reaction substrate is 2,4,4-trimethyl Base-2-pentanol
  • the acyl compound is neodecanoyl chloride
  • the oxidizing agent is hydrogen peroxide
  • the hydrogen peroxide concentration is 30% to 50%
  • the production time of the production process is ⁇ 10 min, preferably, the production time is 3-9 min; more preferably, the production time is 4-8 min; more preferably, the production time is 5-7 min. .
  • the yield of the peroxynonanoic acid-1,1,3,3-tetramethylbutyl ester is ⁇ 65%; preferably, neodecanoic acid-1,1,3,3-tetramethylbutyl ester The yield is ⁇ 70%.
  • the content of the peroxy neodecanoic acid-1,1,3,3-tetramethylbutyl ester is ⁇ 80%; preferably, the peroxy neodecanoic acid-1,1,3,3-tetramethylbutyl ester The content is ⁇ 90%.
  • the target product has a chloride ion content of 0.03 to 0.05% by weight in neodecanoic acid-1,1,3,3-tetramethylbutyl ester, and the content of the other organic peroxide impurities is 0.05 to 0.1 wt. %, the other organic peroxide impurity is H 2 O 2 .
  • the temperature of the oxidative condensation process is from 0 to 160 ° C, preferably from 20 to 130 ° C, more preferably from 40 to 120 ° C, still more preferably from 60 to 100 ° C, still more preferably from 70 to 90 ° C.
  • the post-treatment temperature is 0 to 50 ° C, preferably 0 to 40 ° C, more preferably 5 to 30 ° C, still more preferably 5 to 20 ° C.
  • the flow rate of the 2,4,4-trimethyl-2-pentanol is from 1 to 8 L/h, preferably from 1.5 to 6 L/h, more preferably from 2 to 4 L/h.
  • the acid flow rate is 0.4 to 5 L/h, preferably 0.5 to 4 L/h, more preferably 1 to 3 L/h, still more preferably 1.5 to 2.5 L/h.
  • the lye flow rate is 0.4 to 11 L/h, preferably 0.8 to 7 L/h, more preferably 1 to 6 L/h, still more preferably 1.2 to 5 L/h, still more preferably 1.5 to 3 L/h.
  • the neodecanoyl chloride flow rate is 0.4 to 7 L/h, preferably 0.8 to 6 L/h, more preferably 1 to 5 L/h, still more preferably 1.5 to 4 L/h, still more preferably 2 to 3 L/h.
  • the molar ratio of the acid to 2,4,4-trimethyl-2-pentanol is from 0.3:1 to 1.3:1, preferably from 0.4:1 to 1.2:1, more preferably from 0.5:1 to 1:1, more It is preferably 0.5:1 to 0.8:1.
  • the molar ratio of the hydrogen peroxide to the 2,4,4-trimethyl-2-pentanol is from 0.8:1 to 1.5:1, preferably from 0.9:1 to 1.4:1, more preferably from 1:1 to 1.3:1, more Preferably 1.05:1 to 1.2:1.
  • the molar ratio of the base to 2,4,4-trimethyl-2-pentanol is from 0.9:1 to 1.6:1, preferably from 1:1 to 1.4:1, more preferably from 1.2:1 to 1.3:1.
  • the molar ratio of the neodecanoyl chloride to 2,4,4-trimethyl-2-pentanol is from 0.7:1 to 1.1:1, preferably from 0.8:1 to 1:1, more preferably from 0.8:1 to 0.95:1. .
  • the base is selected from the group consisting of water-soluble metal hydroxides, water-soluble quaternary ammonium hydroxides, water-soluble tertiary amines, water-soluble metal carbonates or water-soluble metal phosphates, preferably alkali metal hydroxides, alkaline earth metal hydroxides Or a water-soluble metal carbonate, more preferably sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate or lithium hydroxide.
  • the acid is selected from all known organic and inorganic acids, preferably sulfuric acid, phosphoric acid or trifluoroacetic acid.
  • the target product of the online full continuous flow production process is tert-butyl 2-ethylhexyl carbonate
  • the reaction substrate is t-butanol
  • the acyl compound is 2-ethylhexyl chloroformate.
  • An ester, the oxidizing agent being hydrogen peroxide, wherein:
  • the hydrogen peroxide has a mass concentration of 30% to 50%.
  • the production time of the production process is ⁇ 10 min, preferably, the production time is 3-9 min; more preferably, the production time is 4-8 min; more preferably, the production time is 5-7 min. .
  • the yield of the tert-butyl 2-ethylhexylcarbonate is ⁇ 70%; preferably, the yield of tert-butyl 2-ethylhexylcarbonate is ⁇ 81%.
  • the content of the tert-butyl 2-ethylhexyl carbonate is ⁇ 95%; preferably, the content of tert-butyl 2-ethylhexyl carbonate is ⁇ 97%.
  • the target product has a chloride ion content of 0.03 to 0.05 wt% in 2-ethylhexylcarbonate tert-butyl ester and a content of other organic peroxide impurities of 0.05 to 0.08 wt%, and the other organic peroxide impurities. It is H 2 O 2 and di-tert-butyl peroxide.
  • the temperature of the oxidative condensation process is from 0 to 160 ° C, preferably from 20 to 130 ° C, more preferably from 40 to 120 ° C, still more preferably from 60 to 100 ° C, still more preferably from 70 to 90 ° C.
  • the post-treatment temperature is 0 to 50 ° C, preferably 0 to 40 ° C, more preferably 5 to 30 ° C, still more preferably 5 to 20 ° C.
  • the t-butanol flow rate is from 1 to 8 L/h, preferably from 1.5 to 6 L/h, more preferably from 2 to 4 L/h.
  • the acid flow rate is 0.4 to 5 L/h, preferably 0.5 to 4 L/h, more preferably 1 to 3 L/h, still more preferably 1.5 to 2.5 L/h.
  • the lye flow rate is 0.4 to 9 L/h, preferably 0.8 to 7 L/h, more preferably 1 to 6 L/h, still more preferably 1.2 to 5 L/h, still more preferably 1.5 to 3 L/h.
  • the flow rate of the 2-ethylhexyl chloroformate is 0.4 to 7 L/h, preferably 0.8 to 6 L/h, more preferably 1 to 5 L/h, still more preferably 1.5 to 4 L/h, still more preferably 2 to 3 L/h.
  • the molar ratio of the acid to tert-butanol is from 0.3:1 to 1.3:1, preferably from 0.4:1 to 1.2:1, more preferably from 0.5:1 to 1:1, still more preferably from 0.5:1 to 0.8:1.
  • the molar ratio of the hydrogen peroxide to the tert-butanol is from 0.8:1 to 1.5:1, preferably from 0.9:1 to 1.4:1, more preferably from 1:1 to 1.3:1, still more preferably from 1.05:1 to 1.2:1.
  • the molar ratio of the base to tert-butanol is from 0.9:1 to 1.6:1, preferably from 1:1 to 1.4:1, more preferably from 1.2:1 to 1.3:1.
  • the molar ratio of 2-ethylhexyl chloroformate to tert-butanol is from 0.5:1 to 1.1:1, preferably from 0.6:1 to 1:1, more preferably from 0.7:1 to 0.9:1.
  • the base is selected from the group consisting of water-soluble metal hydroxides, water-soluble quaternary ammonium hydroxides, water-soluble tertiary amines, water-soluble metal carbonates or water-soluble metal phosphates, preferably alkali metal hydroxides, alkaline earth metal hydroxides Or a water-soluble metal carbonate, more preferably sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate or lithium hydroxide.
  • the acid is selected from all known organic and inorganic acids, preferably sulfuric acid, phosphoric acid or trifluoroacetic acid.
  • the target product of the online full continuous flow production process is peroxyphenyl neodecanoate
  • the reaction substrate is cumene
  • the acyl compound is neodecanoyl chloride
  • the oxidant is oxygen.
  • the production time of the production process is ⁇ 10 min, preferably, the production time is 3-9 min; more preferably, the production time is 4-8 min; more preferably, the production time is 5 ⁇ 7min.
  • the yield of the cumene peroxy neodecanoate is ⁇ 79%; preferably, the yield of cumene peroxy neodecanoate is ⁇ 81%.
  • the content of the cumene peroxy neodecanoate is ⁇ 89%; preferably, the content of cumene peroxy neodecanoate is ⁇ 94%.
  • the target product has a chloride ion content of 0.03 to 0.05% by weight in cumene neodecanoate, a content of other organic peroxide impurities of 0.05 to 0.1% by weight, and the other peroxide impurities are two different.
  • Propylbenzene hydrogen peroxide is a compound that has a chloride ion content of 0.03 to 0.05% by weight in cumene neodecanoate, a content of other organic peroxide impurities of 0.05 to 0.1% by weight, and the other peroxide impurities are two different.
  • Propylbenzene hydrogen peroxide Propylbenzene hydrogen peroxide.
  • the temperature of the oxidative condensation process is 0 to 180 ° C, preferably 0 to 150 ° C, preferably 20 to 130 ° C, more preferably 40 to 120 ° C, still more preferably 60 to 100 ° C, still more preferably 70 to 90 ° C.
  • the post-treatment temperature is 0 to 60 ° C, preferably 0 to 50 ° C, more preferably 0 to 40 ° C, still more preferably 0 to 30 ° C, still more preferably 5 to 30 ° C.
  • the cumene flow rate is 0.2 to 8 L/h, preferably 0.5 to 6 L/h, more preferably 1.5 to 4 L/h, still more preferably 2 to 3 L/h.
  • the lye flow rate is 0.4 to 9 L/h, preferably 0.8 to 7 L/h, more preferably 1 to 6 L/h, still more preferably 1.2 to 5 L/h, still more preferably 1.5 to 3 L/h.
  • the neodecanoyl chloride flow rate is 0.4 to 7 L/h, preferably 0.8 to 6 L/h, more preferably 1 to 5 L/h, still more preferably 1.5 to 4 L/h, still more preferably 2 to 3 L/h.
  • the molar ratio of oxygen to cumene is from 0.8:1 to 2.2:1, preferably from 1.3:1 to 2.1:1, more preferably from 1.5:1 to 2:1.
  • the molar ratio of the base to cumene is from 1:1 to 1.8:1, preferably from 1.2:1 to 1.6:1, more preferably from 1.3:1 to 1.5:1.
  • the molar ratio of the neodecanoyl chloride to cumene is from 0.5:1 to 1.1:1, preferably from 0.6:1 to 1:1, more preferably from 0.7:1 to 0.9:1.
  • the base is selected from the group consisting of water-soluble metal hydroxides, water-soluble quaternary ammonium hydroxides, water-soluble tertiary amines, water-soluble metal carbonates, water-soluble metal phosphates, preferably alkali metal hydroxides, alkaline earth metal hydroxides. Or a water-soluble metal carbonate, more preferably sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate or lithium hydroxide.
  • the acid is selected from all known organic and inorganic acids, preferably sulfuric acid, phosphoric acid or trifluoroacetic acid.
  • the target product of the online full continuous flow production process is t-butyl isopropyl acrylate
  • the reaction substrate is t-butanol
  • the acyl compound is isopropyl chloroformate
  • the oxidant is hydrogen peroxide
  • the hydrogen peroxide has a mass concentration of 30% to 50%.
  • the production time of the production process is ⁇ 10 min, preferably, the production time is 3-9 min; more preferably, the production time is 4-8 min; more preferably, the production time is 5-7 min. .
  • the yield of the tert-butyl isopropyl peroxycarbonate is ⁇ 70.5%; preferably, the yield of tert-butyl isopropylperoxycarbonate is ⁇ 80%.
  • the content of the tert-butyl peroxyperoxycarbonate is ⁇ 95%; preferably, the content of t-butyl isopropylperoxycarbonate is ⁇ 97%.
  • the target product has a chloride ion content of 0.03 to 0.05% by weight in tert-butyl peroxydicarbonate, a content of other organic peroxide impurities of 0.05 to 0.08% by weight, and the other organic peroxide impurity is H. 2 O 2 and di-tert-butyl peroxide.
  • the temperature of the oxidative condensation process is from 0 to 160 ° C, preferably from 20 to 130 ° C, more preferably from 40 to 120 ° C, still more preferably from 60 to 100 ° C, still more preferably from 70 to 90 ° C.
  • the post-treatment temperature is 0 to 50 ° C, preferably 0 to 40 ° C, more preferably 5 to 30 ° C, still more preferably 5 to 20 ° C.
  • the molar ratio of the acid to tert-butanol is from 0.3:1 to 1.3:1, preferably from 0.4:1 to 1.2:1, more preferably from 0.5:1 to 1:1, still more preferably from 0.5:1 to 0.8:1.
  • the molar ratio of the hydrogen peroxide to the tert-butanol is from 0.8:1 to 1.5:1, preferably from 0.9:1 to 1.4:1, more preferably from 1:1 to 1.3:1, still more preferably from 1.05:1 to 1.2:1.
  • the molar ratio of the base to tert-butanol is from 0.9:1 to 1.6:1, preferably from 1:1 to 1.4:1, more preferably from 1.2:1 to 1.3:1.
  • the molar ratio of isopropyl chloroformate to tert-butanol is from 0.5:1 to 1.1:1, preferably from 0.6:1 to 1:1, more preferably from 0.7:1 to 0.9:1.
  • the base is selected from the group consisting of water-soluble metal hydroxides, water-soluble quaternary ammonium hydroxides, water-soluble tertiary amines, water-soluble metal carbonates, water-soluble metal phosphates, preferably alkali metal hydroxides, alkaline earth metal hydroxides. Or a water-soluble metal carbonate, more preferably sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate or lithium hydroxide.
  • the acid is selected from all known organic and inorganic acids, preferably sulfuric acid, phosphoric acid or trifluoroacetic acid.
  • the target product of the online full continuous flow production process is t-amyl 2-ethylhexyl carbonate
  • the reaction substrate is tert-amyl alcohol
  • the acyl compound is 2-ethylhexyl chloroformate.
  • the oxidizing agent is hydrogen peroxide, wherein: preferred:
  • the hydrogen peroxide has a mass concentration of 30% to 50%.
  • the production time of the production process is ⁇ 10 min, preferably, the production time is 3-9 min; more preferably, the production time is 4-8 min; more preferably, the production time is 5-7 min. .
  • the target product has a chloride ion content of 0.03 to 0.05 wt% in 2-ethylhexylcarbonate t-amyl ester and a content of other organic peroxide impurities of 0.05 to 0.08 wt%, and the other organic peroxide impurities It is H 2 O 2 and di-tert-amyl peroxide.
  • the temperature of the oxidative condensation process is from 0 to 160 ° C, preferably from 20 to 130 ° C, more preferably from 40 to 120 ° C, still more preferably from 60 to 100 ° C, still more preferably from 70 to 90 ° C.
  • the post-treatment temperature is 0 to 50 ° C, preferably 0 to 40 ° C, more preferably 5 to 30 ° C, still more preferably 5 to 20 ° C.
  • the yield of the tert-amyl 2-ethylhexylcarbonate is ⁇ 70%; preferably, the yield of tert-amyl 2-ethylhexylcarbonate is ⁇ 81%.
  • the content of the tert-amyl 2-ethylhexyl carbonate is ⁇ 95%; preferably, the content of the tert-amyl 2-ethylhexyl carbonate is ⁇ 97%
  • the molar ratio of the acid to tert-amyl alcohol is from 0.3:1 to 1.3:1, preferably from 0.4:1 to 1.2:1, more preferably from 0.5:1 to 1:1, still more preferably from 0.5:1 to 0.8:1.
  • the molar ratio of the hydrogen peroxide to the tert-amyl alcohol is from 0.8:1 to 1.5:1, preferably from 0.9:1 to 1.4:1, more preferably from 1:1 to 1.3:1, still more preferably from 1.05:1 to 1.2:1.
  • the molar ratio of the base to tert-amyl alcohol is from 0.9:1 to 1.6:1, preferably from 1:1 to 1.4:1, more preferably from 1.2:1 to 1.3:1.
  • the molar ratio of 2-ethylhexyl chloroformate to tert-amyl alcohol is from 0.5:1 to 1.1:1, preferably from 0.6:1 to 1:1, more preferably from 0.7:1 to 0.9:1.
  • the base is selected from the group consisting of water-soluble metal hydroxides, water-soluble quaternary ammonium hydroxides, water-soluble tertiary amines, water-soluble metal carbonates, water-soluble metal phosphates, preferably alkali metal hydroxides, alkaline earth metal hydroxides. Or a water-soluble metal carbonate, more preferably sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate or lithium hydroxide.
  • the acid is selected from all known organic and inorganic acids, preferably sulfuric acid, phosphoric acid or trifluoroacetic acid.
  • mass concentration of the reaction substrate, oxidant and condensing agent used in actual production will have a deviation of mass concentration of ⁇ 3 percentage points; ⁇ 3 °C deviation; production time will have a deviation of ⁇ 3 s.
  • the production scale can be flexibly changed without re-adjusting the optimized process conditions and parameters, and the production process is flexible; no amplification effect makes the production process stable and reliable, and fluctuations in process conditions and parameters will not affect product quality.
  • the quality of the product is easy to control; this also greatly enhances the safety of the production process.
  • the continuous flow process of the invention has good stability and reliability, and thus the product quality is stable and reproducible; the process has no amplification effect, and the problem of the amplification effect of the industrial process of the organic peroxide continuous flow process is solved;
  • the production-type integrated continuous flow reactor has short production time, small volume and small floor space because it does not need to delay the pipeline, which greatly saves the plant land and improves the production efficiency.
  • the present invention has developed a specialized integrated reactor.
  • the reactor may be a modular structure, the structure and quantity of the design module, the modules included in each temperature zone, and the development of specific process conditions and parameters, including the division and temperature setting of each temperature zone, etc.
  • the synergy of various factors makes this continuous flow process possible. It is also possible to further combine the temperature and material concentration, the material ratio and the material flow rate to match the reaction progress, and obtain a better reaction effect.
  • the production process of the invention can complete the reaction of preparing organic peroxide quickly and continuously at high temperature, and the total reaction time can be shortened to 15 minutes or even shortened by the optimization of functional unit division and temperature setting and the synergy of functional units. In a few minutes, the efficiency of the process is greatly improved. It can be seen that the production process of the present invention breaks through the limitations of the prior art, and achieves high efficiency and high quality production of organic peroxides under the harsh and dangerous conditions that cannot be realized by the prior art, and avoids alkyl groups.
  • the steps of purification, storage and transportation of peroxides enable the production and use of organic peroxides, which not only ensures high-quality and efficient production of organic peroxides, but also seamlessly links with downstream processes and synchronizes with each other. Avoid the storage and transportation steps of the target product organic peroxide. Moreover, the production process does not have an amplification effect, is very suitable for industrial production, and can realize the ready-to-use use of organic peroxides, without the need of cold chain transportation and storage, greatly improving the safety of production and use, and reducing the cost. Is a major breakthrough in this field.
  • the plug-and-production integrated continuous flow reactor adopts a unitized structure including an oxidative condensation unit and a post-processing unit, wherein:
  • the oxidative condensation unit is used to react the reaction substrate, the oxidizing agent and the condensing agent to form a peroxycarboxylic acid ester, a peroxycarbonate and a peroxyketal
  • the post-treatment unit is used for purification and washing of the organic peroxide.
  • the organic peroxide is selected from the group consisting of peroxycarboxylic acid esters, peroxycarbonates, and peroxyketals.
  • the temperature of the oxidative condensation unit is 0 to 200 ° C, preferably 0 to 180 ° C, more preferably 0 to 160 ° C, still more preferably 0 to 140 ° C, still more preferably 5 to 130 ° C.
  • the temperature of the post-treatment unit is 0 to 60 ° C, preferably 0 to 50 ° C, more preferably 0 to 40 ° C, still more preferably 0 to 30 ° C, still more preferably 5 to 30 ° C.
  • the plug-and-play integrated continuous flow reactor employs a unitized structure, each of the units independently comprising more than one reactor A module or a set of reactor modules, wherein the reactor module group is composed of a plurality of reactor modules connected in series or in parallel, and the units are connected in series with each other.
  • the plug-and-play integrated continuous flow reactor employs a unitized structure, each of the units comprising at least one temperature zone, each The temperature zone independently comprises more than one reactor module or group of reactor modules, wherein the reactor module group consists of a plurality of reactor modules connected in series or in parallel, with each temperature zone being connected in series with each other.
  • the unit further includes a buffer between the units, and the buffer is a container having a certain volume, which is mainly used for buffering the pressure fluctuation of the system and balancing the flow difference, so that the system works more smoothly.
  • the number of the integrated continuous flow reactor feed ports is one or more, and the number of the integrated continuous flow reactor discharge ports is one or more.
  • the reactor module is optionally any reactor capable of realizing a continuous flow process, the reactor being selected from the group consisting of a microreactor, a Tandem loop reactor, and a tube. Any one or any of a variety of reactors (Tubularreactor).
  • the microreactor also known as a microstructure reactor or a microchannel reactor, is a device in which a chemical reaction occurs in a limited area with a general lateral dimension of 1 mm or less. The form is a miniature size channel.
  • a tandem coil reactor that is, a reactor in which a coil reactor is connected in series by a pipe, wherein the coil reactor is in the form of a tubular reactor.
  • the tubular reactor is a continuous operation reactor with a tubular shape and a large aspect ratio which appeared in the middle of the last century.
  • Such a reactor can be very long; it can be a single tube or a plurality of tubes in parallel; it can be an empty tube or a filling tube.
  • the reactor may be one or more.
  • the reactor channel is made of single crystal silicon, special glass, ceramic, stainless steel or metal alloy coated with a corrosion resistant coating, and polytetrafluoroethylene.
  • reactor modules, the reactor module groups, the reactor modules and the reactor module groups are respectively connected in series or in parallel.
  • continuous flow production process is carried out in a plug-and-play integrated continuous flow reactor comprising six temperature zones.
  • the oxidative condensation reaction unit of the continuous flow production process comprises four temperature zones, namely a temperature zone 1, a temperature zone 2, a temperature zone 3 and a temperature zone 4, and the post-processing unit comprises two temperature zones, respectively Temperature zone 5 and temperature zone 6.
  • the integrated reactor is actually 5 temperature zones, and the temperature zone 1 (temperature zone 1) + Temperature zone 2), temperature zone 3, temperature zone 4, temperature zone 5 and temperature zone 6, others and so on.
  • the continuous flow production process includes the following steps:
  • reaction substrate is an alcohol or an alkane
  • condensing agent is an alkali liquid and an acyl compound in the production of a peroxycarboxylic acid ester or a peroxycarbonate, and an acid liquid and a condensation raw material in the production of a peroxy ketal.
  • the condensation feedstock is an alcohol or a ketone.
  • reaction liquid flowing out of the temperature zone 4 enters the aftertreatment unit, and is post-treated through the temperature zone 5 and the temperature zone 6 to obtain the target product organic peroxide, and the organic peroxide is selected from the group consisting of peroxycarboxylic acid esters. , peroxycarbonate, peroxy ketal.
  • the target product organic peroxide is a product conforming to the standard of commercial industrial products. Further, the chloride ion content of the target product organic peroxide is ⁇ 0.05wt%, and the content of other organic peroxide impurities is ⁇ 0.1. Wt%, the other organic peroxide impurities are selected from any one or any of a plurality of H 2 O 2 , an alkane peroxide, a dialkyl peroxide.
  • the temperature of the temperature zone 1 is 0 to 100 ° C, preferably 0 to 80 ° C, more preferably 0 to 60 ° C, still more preferably 0 to 40 ° C, still more preferably 5 to 30 ° C, still more preferably 5 to 20 ° C.
  • the temperature of the temperature zone 2 is 10 to 200 ° C, preferably 20 to 180 ° C, more preferably 30 to 160 ° C, still more preferably 40 to 130 ° C, still more preferably 50 to 120 ° C, still more preferably 60 to 110 ° C, More preferably, it is 70 to 100 ° C, and more preferably 80 to 90 ° C.
  • the temperature of the temperature zone 3 is 0 to 60 ° C, preferably 0 to 50 ° C, preferably 0 to 40 ° C, more preferably 5 to 30 ° C, still more preferably 5 to 20 ° C.
  • the temperature of the temperature zone 4 is 5 to 100 ° C, preferably 20 to 90 ° C, more preferably 30 to 80 ° C, still more preferably 40 to 70 ° C, still more preferably 50 to 60 ° C.
  • the temperature of the temperature zone 5 is 0 to 60 ° C, preferably 0 to 50 ° C, preferably 0 to 40 ° C, more preferably 5 to 30 ° C, still more preferably 5 to 20 ° C.
  • the temperature of the temperature zone 6 is 0 to 60 ° C, preferably 0 to 50 ° C, preferably 0 to 40 ° C, more preferably 5 to 30 ° C, still more preferably 5 to 20 ° C.
  • the temperature in the temperature zone will have a deviation of ⁇ 3 °C.
  • reaction substrate of the step (a) is preferably selected from the group consisting of tert-butanol, tert-amyl alcohol, cumene, 1,4-diisopropylbenzene, p-mentane, decane, tetrahydronaphthalene, 2, 4, 4-trimethyl-2-pentanol, 1,3-diisopropylbenzene, dihydroxy-1,4-diisopropylbenzene, dihydroxy-1,3-diisopropylbenzene.
  • reaction substrate has a flow rate of 0.2 to 10 L/h, preferably 0.5 to 8 L/h, more preferably 1 to 6 L/h.
  • the acid of step (a) is selected from all known organic and inorganic acids, preferably sulfuric acid, acetic acid or hydrochloric acid.
  • the acid solution has a mass concentration of 50% to 90%, preferably 60% to 80%, more preferably 70% to 80%.
  • the acid flow rate is 0.2 to 5 L/h, preferably 0.4 to 4 L/h, more preferably 0.5 to 3 L/h.
  • the base of the step (a) is selected from the group consisting of water-soluble metal hydroxides, water-soluble quaternary ammonium hydroxides, water-soluble tertiary amines, water-soluble metal carbonates or water-soluble metal phosphates, preferably alkali metal hydroxides.
  • the material, the alkaline earth metal hydroxide or the water-soluble metal carbonate is more preferably sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate or lithium hydroxide.
  • the alkali liquid has a mass concentration of 5% to 45%, preferably 15% to 35%, more preferably 20% to 30%.
  • the lye flow rate is 0.2 to 10 L/h, preferably 0.3 to 9 L/h, more preferably 0.5 to 8 L/h.
  • the acyl compound in the condensing agent in the step (a) is selected from the group consisting of acetyl chloride, propionyl chloride, butyryl chloride, isobutyryl chloride, valeryl chloride, 2-methylbutyryl chloride, pivaloyl chloride, 2-methylpentanoyl chloride , 2-ethylbutyryl chloride, 2-ethylhexanoyl chloride, decanoyl chloride, 2,4,4-trimethylpentanoyl chloride, 3,5,5-trimethylhexanoyl chloride, neodecanoyl chloride, decanoyl chloride, laurel Acid chloride, benzoyl chloride, 2-methylbenzoyl chloride, 4-methylbenzoyl chloride, 4-chlorobenzoyl chloride, 2,4-dichlorobenzoyl chloride, naphthoyl chloride, methyl chloroformate, chloroformic acid Ethyl
  • the flow rate of the acyl compound or the condensation raw material is 0.2 to 8 L/h, preferably 0.3 to 6 L/h, more preferably 0.5 to 4 L/h.
  • the molar ratio of the acid to the reaction substrate is from 0.3:1 to 1.5:1, preferably from 0.4:1 to 1.2:1, more preferably from 0.5:1 to 1:1.
  • the molar ratio of the oxidizing agent to the reaction substrate is from 0.8:1 to 2.2:1, preferably from 0.9:1 to 2.1:1, more preferably from 1:1 to 2:1, still more preferably from 1.3:1 to 1.8:1.
  • the molar ratio of the base to the reaction substrate is from 0.7:1 to 2:1, preferably from 0.9:1 to 1.8:1, more preferably from 1:1 to 1.6:1, still more preferably from 1:1 to 1.4:1.
  • the molar ratio of the acyl compound to the reaction substrate is from 0.5:1 to 1.2:1, preferably from 0.6:1 to 1.1:1, more preferably from 0.7:1 to 1:1.
  • the molar ratio of the condensation raw material to the reaction substrate is from 0.5:1 to 1.2:1, preferably from 0.6:1 to 1.1:1, more preferably from 0.7:1 to 1:1.
  • the oxidizing agent is selected from the group consisting of hydrogen peroxide and oxygen.
  • the target product of the online full continuous flow production process is t-butyl peroxy neodecanoate
  • the reaction substrate is t-butanol
  • the acyl compound is neodecanoyl chloride
  • the oxidant is hydrogen peroxide
  • the temperature of the temperature zone 1 is preferably 5 to 70 ° C, more preferably 5 to 60 ° C, still more preferably 5 to 40 ° C, still more preferably 5 to 30 ° C, still more preferably 5 to 20 ° C.
  • the temperature of the temperature zone 2 is 30 to 160 ° C, more preferably 40 to 130 ° C, still more preferably 50 to 120 ° C, still more preferably 60 to 110 ° C, still more preferably 70 to 100 ° C, still more preferably 80 to 90 ° C.
  • the temperature of the temperature zone 3 is 0 to 40 ° C, more preferably 5 to 30 ° C, still more preferably 5 to 20 ° C.
  • the temperature of the temperature zone 4 is 20 to 90 ° C, more preferably 30 to 80 ° C, still more preferably 40 to 70 ° C, still more preferably 50 to 60 ° C.
  • the temperature of the temperature zone 5 is 0 to 50 ° C, preferably 0 to 40 ° C, more preferably 5 to 30 ° C, still more preferably 5 to 20 ° C.
  • the temperature of the temperature zone 6 is 0 to 50 ° C, preferably 0 to 40 ° C, more preferably 5 to 30 ° C, still more preferably 5 to 20 ° C.
  • the production time of the production process is ⁇ 10 min, preferably, the production time is 3-9 min; more preferably, the production time is 4-8 min; more preferably, the production time is 5-7 min. .
  • the yield of the tert-butyl peroxy neodecanoate is ⁇ 68%; preferably, the yield of t-butyl peroxy neodecanoate is ⁇ 81%.
  • the content of the tert-butyl peroxy neodecanoate is ⁇ 87%; preferably, the content of t-butyl peroxy neodecanoate is ⁇ 91%.
  • the target product has a chloride ion content of 0.03 to 0.05% by weight in tert-butyl peroxy neodecanoate, a content of other organic peroxide impurities of 0.05 to 0.08% by weight, and the other organic peroxide impurity is H 2 . O 2 and di-tert-butyl peroxide.
  • the post-treatment temperature is 0 to 50 ° C, preferably 0 to 40 ° C, more preferably 5 to 30 ° C, still more preferably 5 to 20 ° C.
  • the t-butanol flow rate is from 1 to 8 L/h, preferably from 1.5 to 6 L/h, more preferably from 2 to 4 L/h.
  • the acid flow rate is 0.4 to 5 L/h, preferably 0.5 to 4 L/h, more preferably 1 to 3 L/h, still more preferably 1.5 to 2.5 L/h.
  • the lye flow rate is 0.4 to 9 L/h, preferably 0.8 to 7 L/h, more preferably 1 to 6 L/h, still more preferably 1.2 to 5 L/h, still more preferably 1.5 to 3 L/h.
  • the neodecanoyl chloride flow rate is 0.4 to 7 L/h, preferably 0.8 to 6 L/h, more preferably 1 to 5 L/h, still more preferably 1.5 to 4 L/h, still more preferably 2 to 3 L/h.
  • the molar ratio of the acid to tert-butanol is from 0.3:1 to 1.3:1, preferably from 0.4:1 to 1.2:1, more preferably from 0.5:1 to 1:1, still more preferably from 0.5:1 to 0.8:1.
  • the molar ratio of the hydrogen peroxide to the tert-butanol is from 0.8:1 to 1.5:1, preferably from 0.9:1 to 1.4:1, more preferably from 1:1 to 1.3:1, still more preferably from 1.05:1 to 1.2:1.
  • the molar ratio of the base to tert-butanol is from 0.9:1 to 1.6:1, preferably from 1:1 to 1.4:1, more preferably from 1.2:1 to 1.3:1.
  • the molar ratio of the neodecanoyl chloride to tert-butanol is from 0.5:1 to 1.1:1, preferably from 0.6:1 to 1:1, more preferably from 0.7:1 to 0.9:1.
  • the hydrogen peroxide concentration is 30% to 50%
  • the base is selected from the group consisting of water-soluble metal hydroxides, water-soluble quaternary ammonium hydroxides, water-soluble tertiary amines, water-soluble metal carbonates or water-soluble metal phosphates, preferably alkali metal hydroxides, alkaline earth metal hydroxides Or a water-soluble metal carbonate, more preferably sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate or lithium hydroxide.
  • the acid is selected from all known organic and inorganic acids, preferably sulfuric acid, phosphoric acid or trifluoroacetic acid.
  • the reaction substrate is 2,4,4-trimethyl Base-2-pentanol
  • the acyl compound is neodecanoyl chloride
  • the oxidizing agent is hydrogen peroxide
  • the temperature of the temperature zone 1 is preferably 5 to 70 ° C, more preferably 5 to 60 ° C, still more preferably 5 to 40 ° C, still more preferably 5 to 30 ° C, still more preferably 5 to 20 ° C.
  • the temperature of the temperature zone 2 is 30 to 160 ° C, more preferably 40 to 130 ° C, still more preferably 50 to 120 ° C, still more preferably 60 to 110 ° C, still more preferably 70 to 100 ° C, still more preferably 80 to 90 ° C.
  • the temperature of the temperature zone 3 is 0 to 40 ° C, more preferably 5 to 30 ° C, still more preferably 5 to 20 ° C.
  • the temperature of the temperature zone 4 is 20 to 90 ° C, more preferably 30 to 80 ° C, still more preferably 40 to 70 ° C, still more preferably 50 to 60 ° C.
  • the temperature of the temperature zone 5 is 0 to 50 ° C, preferably 0 to 40 ° C, more preferably 5 to 30 ° C, still more preferably 5 to 20 ° C.
  • the temperature of the temperature zone 6 is 0 to 50 ° C, preferably 0 to 40 ° C, more preferably 5 to 30 ° C, still more preferably 5 to 20 ° C.
  • the production time of the production process is ⁇ 10 min, preferably, the production time is 3-9 min; more preferably, the production time is 4-8 min; more preferably, the production time is 5-7 min. .
  • the yield of the peroxynonanoic acid-1,1,3,3-tetramethylbutyl ester is ⁇ 65%; preferably, neodecanoic acid-1,1,3,3-tetramethylbutyl ester The yield is ⁇ 70%.
  • the content of the peroxy neodecanoic acid-1,1,3,3-tetramethylbutyl ester is ⁇ 80%; preferably, the peroxy neodecanoic acid-1,1,3,3-tetramethylbutyl ester The content is ⁇ 90%.
  • the target product has a chloride ion content of 0.03 to 0.05% by weight in neodecanoic acid-1,1,3,3-tetramethylbutyl ester, and the content of the other organic peroxide impurities is 0.05 to 0.1 wt. %, the other organic peroxide impurity is H 2 O 2 .
  • the hydrogen peroxide concentration is 30% to 50%
  • the flow rate of the 2,4,4-trimethyl-2-pentanol is from 1 to 8 L/h, preferably from 1.5 to 6 L/h, more preferably from 2 to 4 L/h.
  • the acid flow rate is 0.4 to 5 L/h, preferably 0.5 to 4 L/h, more preferably 1 to 3 L/h, still more preferably 1.5 to 2.5 L/h.
  • the lye flow rate is 0.4 to 11 L/h, preferably 0.8 to 7 L/h, more preferably 1 to 6 L/h, still more preferably 1.2 to 5 L/h, still more preferably 1.5 to 3 L/h.
  • the neodecanoyl chloride flow rate is 0.4 to 7 L/h, preferably 0.8 to 6 L/h, more preferably 1 to 5 L/h, still more preferably 1.5 to 4 L/h, still more preferably 2 to 3 L/h.
  • the molar ratio of the acid to 2,4,4-trimethyl-2-pentanol is from 0.3:1 to 1.3:1, preferably from 0.4:1 to 1.2:1, more preferably from 0.5:1 to 1:1, more It is preferably 0.5:1 to 0.8:1.
  • the molar ratio of the hydrogen peroxide to the 2,4,4-trimethyl-2-pentanol is from 0.8:1 to 1.5:1, preferably from 0.9:1 to 1.4:1, more preferably from 1:1 to 1.3:1, more Preferably 1.05:1 to 1.2:1.
  • the molar ratio of the base to 2,4,4-trimethyl-2-pentanol is from 0.9:1 to 1.6:1, preferably from 1:1 to 1.4:1, more preferably from 1.2:1 to 1.3:1.
  • the molar ratio of the neodecanoyl chloride to 2,4,4-trimethyl-2-pentanol is from 0.7:1 to 1.1:1, preferably from 0.8:1 to 1:1, more preferably from 0.8:1 to 0.95:1. .
  • the base is selected from the group consisting of water-soluble metal hydroxides, water-soluble quaternary ammonium hydroxides, water-soluble tertiary amines, water-soluble metal carbonates or water-soluble metal phosphates, preferably alkali metal hydroxides, alkaline earth metal hydroxides Or a water-soluble metal carbonate, more preferably sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate or lithium hydroxide.
  • the acid is selected from all known organic and inorganic acids, preferably sulfuric acid, phosphoric acid or trifluoroacetic acid.
  • the target product of the online full continuous flow production process is tert-butyl 2-ethylhexyl carbonate, the reaction substrate is tert-butanol, and the acyl compound is 2-ethylhexyl chloroformate.
  • the oxidizing agent is hydrogen peroxide, wherein, preferred:
  • the temperature of the temperature zone 1 is preferably 5 to 70 ° C, more preferably 5 to 60 ° C, still more preferably 5 to 40 ° C, still more preferably 5 to 30 ° C, still more preferably 5 to 20 ° C.
  • the temperature of the temperature zone 2 is 30 to 160 ° C, more preferably 40 to 130 ° C, still more preferably 50 to 120 ° C, still more preferably 60 to 110 ° C, still more preferably 70 to 100 ° C, still more preferably 80 to 90 ° C.
  • the temperature of the temperature zone 3 is 0 to 40 ° C, more preferably 5 to 30 ° C, still more preferably 5 to 20 ° C.
  • the temperature of the temperature zone 4 is 10 to 90 ° C, more preferably 20 to 80 ° C, still more preferably 30 to 70 ° C, still more preferably 40 to 60 ° C.
  • the temperature of the temperature zone 5 is 0 to 50 ° C, preferably 0 to 40 ° C, more preferably 5 to 30 ° C, still more preferably 5 to 20 ° C.
  • the temperature of the temperature zone 6 is 0 to 50 ° C, preferably 0 to 40 ° C, more preferably 5 to 30 ° C, still more preferably 5 to 20 ° C.
  • the production time of the production process is ⁇ 10 min, preferably, the production time is 3-9 min; more preferably, the production time is 4-8 min; more preferably, the production time is 5-7 min. .
  • the hydrogen peroxide concentration is 30% to 50%
  • the yield of the tert-butyl 2-ethylhexylcarbonate is ⁇ 70%; preferably, the yield of tert-butyl 2-ethylhexylcarbonate is ⁇ 81%.
  • the content of the tert-butyl 2-ethylhexyl carbonate is ⁇ 95%; preferably, the content of tert-butyl 2-ethylhexyl carbonate is ⁇ 97%.
  • the target product has a chloride ion content of 0.03 to 0.05 wt% in 2-ethylhexylcarbonate tert-butyl ester and a content of other organic peroxide impurities of 0.05 to 0.08 wt%, and the other organic peroxide impurities. It is H 2 O 2 and di-tert-butyl peroxide.
  • the t-butanol flow rate is from 1 to 8 L/h, preferably from 1.5 to 6 L/h, more preferably from 2 to 4 L/h.
  • the acid flow rate is 0.4 to 5 L/h, preferably 0.5 to 4 L/h, more preferably 1 to 3 L/h, still more preferably 1.5 to 2.5 L/h.
  • the lye flow rate is 0.4 to 9 L/h, preferably 0.8 to 7 L/h, more preferably 1 to 6 L/h, still more preferably 1.2 to 5 L/h, still more preferably 1.5 to 3 L/h.
  • the flow rate of the 2-ethylhexyl chloroformate is 0.4 to 7 L/h, preferably 0.8 to 6 L/h, more preferably 1 to 5 L/h, still more preferably 1.5 to 4 L/h, still more preferably 2 to 3 L/h.
  • the molar ratio of the acid to tert-butanol is from 0.3:1 to 1.3:1, preferably from 0.4:1 to 1.2:1, more preferably from 0.5:1 to 1:1, still more preferably from 0.5:1 to 0.8:1.
  • the molar ratio of the hydrogen peroxide to the tert-butanol is from 0.8:1 to 1.5:1, preferably from 0.9:1 to 1.4:1, more preferably from 1:1 to 1.3:1, still more preferably from 1.05:1 to 1.2:1.
  • the molar ratio of the base to tert-butanol is from 0.9:1 to 1.6:1, preferably from 1:1 to 1.4:1, more preferably from 1.2:1 to 1.3:1.
  • the molar ratio of 2-ethylhexyl chloroformate to tert-butanol is from 0.5:1 to 1.1:1, preferably from 0.6:1 to 1:1, more preferably from 0.7:1 to 0.9:1.
  • the base is selected from the group consisting of water-soluble metal hydroxides, water-soluble quaternary ammonium hydroxides, water-soluble tertiary amines, water-soluble metal carbonates or water-soluble metal phosphates, preferably alkali metal hydroxides, alkaline earth metal hydroxides Or a water-soluble metal carbonate, more preferably sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate or lithium hydroxide.
  • the acid is selected from all known organic and inorganic acids, preferably sulfuric acid, phosphoric acid or trifluoroacetic acid.
  • the target product of the online full continuous flow production process is peroxyphenyl neodecanoate
  • the reaction substrate is cumene
  • the acyl compound is neodecanoyl chloride
  • the oxidant is oxygen.
  • the temperature of the temperature zone 1 is preferably 0 to 80 ° C, more preferably 10 to 70 ° C, still more preferably 20 to 60 ° C, still more preferably 30 to 40 ° C.
  • the temperature of the temperature zone 2 is preferably 20 to 180 ° C, more preferably 30 to 150 ° C, still more preferably 40 to 130 ° C, still more preferably 50 to 120 ° C, still more preferably 60 to 110 ° C, still more preferably 70 to 100 ° C, more preferably 80 to 90 ° C.
  • the temperature of the temperature zone 3 is preferably 0 to 50 ° C, preferably 0 to 40 ° C, more preferably 5 to 30 ° C, still more preferably 5 to 20 ° C.
  • the temperature of the temperature zone 4 is preferably from 10 to 100 ° C, more preferably from 20 to 80 ° C, still more preferably from 30 to 60 ° C, still more preferably from 40 to 50 ° C.
  • the temperature of the temperature zone 5 is preferably 0 to 50 ° C, preferably 0 to 40 ° C, more preferably 5 to 30 ° C, still more preferably 5 to 20 ° C.
  • the temperature of the temperature zone 6 is preferably 0 to 50 ° C, preferably 0 to 40 ° C, more preferably 5 to 30 ° C, still more preferably 5 to 20 ° C.
  • the production time of the production process is ⁇ 10 min, preferably, the production time is 3-9 min; more preferably, the production time is 4-8 min; more preferably, the production time is 5-7 min. .
  • the yield of the cumene peroxy neodecanoate is ⁇ 79%; preferably, the yield of cumene peroxy neodecanoate is ⁇ 81%.
  • the content of the cumene peroxy neodecanoate is ⁇ 89%; preferably, the content of cumene peroxy neodecanoate is ⁇ 94%.
  • the target product has a chloride ion content of 0.03 to 0.05% by weight in cumene neodecanoate, a content of other organic peroxide impurities of 0.05 to 0.1% by weight, and the other peroxide impurities are two different.
  • Propylbenzene hydrogen peroxide is a compound that has a chloride ion content of 0.03 to 0.05% by weight in cumene neodecanoate, a content of other organic peroxide impurities of 0.05 to 0.1% by weight, and the other peroxide impurities are two different.
  • Propylbenzene hydrogen peroxide Propylbenzene hydrogen peroxide.
  • the cumene flow rate is 0.2 to 8 L/h, preferably 0.5 to 6 L/h, more preferably 1.5 to 4 L/h, still more preferably 2 to 3 L/h.
  • the lye flow rate is 0.4 to 9 L/h, preferably 0.8 to 7 L/h, more preferably 1 to 6 L/h, still more preferably 1.2 to 5 L/h, still more preferably 1.5 to 3 L/h.
  • the neodecanoyl chloride flow rate is 0.4 to 7 L/h, preferably 0.8 to 6 L/h, more preferably 1 to 5 L/h, still more preferably 1.5 to 4 L/h, still more preferably 2 to 3 L/h.
  • the molar ratio of oxygen to cumene is from 0.8:1 to 2.2:1, preferably from 1.3:1 to 2.1:1, more preferably from 1.5:1 to 2:1.
  • the molar ratio of the base to cumene is from 1:1 to 1.8:1, preferably from 1.2:1 to 1.6:1, more preferably from 1.3:1 to 1.5:1.
  • the molar ratio of the neodecanoyl chloride to cumene is from 0.5:1 to 1.1:1, preferably from 0.6:1 to 1:1, more preferably from 0.7:1 to 0.9:1.
  • the base is selected from the group consisting of water-soluble metal hydroxides, water-soluble quaternary ammonium hydroxides, water-soluble tertiary amines, water-soluble metal carbonates or water-soluble metal phosphates, preferably alkali metal hydroxides, alkaline earth metal hydroxides Or a water-soluble metal carbonate, more preferably sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate or lithium hydroxide.
  • the acid is selected from all known organic and inorganic acids, preferably sulfuric acid, phosphoric acid or trifluoroacetic acid.
  • the target product of the online full continuous flow production process is t-butyl isopropyl acrylate
  • the reaction substrate is t-butanol
  • the acyl compound is isopropyl chloroformate
  • the oxidant is hydrogen peroxide
  • the temperature of the temperature zone 1 is preferably 5 to 70 ° C, more preferably 5 to 60 ° C, still more preferably 5 to 40 ° C, still more preferably 5 to 30 ° C, still more preferably 5 to 20 ° C.
  • the temperature of the temperature zone 2 is 30 to 160 ° C, more preferably 40 to 130 ° C, still more preferably 50 to 120 ° C, still more preferably 60 to 110 ° C, still more preferably 70 to 100 ° C, still more preferably 80 to 90 ° C.
  • the temperature of the temperature zone 3 is 0 to 40 ° C, more preferably 5 to 30 ° C, still more preferably 5 to 20 ° C.
  • the temperature of the temperature zone 4 is 20 to 90 ° C, more preferably 30 to 80 ° C, still more preferably 40 to 70 ° C, still more preferably 50 to 60 ° C.
  • the temperature of the temperature zone 5 is 0 to 50 ° C, preferably 0 to 40 ° C, more preferably 5 to 30 ° C, still more preferably 5 to 20 ° C.
  • the temperature of the temperature zone 6 is 0 to 50 ° C, preferably 0 to 40 ° C, more preferably 5 to 30 ° C, still more preferably 5 to 20 ° C.
  • the production time of the production process is ⁇ 10 min, preferably, the production time is 3-9 min; more preferably, the production time is 4-8 min; more preferably, the production time is 5-7 min. .
  • the yield of the tert-butyl isopropyl peroxycarbonate is ⁇ 70.5%; preferably, the yield of tert-butyl isopropylperoxycarbonate is ⁇ 80%.
  • the content of the tert-butyl peroxyperoxycarbonate is ⁇ 95%; preferably, the content of t-butyl isopropylperoxycarbonate is ⁇ 97%.
  • the target product has a chloride ion content of 0.03 to 0.05% by weight in tert-butyl peroxydicarbonate, a content of other organic peroxide impurities of 0.05 to 0.08% by weight, and the other organic peroxide impurity is H. 2 O 2 and di-tert-butyl peroxide.
  • the t-butanol flow rate is from 1 to 8 L/h, preferably from 1.5 to 6 L/h, more preferably from 2 to 4 L/h.
  • the acid flow rate is 0.4 to 5 L/h, preferably 0.5 to 4 L/h, more preferably 1 to 3 L/h, still more preferably 1.5 to 2.5 L/h.
  • the lye flow rate is 0.4 to 9 L/h, preferably 0.8 to 7 L/h, more preferably 1 to 6 L/h, still more preferably 1.2 to 5 L/h, still more preferably 1.5 to 3 L/h.
  • the flow rate of the isopropyl chloroformate is 0.4 to 7 L/h, preferably 0.8 to 6 L/h, more preferably 1 to 5 L/h, still more preferably 1.5 to 4 L/h, still more preferably 2 to 3 L/h.
  • the molar ratio of the acid to tert-butanol is from 0.3:1 to 1.3:1, preferably from 0.4:1 to 1.2:1, more preferably from 0.5:1 to 1:1, still more preferably from 0.5:1 to 0.8:1.
  • the molar ratio of the hydrogen peroxide to the tert-butanol is from 0.8:1 to 1.5:1, preferably from 0.9:1 to 1.4:1, more preferably from 1:1 to 1.3:1, still more preferably from 1.05:1 to 1.2:1.
  • the molar ratio of the base to tert-butanol is from 0.9:1 to 1.6:1, preferably from 1:1 to 1.4:1, more preferably from 1.2:1 to 1.3:1.
  • the molar ratio of isopropyl chloroformate to tert-butanol is from 0.5:1 to 1.1:1, preferably from 0.6:1 to 1:1, more preferably from 0.7:1 to 0.9:1.
  • the hydrogen peroxide concentration is 30% to 50%
  • the base is selected from the group consisting of water-soluble metal hydroxides, water-soluble quaternary ammonium hydroxides, water-soluble tertiary amines, water-soluble metal carbonates or water-soluble metal phosphates, preferably alkali metal hydroxides, alkaline earth metal hydroxides Or a water-soluble metal carbonate, more preferably sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate or lithium hydroxide.
  • the acid is selected from all known organic and inorganic acids, preferably sulfuric acid, phosphoric acid or trifluoroacetic acid.
  • the target product of the online full continuous flow production process is t-amyl 2-ethylhexyl carbonate
  • the reaction substrate is tert-amyl alcohol
  • the acyl compound is 2-ethylhexyl chloroformate.
  • the oxidizing agent is hydrogen peroxide, wherein: preferred:
  • the temperature of the temperature zone 1 is preferably 5 to 70 ° C, more preferably 5 to 60 ° C, still more preferably 5 to 40 ° C, still more preferably 5 to 30 ° C, still more preferably 5 to 20 ° C.
  • the temperature of the temperature zone 2 is 30 to 160 ° C, more preferably 40 to 130 ° C, still more preferably 50 to 120 ° C, still more preferably 60 to 110 ° C, still more preferably 70 to 100 ° C, still more preferably 80 to 90 ° C.
  • the temperature of the temperature zone 3 is 0 to 40 ° C, more preferably 5 to 30 ° C, still more preferably 5 to 20 ° C.
  • the temperature of the temperature zone 4 is 20 to 90 ° C, more preferably 30 to 80 ° C, still more preferably 40 to 70 ° C, still more preferably 50 to 60 ° C.
  • the temperature of the temperature zone 5 is 0 to 50 ° C, preferably 0 to 40 ° C, more preferably 5 to 30 ° C, still more preferably 5 to 20 ° C.
  • the temperature of the temperature zone 6 is 0 to 50 ° C, preferably 0 to 40 ° C, more preferably 5 to 30 ° C, still more preferably 5 to 20 ° C.
  • the production time of the production process is ⁇ 10 min, preferably, the production time is 3-9 min; more preferably, the production time is 4-8 min; more preferably, the production time is 5-7 min. .
  • the yield of the tert-amyl 2-ethylhexylcarbonate is ⁇ 70%; preferably, the yield of tert-amyl 2-ethylhexylcarbonate is ⁇ 81%.
  • the content of the tert-amyl 2-ethylhexylcarbonate is ⁇ 95%; preferably, the content of the tert-amyl 2-ethylhexylcarbonate is ⁇ 97%.
  • the target product has a chloride ion content of 0.03 to 0.05 wt% in 2-ethylhexylcarbonate t-amyl ester and a content of other organic peroxide impurities of 0.05 to 0.08 wt%, and the other organic peroxide impurities It is H 2 O 2 and di-tert-amyl peroxide.
  • the flow rate of the tert-amyl alcohol is 1 to 8 L/h, preferably 1.5 to 6 L/h, more preferably 2 to 4 L/h.
  • the acid flow rate is 0.4 to 5 L/h, preferably 0.5 to 4 L/h, more preferably 1 to 3 L/h, still more preferably 1.5 to 2.5 L/h.
  • the lye flow rate is 0.4 to 9 L/h, preferably 0.8 to 7 L/h, more preferably 1 to 6 L/h, still more preferably 1.2 to 5 L/h, still more preferably 1.5 to 3 L/h.
  • the flow rate of the 2-ethylhexyl chloroformate is 0.4 to 7 L/h, preferably 0.8 to 6 L/h, more preferably 1 to 5 L/h, still more preferably 1.5 to 4 L/h, still more preferably 2 to 3 L/h.
  • the molar ratio of the acid to tert-amyl alcohol is from 0.3:1 to 1.3:1, preferably from 0.4:1 to 1.2:1, more preferably from 0.5:1 to 1:1, still more preferably from 0.5:1 to 0.8:1.
  • the molar ratio of the hydrogen peroxide to the tert-amyl alcohol is from 0.8:1 to 1.5:1, preferably from 0.9:1 to 1.4:1, more preferably from 1:1 to 1.3:1, still more preferably from 1.05:1 to 1.2:1.
  • the molar ratio of the base to tert-amyl alcohol is from 0.9:1 to 1.6:1, preferably from 1:1 to 1.4:1, more preferably from 1.2:1 to 1.3:1.
  • the molar ratio of 2-ethylhexyl chloroformate to tert-amyl alcohol is from 0.5:1 to 1.1:1, preferably from 0.6:1 to 1:1, more preferably from 0.7:1 to 0.9:1.
  • the hydrogen peroxide concentration is 30% to 50%
  • the base is selected from the group consisting of water-soluble metal hydroxides, water-soluble quaternary ammonium hydroxides, water-soluble tertiary amines, water-soluble metal carbonates or water-soluble metal phosphates, preferably alkali metal hydroxides, alkaline earth metal hydroxides Or a water-soluble metal carbonate, more preferably sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate or lithium hydroxide.
  • the acid is selected from all known organic and inorganic acids, preferably sulfuric acid, phosphoric acid or trifluoroacetic acid.
  • reaction substrate, oxidant and condensing agent used in actual production have a deviation of ⁇ 2 percentage points of mass concentration; the temperature of the temperature zone will be ⁇ 3. Deviation of °C; production time will have a deviation of ⁇ 5s.
  • the present invention provides a scheme for the direct and continuous production of an organic peroxide from a reaction substrate, i.e., a plurality of reactants are continuously fed into the reactor, and the reaction product is continuously collected.
  • a reaction substrate i.e., a plurality of reactants are continuously fed into the reactor, and the reaction product is continuously collected.
  • the stability and reliability are good, so the product quality is stable and reproducible; the process has no amplification effect, and the problem of the amplification effect of the industrial process of the organic peroxide continuous flow process is also solved; and the integrated continuous flow reaction Because there is no need to delay the pipeline, the volume is small and the floor space is small, which greatly saves the land for the plant.
  • a second object of the present invention is to provide a plug-and-play integrated continuous flow reactor dedicated to any one form of online full continuous flow production process as described above, said integrated continuous flow reactor
  • a unitary structure comprising an oxidative condensation unit and a post-treatment unit, wherein: the oxidative condensation unit is used to react a reaction substrate, an oxidizing agent and a condensing agent to form a peroxycarboxylic acid ester, a peroxycarbonate and a peroxy ketal
  • the post-treatment unit is used for purification and washing of the organic peroxide, and the organic peroxide is selected from the group consisting of a peroxycarboxylic acid ester, a peroxycarbonate, and a peroxyketal.
  • a third object of the present invention is to provide a plug-and-play integrated continuous flow reactor dedicated to any form of on-line full continuous flow production as described above, said integrated continuous flow reactor
  • each of the units independently comprises more than one reactor module or group of reactor modules, wherein the reactor module group is composed of a plurality of reactor modules connected in series or in parallel, and the units are connected in series with each other.
  • a fourth object of the present invention is to provide a plug-and-play integrated continuous flow reactor dedicated to any one form of online full continuous flow production process as described above, said integrated continuous flow reactor Using a unitized structure, each of said units comprises at least one temperature zone, each temperature zone independently comprising more than one reactor module or group of reactor modules, wherein the reactor module group is connected in series or in parallel by a plurality of reactor modules Composition, each temperature zone is connected in series with each other.
  • the above three continuous flow reactors can further be:
  • the unit further includes a buffer between the units, and the buffer is a container having a certain volume, which is mainly used for buffering the pressure fluctuation of the system and balancing the flow difference, so that the system works more smoothly.
  • the number of the integrated continuous flow reactor feed ports is one or more, and the number of the integrated continuous flow reactor discharge ports is one or more.
  • the reactor module is optionally any reactor capable of realizing a continuous flow process, the reactor being selected from the group consisting of a microreactor, a Tandem loop reactor, and a tube. Any one or any of a variety of reactors (Tubularreactor).
  • the microreactor also known as a microstructure reactor or a microchannel reactor, is a device in which a chemical reaction occurs in a limited area with a general lateral dimension of 1 mm or less. The form is a miniature size channel.
  • a tandem coil reactor that is, a reactor in which a coil reactor is connected in series by a pipe, wherein the coil reactor is in the form of a tubular reactor.
  • the tubular reactor is a continuous operation reactor with a tubular shape and a large aspect ratio which appeared in the middle of the last century.
  • Such a reactor can be very long; it can be a single tube or a plurality of tubes in parallel; it can be an empty tube or a filling tube.
  • the reactor may be one or more.
  • the reactor channel is made of single crystal silicon, special glass, ceramic, stainless steel or metal alloy coated with a corrosion resistant coating, and polytetrafluoroethylene.
  • reactor modules, the reactor module groups, the reactor modules and the reactor module groups are respectively connected in series or in parallel.
  • the integrated continuous flow reactor comprises six temperature zones.
  • the oxidative condensation reaction unit of the integrated continuous flow reactor comprises four temperature zones, namely, a temperature zone 1, a temperature zone 2, a temperature zone 3 and a temperature zone 4, and the post-processing unit comprises two temperature zones. It is temperature zone 5 and temperature zone 6, respectively.
  • the temperature of the temperature zone 1 is 0 to 100 ° C, preferably 0 to 80 ° C, more preferably 0 to 60 ° C, still more preferably 0 to 40 ° C, still more preferably 5 to 30 ° C, still more preferably 5 to 20 ° C.
  • the temperature of the temperature zone 2 is 10 to 200 ° C, preferably 20 to 180 ° C, more preferably 30 to 160 ° C, still more preferably 40 to 130 ° C, still more preferably 50 to 120 ° C, still more preferably 60 to 110 ° C, More preferably, it is 70 to 100 ° C, and more preferably 80 to 90 ° C.
  • the temperature of the temperature zone 3 is 0 to 60 ° C, preferably 0 to 50 ° C, preferably 0 to 40 ° C, more preferably 5 to 30 ° C, still more preferably 5 to 20 ° C.
  • the temperature of the temperature zone 4 is 5 to 100 ° C, preferably 20 to 90 ° C, more preferably 30 to 80 ° C, still more preferably 40 to 70 ° C, still more preferably 50 to 60 ° C.
  • the temperature of the temperature zone 5 is 0 to 60 ° C, preferably 0 to 50 ° C, preferably 0 to 40 ° C, more preferably 5 to 30 ° C, still more preferably 5 to 20 ° C.
  • the temperature of the temperature zone 6 is 0 to 60 ° C, preferably 0 to 50 ° C, preferably 0 to 40 ° C, more preferably 5 to 30 ° C, still more preferably 5 to 20 ° C.
  • a fifth object of the present invention is to provide a chemical production process comprising the online continuous continuous flow production process for directly preparing an organic peroxide from an alcohol or an alkane according to the present invention, and one or more Subsequent production process.
  • the chemical production process may be a polymerization process, and the organic peroxide produced by the online full continuous flow production process of the present invention acts as an initiator of the polymerization process, and seamlessly interfaces the process of the present invention with the polymerization process. It can form a complete continuous production and use of organic peroxides, subvert the existing production-storage-transport-storage-use production mode, and realize a new production mode of production and use.
  • a sixth object of the present invention is to provide a chemical production facility comprising the plug-and-production integrated continuous flow reactor of the online full continuous flow production process of any one of the forms described in the present invention, And one or more subsequent production equipment.
  • the chemical production equipment may be a polymer production equipment
  • the plug-and-play integrated continuous flow reactor of the present invention can directly interface with the polymerization tank, and can form an organic peroxide production and use.
  • the full continuous production equipment subverting the existing production-storage-transport-storage-use production mode, to achieve a new production mode of production and use.
  • the present invention has the following beneficial effects:
  • the invention completely improves the prior art process for producing organic peroxide by integrating the reaction process and the advantages of the plug-and-production integrated continuous flow reactor, and realizes the safe starting material (alcohol or alkane for the first time).
  • Direct production of highly hazardous organic peroxides, macroscopically non-hazardous alkyl peroxides (intermediate products) accumulation, purification and residence waiting processes, avoiding the purification, storage and transport steps of alkyl peroxides It realizes the production and use of organic peroxides at the same time, and realizes the on-line manufacturing.
  • the production and use of the products are carried out at the same time, and the downstream processes and equipment are seamlessly connected and synchronized to the production mode.
  • the production process of the present invention is completely different from the prior art process, only through one-step reaction, and the reaction process and the post-treatment process are integrated into a complete production process, which is directly produced in a short time (within 15 minutes). Products that meet the standards of commercially available industrial products have achieved high quality and high efficiency production.
  • the production process of the invention has strong versatility, and the organic integration of the reaction process and the reactor organically breaks the existing defects that the production process of different organic peroxides cannot be universalized, by adjusting different process parameters and reactor parameters.
  • the production of different kinds of organic peroxides can be realized on the same plug-and-production integrated continuous flow reactor, which meets various needs of users and improves production efficiency.
  • the production process of the invention is safe and efficient, and the obtained organic peroxide product has high yield and content, greatly reduces production cost, improves safety of production of organic peroxides and production of downstream products, and realizes organic peroxidation. High efficiency, high quality and large-scale production.
  • the invention solves the problem of industrialized amplification of the organic peroxide continuous flow process, the production process of the invention has no amplification effect, greatly reduces the difficulty of industrial application, and does not need to go through complicated and complicated times when it is enlarged to industrialization. Step-by-step amplification and adjustment of process conditions and parameters can be scaled up to the required production scale, greatly saving manpower and material resources and project development time.
  • the safety of the production process of the present invention is greatly improved, the relatively small liquid holding capacity and excellent heat transfer characteristics of the continuous flow reactor, and the shorter reaction time (within 15 minutes) make the process more Safety.
  • the liquid holding capacity of the reactor refers to the total volume of the reaction materials stored in the reactor at any time when the operation reaches a steady state.
  • the reaction time of the invention is greatly shortened, the reaction time is shortened by 95%, and the reaction efficiency is greatly improved.
  • the product quality is stable and reproducible due to stable flow rate and stable production process.
  • the integrated continuous flow reactor is small in size and small in area, which greatly saves the land for the plant.
  • Figure 1 is a process diagram of the continuous production process of the present invention
  • Figure 2 is a schematic illustration of the integrated reactor of the present invention.
  • NSC904 2,4,4-trimethyl-2-pentanol
  • IPCF isopropyl chloroformate
  • ACL Acetyl chloride
  • the concentrations in the examples of the present invention are all mass concentrations, and the content of the target product is measured by effective oxygen content titration (iodine method), the chloride ion content is detected by an ion detector, and other organic peroxides are passed through high performance liquid chromatography (HPLC), the target product of the present invention has a chloride ion content of 0.03 to 0.05%, and other organic peroxide content of 0.05 to 0.1%, and the other organic peroxide impurities are selected from the group consisting of H 2 O 2 and alkane peroxide. Any one or any of a plurality of dialkyl peroxides. There is no need to delay the line in the reactor.
  • reaction substrate, oxidant and condensing agent used in actual production have a deviation of ⁇ 2 percentage points of mass concentration; the temperature of the temperature zone will be ⁇ 3. Deviation of °C; production time will have a deviation of ⁇ 5s.
  • the raw material 1 sulfuric acid solution
  • the raw material 2 reaction substrate
  • the raw material 3 aqueous hydrogen peroxide solution
  • the raw material 4 alkaline solution
  • the raw material 5 acyl compound
  • the feed rate 1 represents the feed rate of the feedstock 1
  • the feed rate 2 represents the feed rate of the feedstock 2
  • the feed rate 3 represents the feed rate of the feedstock 3
  • the feed rate 4 represents the feed rate of the feedstock 4
  • Feed rate 5 represents the feed rate of feedstock 5.
  • raw material 1 sulfur solution
  • raw material 2 reaction substrate
  • raw material 3 aqueous hydrogen peroxide solution
  • raw material 4 acid solution
  • raw material 5 condensation raw material
  • the feed rate 1 represents the feed rate of the feedstock 1
  • the feed rate 2 represents the feed rate of the feedstock 2
  • the feed rate 3 represents the feed rate of the feedstock 3
  • the feed rate 4 represents the feed rate of the feedstock 4
  • Feed rate 5 represents the feed rate of feedstock 5.
  • the raw material 1 (alkaline solution), the raw material 2 (reaction substrate), the raw material 3 (oxygen), the raw material 4 (alkaline solution), and the raw material 5 (acyl compound) are sequentially conveyed by a constant flow pump.
  • the continuous reactor enters the temperature zone 1 to the temperature zone 4 in turn, and the reaction is complete; the reaction liquid flowing out of the temperature zone 4 enters the temperature zone 5 and the temperature zone 6 for post-treatment to obtain a pure product.
  • the feed rate 1 represents the feed rate of the feedstock 1
  • the feed rate 2 represents the feed rate of the feedstock 2
  • the feed rate 3 represents the feed rate of the feedstock 3
  • the feed rate 4 represents the feed rate of the feedstock 4
  • Feed rate 5 represents the feed rate of feedstock 5.
  • Examples 84 and 85 employ the procedures of Examples 27-28, and Examples 78-83 and Examples 86-92 employ the procedures of Examples 1-12.
  • the continuous flow production of the organic peroxide of the present invention has a great advantage in time, from several hours or even ten hours of the existing process to less than 10 minutes, and in the overall The yield and content are somewhat improved compared to the prior art. Meanwhile, it can be seen from Examples 11 and 12, 25 and 26, 37 and 38, 49 and 50, 61 and 62, 73 and 74, 76 and 77, 91 and 92 that the yield does not change after scale-up, and the production time is also Not increasing again, indicating that the present invention does not have an amplification effect.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé de production d'écoulement entièrement continu pour la préparation directe d'un peroxyde organique à partir d'un alcool ou d'un alcane. Le procédé de production utilise un alcool ou un alcane sans danger, en tant que matière première de départ pour une réaction directe de façon à obtenir le peroxyde spécifié. Le procédé de production est mis en oeuvre dans un réacteur à flux continu intégré, la matière première de départ sécurisée, c'est-à-dire l'alcool ou l'alcane, est ajoutée en continu au niveau de l'entrée d'alimentation du réacteur à flux continu intégré, et la sortie de décharge du réacteur à flux continu intégré fournie en continu le peroxyde spécifié. Le procédé de production selon l'invention est sûr et efficace et peut réaliser une production in situ sans effets d'amplification. Par comparaison aux procédés de production classiques, le temps de production du processus de production selon l'invention est raccourci à 15 minutes. Le produit peut être utilisé tout en étant fabriqué avec zéro stock, sans aucun effet d'amplification. Les indices de produit sont stables et ont une bonne reproductibilité.
PCT/CN2018/100115 2017-08-12 2018-08-10 Procédé de production d'écoulement en ligne entièrement continu pour la préparation directe de peroxyde organique à partir d'alcool ou d'alcane WO2019034006A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP2020516679A JP6925079B2 (ja) 2017-08-12 2018-08-10 アルコール又はアルカンから有機過酸化物を直接製造するオンライン完全連続ストリーム生産プロセス
EP18846139.6A EP3666754B1 (fr) 2017-08-12 2018-08-10 Procédé de production d'écoulement entièrement continu pour la préparation directe de peroxyde organique à partir d'alcool ou d'alcane
US16/787,029 US10919849B2 (en) 2017-08-12 2020-02-11 Online continuous flow process for the preparation of organic peroxides direct from alcohols or alkanes

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
CN201710688671 2017-08-12
CN201710688671.5 2017-08-12
CN201810887206 2018-08-06
CN201810887206.9 2018-08-06
CN201810900615.8 2018-08-09
CN201810900615.8A CN109553560A (zh) 2017-08-12 2018-08-09 一种由醇或烷烃直接制备有机过氧化物的在线全连续流生产工艺

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US16/787,029 Continuation US10919849B2 (en) 2017-08-12 2020-02-11 Online continuous flow process for the preparation of organic peroxides direct from alcohols or alkanes

Publications (1)

Publication Number Publication Date
WO2019034006A1 true WO2019034006A1 (fr) 2019-02-21

Family

ID=65362714

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2018/100115 WO2019034006A1 (fr) 2017-08-12 2018-08-10 Procédé de production d'écoulement en ligne entièrement continu pour la préparation directe de peroxyde organique à partir d'alcool ou d'alcane

Country Status (1)

Country Link
WO (1) WO2019034006A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110128314A (zh) * 2019-06-12 2019-08-16 江西师范大学 一种连续生产2,2-双(过氧化叔丁基)丁烷的方法

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101479239A (zh) 2006-04-27 2009-07-08 阿克马法国公司 用于合成选定的有机过氧化物的方法
CN102336694A (zh) 2010-07-27 2012-02-01 中国石油化工集团公司 双(叔丁基过氧基)缩酮的合成方法
CN102558399A (zh) 2011-12-28 2012-07-11 淄博正华助剂股份有限公司 溶剂型质量分数75%过氧化新癸酸特丁酯的制备方法
CN102617432A (zh) 2012-03-15 2012-08-01 上虞绍风化工有限公司 过氧化-2-乙基己基碳酸叔丁酯的制备方法
CN104592080A (zh) * 2014-11-26 2015-05-06 淄博正华助剂股份有限公司 连续流制备过氧化新癸酸特丁酯(bnp)的方法
CN106588734A (zh) 2016-12-16 2017-04-26 中石化炼化工程（集团）股份有限公司 一种异丙苯氧化制备过氧化氢异丙苯的方法及装置
WO2017072190A1 (fr) * 2015-10-26 2017-05-04 Arkema France Synthèse de peroxydes organiques à l'aide d'un réacteur de mélange à écoulement oscillant

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101479239A (zh) 2006-04-27 2009-07-08 阿克马法国公司 用于合成选定的有机过氧化物的方法
CN102336694A (zh) 2010-07-27 2012-02-01 中国石油化工集团公司 双(叔丁基过氧基)缩酮的合成方法
CN102558399A (zh) 2011-12-28 2012-07-11 淄博正华助剂股份有限公司 溶剂型质量分数75%过氧化新癸酸特丁酯的制备方法
CN102617432A (zh) 2012-03-15 2012-08-01 上虞绍风化工有限公司 过氧化-2-乙基己基碳酸叔丁酯的制备方法
CN104592080A (zh) * 2014-11-26 2015-05-06 淄博正华助剂股份有限公司 连续流制备过氧化新癸酸特丁酯(bnp)的方法
WO2017072190A1 (fr) * 2015-10-26 2017-05-04 Arkema France Synthèse de peroxydes organiques à l'aide d'un réacteur de mélange à écoulement oscillant
CN106588734A (zh) 2016-12-16 2017-04-26 中石化炼化工程（集团）股份有限公司 一种异丙苯氧化制备过氧化氢异丙苯的方法及装置

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
"New crosslinker di tert-butyl Study on the synthesis of diisopropylperoxide", CHEMICAL WORLD, vol. 1, 2008, pages 38 - 41
CHEMICAL ABSTRACTS, Columbus, Ohio, US; abstract no. 15667-10-4
See also references of EP3666754A4 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110128314A (zh) * 2019-06-12 2019-08-16 江西师范大学 一种连续生产2,2-双(过氧化叔丁基)丁烷的方法

Similar Documents

Publication Publication Date Title
US10919849B2 (en) Online continuous flow process for the preparation of organic peroxides direct from alcohols or alkanes
US10947189B2 (en) Online continuous flow process for the synthesis of organic peroxides using hydrogen peroxide as raw material
Zhang et al. Continuous synthesis of methyl ethyl ketone peroxide in a microreaction system with concentrated hydrogen peroxide
CN106278861A (zh) 一种制备取代苯乙酸的方法
CN107698480B (zh) 一种无放大效应的过氧化新癸酸叔丁酯的连续流合成工艺
CN111056934B (zh) 一种微反应器内制备α-羟基酮光引发剂的方法
CN106588734B (zh) 一种异丙苯氧化制备过氧化氢异丙苯的方法及装置
CN107501059B (zh) 一种绿色环保的4-(4’-烷基环己基)环己酮的合成方法
CN117986162B (zh) 一种乙基磺酰氯的制备方法
WO2019034006A1 (fr) Procédé de production d'écoulement en ligne entièrement continu pour la préparation directe de peroxyde organique à partir d'alcool ou d'alcane
WO2019034004A1 (fr) Procédé de production en ligne à flux continu complet pour la préparation directe de peroxyde organique à l'aide de peroxyde d'hydrogène en tant que matière première
CN104262109B (zh) 一种间苯二酚的合成方法
CN106279097A (zh) 一种丙烯基‑1,3‑磺酸内酯的制备方法
Hermans et al. The reaction of benzoyl peroxide with cyclohexane and cyclohexene. Contribution to the mechanism of the catalyzing action of peroxides in the polymerization of vinyl derivatives
CN114315575A (zh) 一种光引发剂中间体的制备方法及其应用
CN109384699B (zh) 一种以双氧水为原料直接制备有机过氧化物的在线全连续流生产工艺
CN115057886B (zh) 一种c15膦盐的制备方法
CN110922297A (zh) 一种光催化氯化制备联苯二氯苄的方法
CN109678773A (zh) 一种过氧化-2-乙基己酸叔丁酯的制备方法
CN117050011B (zh) 一种以醋酸乙烯酯为原料合成2-甲基喹啉的方法
WO2023182349A1 (fr) Procédé de production d'ester d'acide salicylique
CN205368190U (zh) 一种n,n-二乙基羟胺生产系统
CN115448830A (zh) 一种光促进含有饱和碳氢键的化合物氧化的方法
CN114933527A (zh) 一种微通道内连续合成邻甲基苯甲酰氯的方法
CN104628567B (zh) 一种苯甲酰甲酸酯类引发剂的制备方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18846139

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2020516679

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 2018846139

Country of ref document: EP

Effective date: 20200311