CN107698480B - Continuous flow synthesis process of tert-butyl peroxyneodecanoate without amplification effect - Google Patents
Continuous flow synthesis process of tert-butyl peroxyneodecanoate without amplification effect Download PDFInfo
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Abstract
The invention provides a continuous flow synthesis process of tert-butyl peroxyneodecanoate without amplification effect, which takes tert-butyl peroxide, alkali liquor and neodecanoyl chloride as raw materials, and obtains the tert-butyl peroxyneodecanoate by continuously and sequentially carrying out alkalization reaction, esterification reaction and quenching steps, wherein the synthesis process is carried out in an integrated continuous flow reactor, reaction raw materials of tert-butyl peroxide, alkali liquor and neodecanoyl chloride are uninterruptedly added into a feed inlet of the integrated continuous flow reactor, tert-butyl peroxyneodecanoate is obtained at a discharge outlet of the integrated continuous flow reactor, no amplification effect is generated, and the total reaction time is less than or equal to 180 s. Compared with the traditional production process, the temperature is greatly improved, the total reaction time is greatly shortened, no amplification effect exists, the product index is stable, and the reproducibility is good.
Description
Technical Field
The invention relates to the field of chemistry, in particular to a continuous flow synthesis process of tert-butyl peroxyneodecanoate.
Background
Peroxyesters are important organic peroxides, such as tert-butyl peroxyneodecanoate, cumyl peroxyneodecanoate, and 1,1,3, 3-tetramethylbutyl peroxyneodecanoate. Peroxyesters are low-temperature initiators of free radical polymerization reactions, and are widely used in the production fields of polyethylene (LDPE), polyvinyl chloride (PVC), Polystyrene (PS), styrene copolymers (e.g., ABS), Polymethacrylate (PMMA), polyvinyl acetate (PVAc), and the like. At the same time, it is also a high temperature curing agent for unsaturated polyesters.
Since the first peroxyesters were reported to be prepared by Baeyer and Villiger in 1901, many peroxyester products have been made and are reported from laboratory to industrial scale. At present, the majority of peroxyesters are prepared in general by Acylation procedures (Acylation procedures). The basic principle is as follows: the peroxyalcohols are prepared by reacting a peroxyalcohol with an acylating agent (including acid chlorides, acid anhydrides, ketenes, sulfuryl chlorides, carbonyl chlorides, chloroform, carbamoyl chlorides of isocyanates (carbamychloride), etc.). The following reaction is a specific form of this principle:
peroxyesters are very reactive compounds that decompose very readily into highly reactive radicals and oxygen, which release a large amount of heat and even initiate an explosion. As the organic peroxide, it is characterized by a self-accelerated decomposition temperature (SADT), and at or above the SADT, the exothermic rate of decomposition reaction of the organic peroxide is unbalanced with the rate of heat dissipation from the environment, i.e., the heat of the system is continuously accumulated, and in this case, the organic peroxide can cause dangerous self-accelerated decomposition reaction by thermal decomposition and explosion or fire in adverse environments. Contact with incompatible species and increased mechanical stress can lead to decomposition at or below SADT.
Different organic peroxides may have a large difference in self-decomposition acceleration temperature and thermal stability. Meanwhile, due to the structural difference, the synthesis routes and the required raw materials of different organic peroxides are different, and the physical and chemical properties of the raw materials are also different. The numerous differences result in the absence of a so-called "universal" process which is applicable to all organic peroxides, and the synthesis processes of different organic peroxides cannot be transplanted and used. The synthesis of each specific organic peroxide requires the specific design and development of individually adapted processes, conditions and parameters according to its self-accelerating decomposition temperature and thermal stability as well as the physical and chemical properties of the raw materials used. For example, diisobutyryl peroxide has a self-decomposition acceleration temperature (SADT) of 0 ℃ and a 10 hour half-life corresponding to a temperature of 23 ℃; the self-decomposition accelerating temperature (SADT) of the cumyl peroxyneodecanoate is 10 ℃, and the temperature corresponding to the 10-hour half-life period is 38 ℃; the self-decomposition acceleration temperature (SADT) of t-butylperoxypivalate is 20 ℃ and the temperature corresponding to the 10-hour half-life is 57 ℃; the self-decomposition accelerating temperature (SADT) of the tert-butyl peroxy-2-hexylacetate is 35 ℃ and the temperature corresponding to the 10-hour half-life is 72 ℃; for t-butyl peroxide (TBHP), the self-decomposition acceleration temperature (SADT) is as high as 80 ℃, with a 10 hour half-life corresponding to a temperature of 98 ℃.
Tert-butyl peroxyneodecanoate, abbreviated as BNP, is mainly used as an excellent low-temperature initiator for high-pressure polyethylene (LDPE), is mainly used in a tubular process, can be used together with tert-butyl peroxypivalate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxybenzoate and the like as initiators to form a composite initiator system, and has better polymerization effect. Is a high temperature curing agent for unsaturated polyesters. Can be used as polymerization initiator of vinyl chloride, styrene or copolymer of styrene and polymerization initiator of methacrylate and vinyl acetate, and the self-accelerated decomposition temperature (SADT) of tert-butyl peroxyneodecanoate is 20 ℃ and the temperature corresponding to 10-hour half-life is 46 ℃.
The BNP is synthesized by tert-butyl peroxide, sodium hydroxide or potassium hydroxide and neodecanoyl chloride. At present, batch process is mostly adopted for production, the reaction temperature is usually below 20 ℃, the yield is more than 90 percent, and the storage temperature is generally lower than-10 ℃. The reaction equation is as follows:
batch process is to wait for a certain time (including the reaction time, temperature reduction time, temperature rise time, heat preservation time of each step, interval waiting time of each operation and the like) after raw materials are added into a reactor, discharge products once after the reaction meets certain requirements, namely, the production mode of the products is divided into batches, and each batch can only produce a limited fixed number of products (the number of the products depends on the volume of the reactor). The total reaction time of the batch process refers to the total time from raw materials to the prepared product, and comprises the charging time, the reaction time, the discharging time, the material transferring time, the cooling time, the heating time, the heat preservation time, the interval waiting time of each operation and the like of each step. In the intermittent process operation process, the state parameters of the composition, the temperature and the like of materials (including intermediate products and final products) in the reactor can change along with time, the process is an unstable process, the production process and the product quality have great uncertainty, and the quality of downstream products is directly unstable and difficult to control.
The most important features of a batch process are two-fold, one is the presence of "stops" or "interruptions" in the process, and the other is that the production of products is spaced apart, i.e., there are batches of product and only a fixed amount of product is available for a batch. That is, for each batch of production, a fixed number of starting materials are reacted in the order of reaction steps to ultimately yield a limited fixed number of products (products); then, a fixed amount of raw materials are put in, and the next batch of reaction is carried out according to the same steps to obtain a limited fixed amount of products.
There are two ways to implement a batch process: 1) respectively using a plurality of reactors (such as flasks, reaction kettles and the like), wherein each reaction is carried out in one reactor; 2) the method is realized by using a reactor (such as a flask, a reaction kettle and the like), wherein each step of reaction is sequentially completed, a plurality of raw materials are sequentially added according to the reaction progress in the reaction process, namely, after each step of reaction, the raw materials are stopped to wait for further addition of the raw materials for the subsequent reaction. Some documents also refer to mode 2) as continuous (continuous), which is also intermittent in nature because of "standing" in the process, waiting for the addition, or requiring adjustment to a suitable temperature for the next reaction (e.g., warming, cooling, or holding).
The prior art for synthesizing BNP mostly adopts an intermittent technique. There are mainly the following problems:
1. batch operation is inefficient and reaction times are long. Firstly, slowly dripping alkali liquor into tert-butyl hydroperoxide to synthesize tert-butyl sodium (potassium) peroxide, controlling the temperature in the process, and then slowly dripping neodecanoyl chloride to continue the reaction.
2. The reaction of tert-butyl peroxide and alkali liquor or the esterification of the tert-butyl peroxide and neodecanoyl chloride in the second step is exothermic, and a reactor is required to have good heat exchange performance to ensure that the reaction does not fly. Moreover, the product is decomposed at an excessively high temperature, resulting in a decrease in yield. The heat exchange efficiency of the reaction kettle is poor, so that the dropwise adding speed of the reaction needs to be controlled very slowly. Batch process safety is to be improved.
Although a small number of continuous flow processes have been developed, there are problems: the amplification effect inevitably exists, which brings many uncertainties for further industrial application; some continuous flow processes have incomplete reaction in a short time, and increase of the reaction time by delaying the pipeline is required to improve the conversion rate, which results in reduction of the production efficiency.
The Scaling up Effect (Scaling up Effect) refers to the research result obtained from the chemical process (i.e. small scale) experiment (e.g. laboratory scale) performed by small equipment, and the result obtained from the same operation condition is often very different from that obtained from the large scale production apparatus (e.g. industrial scale). The effect on these differences is called the amplification effect. The reason for this is mainly that the temperature, concentration, material residence time distribution in small-scale experimental facilities are different from those in large-scale facilities. That is, the results of the small scale experiments cannot be completely repeated on an industrial scale under the same operating conditions; to achieve the same or similar results on an industrial scale as in small scale experiments, process parameters and operating conditions need to be changed by optimal adjustment. For chemical processes, the amplification effect is a difficult and urgent problem to solve. If not solved, the production process and the product quality have great uncertainty, and firstly, the quality of downstream products is directly unstable and is difficult to control; secondly, the uncertainty can bring about the fluctuation of the technological parameters in the production process, so that the production process cannot be effectively controlled, the production safety cannot be ensured, and a plurality of potential safety hazards are buried in the production process.
Chinese patent CN 101479239a describes a process for the continuous preparation of organic peroxides using plate heat exchangers with high heat exchange capacity, by introducing different reactants at different locations (plates) of the plate heat exchanger, the selected peroxide being continuously prepared at a given temperature. The temperature is given as the temperature above which the organic peroxide becomes heat sensitive, and the final preferred reaction temperature range is 5 to 60 ℃. The synthesis reaction time of the process is in the range of 1 to 45 seconds on a laboratory scale and up to 2 to 3 minutes on an industrial scale. Compared with an intermittent process, the continuous preparation method has certain advantages in production efficiency and safety, but the amplification effect inevitably exists, the reaction time of the industrial scale is 2-180 times of the laboratory scale, the amplification effect which is largely uncertain (the reaction time is prolonged in a very wide range by 2-180 times), and the difficulty of industrialization is greatly increased. The amplification effect which is greatly uncertain brings disadvantages to the industrial application of the process, for example, when the process is amplified to the industrialization, only a method of multiple step-by-step amplification can be adopted, and in order to obtain a result which is consistent with the laboratory scale, the process conditions and parameters are readjusted and optimized in each amplification process, which greatly consumes manpower, material resources and time for project development; even if multiple progressive amplification is adopted, due to the fact that the change range of the amplification effect is too large, a good result of laboratory scale cannot be achieved after amplification can be finally achieved; meanwhile, the stability and reliability of the process can be influenced by the amplification effect which is greatly uncertain, so that the product quality is unstable and is difficult to control; in addition, this also presents a potential safety risk to the manufacturing process.
Chinese patent CN 104592080a describes a continuous flow BNP preparation method, the reaction process is performed in a microreactor, and then it must be further reacted fully through a delay line and cooled, and the product is collected. The yield of more than 98 percent is obtained under the condition of 15-35 ℃. Compared with the batch process, although the advantages of the micro-reactor in mass and heat transfer are utilized, the reaction temperature of the esterification reaction is improved to a certain extent, and the reaction time is shortened, the method still has many defects: firstly, the esterification reaction temperature is still low (15-35 ℃), so that the reaction is insufficient; secondly, in order to further fully react and cool, a delay line is needed to achieve the purpose of reaction. The delay line, as a type of tubular reactor, inevitably has an amplification effect in scaling up to an industrial scale. Namely, the scheme can not completely avoid the problem of amplification effect existing in the intermittent process, and the amplification difficulty of the process is increased, so that the problems of process reliability, product quality stability and production safety exist; thirdly, the use of a delay line due to insufficient reaction results in a long total reaction time, usually at least 5 minutes or more, even as long as 20 minutes, resulting in low production efficiency. In addition, the tubular reactor required for the delay line takes up a certain amount of space, resulting in wasted space.
It can be seen from the prior art that the existing synthesis processes of tert-butyl peroxyneodecanoate all have amplification effects of different degrees, and the reaction total time is too long and the yield is not high due to low reaction temperature, thereby increasing the difficulty of industrialization. Large-scale production cannot be realized, and the application of the method is limited. Therefore, a continuous flow synthesis process of tert-butyl peroxyneodecanoate, which has no amplification effect, is simple to operate, is efficient and is easy for large-scale production, needs to be found.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to solve the technical problem of providing a continuous flow synthesis process of tert-butyl peroxyneodecanoate, which has no amplification effect, is simple to operate, is efficient and is easy for large-scale production.
The continuous synthesis process refers to the connection of production steps of a production system in the production process, and the continuous operation is guaranteed as a whole, but the stay waiting is allowed in each step. Continuous flow synthesis process as one kind of continuous process is one fast and efficient full flow continuous process with short time consumption, high efficiency, easy operation and other features, and the continuous feeding of material to produce product continuously. When the process operation reaches a steady state, the state parameters of the material composition, the temperature and the like at any position in the reactor do not change along with the time, and the process is a steady state process, so the production process and the product quality are stable. In a process comprising a multi-step reaction, if some of the steps are continuous or simply connected, the process may be referred to as a (semi-) continuous process; a continuous flow process (or a full flow continuous process) is only possible if all steps are continuous and the material flows continuously throughout the process, i.e. the feed is continuously added and the product is continuously obtained.
In order to solve the technical problem, the invention provides a continuous flow synthesis process of tert-butyl peroxyneodecanoate, which takes tert-butyl peroxide, alkali liquor and neodecanoyl chloride as raw materials and continuously and sequentially carries out alkalization reaction, esterification reaction and quenching to obtain tert-butyl peroxyneodecanoate, wherein the reaction route is as follows:
the invention innovatively provides a continuous flow synthesis process of tert-butyl peroxyneodecanoate (BNP), which is characterized in that: the synthesis process is carried out in an integrated continuous flow reactor, reaction raw materials of tert-butyl peroxide, alkali liquor and neodecanoyl chloride are uninterruptedly added into a feed inlet of the integrated continuous flow reactor, and tert-butyl peroxyneodecanoate is uninterruptedly obtained at a discharge outlet of the integrated continuous flow reactor.
The invention provides an efficient BNP continuous flow synthesis scheme without amplification effect, namely, three reactants are continuously input into a reactor, and reaction products are continuously collected. The invention integrates the advantages of the reaction process and the reactor, utilizes the temperature zone division and the temperature setting optimization of the functional units and the synergistic effect of the functional units, can fully react without adding a delay pipeline, can shorten the total reaction time to within 3 minutes, greatly improves the efficiency of the process, and has no amplification effect in the synthesis process. Especially, the esterification reaction can be completed at a higher temperature (more than 50 ℃ and even more than 60 ℃), the reaction process is greatly accelerated, high yield of more than 98 percent (even more than 99.5 percent) can be obtained in a shorter time (usually within 180 seconds) without a delay pipeline, the defects of the prior art are overcome, and the high-efficiency, high-quality and large-scale production of BNP is realized.
The stability and the reliability of the continuous flow process are good, so the product quality is stable and the reproducibility is good; the process has no amplification effect, and also solves the problem of amplification effect in the industrialization of the BNP continuous flow process; meanwhile, the integrated continuous flow reactor does not need a delay pipeline, so that the integrated continuous flow reactor is small in size and small in occupied area, and the land for a factory building is greatly saved.
To meet the conditions of the continuous flow process of the present invention, a special integrated reactor was developed. The reactor can be of a modular structure, the organization mode and the number of modules and the modules contained in each temperature zone need to be designed, and targeted process conditions and parameters, including the division and the temperature setting of each temperature zone, need to be developed, and all the factors have synergistic action, so that the continuous flow process is realized. And the temperature, the material concentration, the material ratio and the material flow rate can be further combined to be matched with the reaction process, so that a better reaction effect is obtained. The material comprises raw materials and intermediate products in the reaction process, the material concentration comprises the concentration of the raw materials and the concentration of the intermediate products, the material ratio comprises the ratio of the raw materials and the concentration of the intermediate products, and the material flow rate comprises the flow rate of the raw materials and the flow rate of the intermediate products.
Further, the total reaction time of the synthesis process is less than or equal to 180s, and preferably, the total reaction time is 20-180 s; preferably, the total reaction time is 40-90 s; preferably, the total reaction time is 20-150 s; preferably, the total reaction time is 20-110 s; more preferably, the total reaction time is 20-90 s; more preferably, the total reaction time is 20-70 s; more preferably, the total reaction time is 20-60 s; more preferably, the total reaction time is 30-50 s; more preferably, the total reaction time is 30-40 s. The total reaction time is the time required from the entry of the feedstock into the reactor to the exit of the product from the reactor, and is also referred to as the residence time in a continuous flow process.
Further, the yield of the tert-butyl peroxyneodecanoate is more than or equal to 98 percent; preferably, the yield of the tert-butyl peroxyneodecanoate is more than or equal to 99 percent; more preferably, the yield of the tert-butyl peroxyneodecanoate is more than or equal to 99.5 percent
Further, the content of the tert-butyl peroxyneodecanoate is more than or equal to 89.4 percent; preferably, the content of the tert-butyl peroxyneodecanoate is more than or equal to 90 percent; the content of the tert-butyl peroxyneodecanoate is more than or equal to 92 percent.
Further, the temperature of the alkalization reaction is 5-35 ℃, preferably 5-30 ℃, more preferably 5-20 ℃, more preferably 5-18 ℃, more preferably 5-13 ℃, more preferably 6-11 ℃, more preferably 7-9 ℃.
Further, the temperature of the esterification reaction is 15-65 ℃, preferably 35-60 ℃, more preferably 35-55 ℃, more preferably 35-45 ℃, and more preferably 50-60 ℃.
Further, the temperature of the quenching step is 5-35 ℃, preferably 10-30 ℃.
Further, the alkali liquor is selected from an aqueous solution of potassium hydroxide or sodium hydroxide.
Further, the concentration of the alkali liquor is 5-45%, preferably 15-35%, and more preferably 20-30%.
Further, the concentration of the tert-butyl peroxide is 60 to 85 percent, preferably 65 to 80 percent, and more preferably 70 to 75 percent.
Further, the molar ratio of the alkali to the tert-butyl peroxide is 1.0-1.5: 1, preferably 1.10-1.25: 1, and more preferably 1.18: 1.
Further, the molar ratio of the neodecanoyl chloride to the tert-butyl peroxide is 0.6-1.1: 1, preferably 0.7-0.9: 1, and more preferably 0.75: 1.
Further, in order to match with the continuous flow synthesis process of tert-butyl peroxyneodecanoate, the integrated continuous flow reactor adopts a unit structure and comprises an alkalization unit, an esterification unit and a quenching unit. Wherein: the alkalization unit is used for reacting tert-butyl alcohol peroxide with alkali to generate corresponding tert-butyl peroxy salt and conveying the tert-butyl peroxy salt to the esterification unit; the esterification unit is used for reacting tert-butyl peroxysalt with neodecanoyl chloride to generate tert-butyl peroxyneodecanoate (BNP) and conveying the BNP to the quenching unit; the quenching unit is used for quenching the reaction and outputting reaction mother liquor containing tert-butyl peroxyneodecanoate.
Further, the temperature of the alkalization unit is 5-35 ℃, preferably 5-30 ℃, more preferably 5-20 ℃, more preferably 5-18 ℃, more preferably 5-13 ℃, more preferably 6-11 ℃, more preferably 7-9 ℃.
Further, the temperature of the esterification unit is 15-65 ℃, preferably 35-60 ℃, more preferably 35-55 ℃, more preferably 35-45 ℃, and more preferably 50-60 ℃.
Further, the temperature of the quenching unit is 5-35 ℃, and preferably 10-30 ℃.
Furthermore, in order to match with the continuous flow synthesis process of tert-butyl peroxyneodecanoate, the integrated continuous flow reactor adopts a unit structure, each unit independently comprises more than one reactor module or reactor module group, the reactor module group is formed by connecting a plurality of reactor modules in series or in parallel, and the units are connected in series.
Furthermore, in order to match with the continuous flow synthesis process of tert-butyl peroxyneodecanoate, the integrated continuous flow reactor adopts a unitized structure, each unit corresponds to at least one temperature zone, each temperature zone independently comprises more than one reactor module or reactor module group, the reactor module group is formed by connecting a plurality of reactor modules in series or in parallel, and the temperature zones are connected in series.
Furthermore, a Buffer (Buffer vessel) is further arranged between the units, and the Buffer is a container with a certain volume and is mainly used for buffering pressure fluctuation and balancing flow difference of the system, so that the system works more stably.
Further, the number of the feeding ports of the integrated continuous flow reactor is 1 or more, and the number of the discharging ports of the integrated continuous flow reactor is 1 or more.
Further, the reactor module is any reactor capable of realizing a continuous flow process, and the reactor is selected from any one or more of a Microreactor (micro reactor), a Tandem coil reactor (Tandem loop reactor) and a Tubular reactor (Tubular reactor). The microreactor, also known as a microstructured reactor or microchannel reactor, is a device in which chemical reactions take place in a confined region having a prevalent lateral dimension of 1mm or less, most typically in the form of a microscale channel. The coil reactors are connected in series, namely the coil reactors are connected in series by pipelines, wherein the coil reactors are in the form of coils made of tubular reactors. Tubular reactors are a continuous operating reactor that has a tubular shape and a large length-diameter ratio that has emerged in the middle of the last century. Such reactors can be very long; the single tube can be connected in parallel or the multiple tubes can be connected in parallel; the tube can be empty or filled.
Further, the number of reactors may be one or more.
Furthermore, the material of the reactor channel is monocrystalline silicon, special glass, ceramic, stainless steel or metal alloy coated with a corrosion-resistant coating, and polytetrafluoroethylene.
Furthermore, the reactor modules, the reactor module groups and the reactor modules and the reactor module groups are respectively connected in series or in parallel.
Further, the alkalization unit corresponds to an temperature zone 1, the esterification unit corresponds to an temperature zone 2, and the quenching unit corresponds to an temperature zone 3.
Further, the continuous flow synthesis process was carried out in an integrated continuous flow reactor comprising 3 temperature zones.
Further, the continuous flow synthesis process comprises the following steps:
(a) delivering tert-butyl peroxide and alkali liquor into a temperature region 1, and reacting through the temperature region 1 to generate an intermediate tert-butyl peroxygenated salt;
(b) the reaction liquid flowing out of the temperature zone 1 is mixed with neodecanoyl chloride, enters the temperature zone 2 and flows through the temperature zone 2 until the reaction is complete.
(c) The reaction liquid flowing out of the temperature zone 2 enters the temperature zone 3 to be cooled to quench the reaction, and reaction mother liquid containing tert-butyl peroxyneodecanoate is output.
Further, the temperature of the temperature zone 1 is 5-35 ℃, preferably 5-30 ℃, more preferably 5-20 ℃, more preferably 5-18 ℃, more preferably 5-13 ℃, more preferably 6-11 ℃, more preferably 7-9 ℃.
Further, the temperature of the temperature zone 2 is 15-65 ℃, preferably 35-60 ℃, more preferably 35-55 ℃, more preferably 35-45 ℃, and more preferably 50-60 ℃.
Further, the temperature of the temperature zone 3 is 5-35 ℃, preferably 10-30 ℃.
Further, the alkali liquor in step (a) is selected from an aqueous solution of potassium hydroxide or sodium hydroxide.
Further, the concentration of the alkali liquor is 5-45%, preferably 15-35%, and more preferably 20-30%.
Further, the concentration of the tert-butyl peroxide in the step (a) is 60 to 85 percent, preferably 65 to 80 percent, and more preferably 70 to 75 percent.
Further, the molar ratio of the base to the tert-butyl peroxide is 1.0 to 1.5:1, preferably 1.10 to 1.25:1, and more preferably 1.18: 1.
Further, the molar ratio of neodecanoyl chloride to t-butanol peroxide is 0.6 to 1.1:1, preferably 0.7 to 0.9:1, and more preferably 0.75: 1.
Further, the yield of the tert-butyl peroxyneodecanoate is more than or equal to 98 percent; preferably, the yield of the tert-butyl peroxyneodecanoate is more than or equal to 99 percent; more preferably, the yield of the tert-butyl peroxyneodecanoate is not less than 99.5%.
Further, the content of the tert-butyl peroxyneodecanoate is more than or equal to 89.4 percent; preferably, the content of the tert-butyl peroxyneodecanoate is more than or equal to 90 percent; the content of the tert-butyl peroxyneodecanoate is more than or equal to 92 percent.
It should be noted that, the concentration of t-butyl peroxide used in the actual synthesis (including laboratory, pilot plant, actual production process) has a mass concentration deviation of ± 3 percentage points; the alkali liquor concentration has deviation of mass concentration of +/-3 percentage points; the temperature of the temperature zone has deviation of +/-5 ℃; the total reaction time was biased by + -5 s.
A second object of the present invention is to provide an integrated continuous flow reactor dedicated to the continuous flow synthesis process of tert-butyl peroxyneodecanoate in any form as described above, said integrated continuous flow reactor adopting a unit structure comprising an alkalization unit, an esterification unit and a quenching unit, wherein: the alkalization unit is used for reacting tert-butyl alcohol peroxide with alkali to generate corresponding tert-butyl peroxy salt and conveying the tert-butyl peroxy salt to the esterification unit; the esterification unit is used for reacting tert-butyl peroxy salt with neodecanoyl chloride to generate tert-butyl peroxyneodecanoate, and conveying the tert-butyl peroxyneodecanoate to the quenching unit; the quenching unit is used for quenching the reaction and outputting reaction mother liquor containing tert-butyl peroxyneodecanoate.
The third object of the present invention is to provide an integrated continuous flow reactor dedicated to the continuous flow synthesis process of tert-butyl peroxyneodecanoate in any form as described above, said integrated continuous flow reactor adopts a unit structure, each of said units independently comprises more than one reactor module or reactor module group, 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.
The fourth object of the present invention is to provide an integrated continuous flow reactor dedicated to the continuous flow synthesis process of tert-butyl peroxyneodecanoate in any form as described above, wherein the integrated continuous flow reactor adopts a unit structure, each unit corresponds to at least one temperature zone, each temperature zone independently comprises more than one reactor module or reactor module group, wherein the reactor module group is composed of a plurality of reactor modules connected in series or in parallel, and the temperature zones are connected in series.
The above three continuous flow reactors may further be:
furthermore, a Buffer (Buffer vessel) is further arranged between the units, and the Buffer is a container with a certain volume and is mainly used for buffering pressure fluctuation and balancing flow difference of the system, so that the system works more stably.
Further, the number of the feeding ports of the integrated continuous flow reactor is 1 or more, and the number of the discharging ports of the integrated continuous flow reactor is 1 or more.
Further, the reactor module is any reactor capable of realizing a continuous flow process, and the reactor is selected from any one or more of a Microreactor (micro reactor), a Tandem coil reactor (Tandem loop reactor) and a Tubular reactor (Tubular reactor). The microreactor, also known as a microstructured reactor or microchannel reactor, is a device in which chemical reactions take place in a confined region having a prevalent lateral dimension of 1mm or less, most typically in the form of a microscale channel. The coil reactors are connected in series, namely the coil reactors are connected in series by pipelines, wherein the coil reactors are in the form of coils made of tubular reactors. Tubular reactors are a continuous operating reactor that has a tubular shape and a large length-diameter ratio that has emerged in the middle of the last century. Such reactors can be very long; the single tube can be connected in parallel or the multiple tubes can be connected in parallel; the tube can be empty or filled.
Further, the number of reactors may be one or more.
Furthermore, the reactor modules, the reactor module groups and the reactor modules and the reactor module groups are respectively connected in series or in parallel.
Furthermore, the material of the reactor channel is monocrystalline silicon, special glass, ceramic, stainless steel or metal alloy coated with a corrosion-resistant coating, and polytetrafluoroethylene.
Further, the integrated continuous flow reactor comprises 3 temperature zones.
Further, the alkalization unit corresponds to an temperature zone 1, the esterification unit corresponds to an temperature zone 2, and the quenching unit corresponds to an temperature zone 3.
Further, the temperature of the temperature zone 1 is 5-35 ℃, preferably 5-30 ℃, more preferably 5-20 ℃, more preferably 5-18 ℃, more preferably 5-13 ℃, more preferably 6-11 ℃, more preferably 7-9 ℃.
Further, the temperature of the temperature zone 2 is 15-65 ℃, preferably 35-60 ℃, more preferably 35-55 ℃, and more preferably 35-45 ℃.
Further, the temperature of the temperature zone 3 is 5-35 ℃, preferably 10-30 ℃.
Compared with the prior art, the invention has the following beneficial effects:
1. efficient continuous flow synthesis of BNP is realized on an integrated continuous flow reactor. That is, three reactants are continuously fed into the reactor and the reaction product is continuously collected. By means of the functional unit temperature zone division and the optimization of temperature setting, the full reaction can be realized without adding a delay pipeline, and the efficiency of the process is greatly improved. The total reaction time is at most 180 seconds.
2. The process safety is greatly improved, and the relatively small liquid holding capacity and excellent heat transfer characteristic of the continuous flow reactor and the short reaction time (within 180 seconds) ensure that the process is safer. Wherein the liquid holdup of the reactor is the total volume of the reaction mass present in the reactor at any one time when the operation reaches steady state.
3. When the self-accelerated decomposition temperature of BNP is 20 ℃ and the esterification reaction temperature is set at a relatively low temperature (15 to 35 ℃) in some continuous flow processes, a delay line is required to extend the reaction time in order to achieve a suitable yield, which obviously reduces the efficiency of the continuous reaction. In the process, the esterification reaction in the esterification unit is still very stable at 55 ℃ or even higher, and no obvious decomposition phenomenon is observed. Along with the increase of the temperature, the yield of the reaction is obviously improved, and the high yield of 98 percent can be obtained without a delay pipeline, so that the reaction time is greatly shortened, the reaction can be completed within 3 minutes usually, and the production is more efficient.
4. According to the self-accelerating decomposition temperature and thermal stability of BNP and the physical and chemical properties of used raw materials, three functional units, namely an alkalization unit, an esterification unit and a quenching unit, are designed in the integrated continuous flow reactor, wherein the alkalization unit is used for reacting tert-butyl alcohol peroxide with alkali to generate corresponding tert-butyl sodium (potassium) peroxide and conveying the tert-butyl sodium (potassium) peroxide to the esterification unit; the esterification unit is used for reacting sodium (potassium) tert-butyl peroxide with neodecanoyl chloride to generate tert-butyl peroxyneodecanoate (BNP) and conveying the BNP to the quenching unit; the quenching unit is used for quenching the reaction and outputting reaction mother liquor containing tert-butyl peroxyneodecanoate. Through the synergistic effect of the three functional units, the esterification reaction can be completed at a higher temperature (more than 50 ℃ and even more than 60 ℃), the reaction process is greatly accelerated, a high yield of more than 98 percent (even more than 99.5 percent) can be obtained in a shorter time (usually within 180 seconds) without a delay pipeline, the defects of the prior art are overcome, and the high-efficiency, high-quality and large-scale production of BNP is realized.
5. In the integrated continuous flow reactor, the product quality is stable and the reproducibility is good because the flow rate is stable and the production process is stable.
6. The technology still completes the reaction within 3 minutes on an industrial scale, the product content and the yield are basically the same as those of the technology on a laboratory scale, no amplification effect is found, and the problem of industrial amplification of the BNP continuous flow technology is solved.
7. The integrated continuous flow reactor has small volume and small occupied area due to no need of delay pipelines, thereby greatly saving the land for factory buildings.
Drawings
FIG. 1 is a process diagram of a continuous synthesis process according to example 1 of the present invention;
wherein, T1 is the temperature of temperature zone 1; t2 is the temperature of temperature zone 2; t3 is the temperature of temperature zone 3.
FIG. 2 is a schematic view of an integrated reactor according to the present invention.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
The concentrations in the embodiment of the invention are mass concentrations, the content of the product is detected by High Performance Liquid Chromatography (HPLC), and a delay pipeline is not needed in the reactor.
Example 1
As shown in fig. 1 and fig. 2, a raw material 1 (t-butyl peroxide) and a raw material 2 (potassium hydroxide aqueous solution) are fed into a temperature zone 1 by a constant flow pump, and react with each other through the temperature zone 1 to produce an intermediate t-butyl potassium peroxide. The raw material 3 (neodecanoyl chloride) is conveyed into the temperature zone 2 by using a constant flow pump and flows through the temperature zone 2, and the reaction is completed. The reaction liquid flowing out of the temperature zone 2 enters the temperature zone 3 to be cooled to quench the reaction, and reaction mother liquid is collected. And (4) layering the mother liquor, washing and the like to obtain tert-butyl peroxyneodecanoate. The reaction parameters and results are as follows:
table 1: raw material flow, temperature of temperature zone, reaction time, content and yield
Examples 2 to 19
Using the procedure of example 1, the reaction time, content and yield of tert-butyl peroxyneodecanoate prepared under different reaction parameters were examined, and the conditions and results of the parameters are shown in tables 2 and 3 below.
Table 2: feed concentrations and flow rates for examples 2-19
Table 3: examples 2-19 temperatures, reaction times, contents and yields in the various temperature zones
a the concentration of tert-butanol peroxide used in the actual synthesis deviates by a mass concentration of + -3 percentage points from the concentrations listed in the table.
b the actual concentration of the lye used in the synthesis deviates by a mass concentration of + -3 percentage points from the concentration listed in the table.
c the temperature of the temperature zone in the actual synthesis deviates by + -5 ℃ from the temperatures listed in the table.
d Total reaction time in the actual synthesis deviates by + -5 s from the total reaction time listed in the table.
From examples 8 and 9, examples 11 and 12, and examples 13 and 14, it can be seen that the scale-up of the reaction does not affect the product content and yield, i.e. the process does not have the scale-up effect; from example 16, it can be seen that even if the esterification reaction is carried out at a relatively low temperature of 15 ℃, a delay line is not required, the reaction can be completed in 3 minutes, and a product content of 90.3% and a product yield of 98.6% are obtained; at higher temperatures (above 50 c, even up to above 60 c), the reaction can be completed in a shorter time. This shows that the process is stable, reliable, efficient and suitable for industrial scale-up.
Claims (98)
1. A continuous flow synthesis process of tert-butyl peroxyneodecanoate without amplification effect is characterized in that: the synthesis process is carried out in an integrated continuous flow reactor, reaction raw materials of tert-butyl peroxide, alkali liquor and neodecanoyl chloride are continuously added into a feed inlet of the integrated continuous flow reactor, and tert-butyl peroxyneodecanoate is obtained at a discharge outlet of the integrated continuous flow reactor uninterruptedly, wherein the synthesis process has no amplification effect, and the total reaction time of the synthesis process is less than or equal to 180 s; the integrated continuous flow reactor adopts a unit structure and comprises an alkalization unit, an esterification unit and a quenching unit, wherein: the alkalization unit is used for reacting tert-butyl alcohol peroxide with alkali to generate corresponding tert-butyl peroxy salt and conveying the tert-butyl peroxy salt to the esterification unit; the esterification unit is used for reacting tert-butyl peroxy salt with neodecanoyl chloride to generate tert-butyl peroxyneodecanoate, and conveying the tert-butyl peroxyneodecanoate to the quenching unit; the quenching unit is used for quenching the reaction and outputting reaction mother liquor containing tert-butyl peroxyneodecanoate; wherein:
the temperature of the alkalization unit is 5-35 ℃, the temperature of the esterification unit is 15-65 ℃, and the temperature of the quenching unit is 5-35 ℃.
2. The continuous-flow synthesis process of claim 1, wherein: the total reaction time is 20-180 s.
3. The continuous-flow synthesis process of claim 2, wherein: the total reaction time is 40-90 s.
4. The continuous-flow synthesis process of claim 2, wherein: the total reaction time is 20-150 s.
5. The continuous-flow synthesis process of claim 2, wherein: the total reaction time is 20-110 s.
6. The continuous-flow synthesis process of claim 2, wherein: the total reaction time is 20-90 s.
7. The continuous-flow synthesis process of claim 2, wherein: the total reaction time is 20-70 s.
8. The continuous-flow synthesis process of claim 2, wherein: the total reaction time is 20-60 s.
9. The continuous-flow synthesis process of claim 2, wherein: the total reaction time is 30-50 s.
10. The continuous-flow synthesis process of claim 2, wherein: the total reaction time is 30-40 s.
11. The continuous-flow synthesis process of claim 1, wherein: the yield of the tert-butyl peroxyneodecanoate is more than or equal to 98 percent.
12. The continuous-flow synthesis process of claim 11, wherein: the yield of the tert-butyl peroxyneodecanoate is more than or equal to 99 percent.
13. The continuous-flow synthesis process of claim 11, wherein: the yield of the tert-butyl peroxyneodecanoate is more than or equal to 99.5 percent.
14. The continuous-flow synthesis process of claim 1, wherein: the content of the tert-butyl peroxyneodecanoate is more than or equal to 89.4 percent.
15. The continuous-flow synthesis process of claim 14, wherein: the content of the tert-butyl peroxyneodecanoate is more than or equal to 90 percent.
16. The continuous-flow synthesis process of claim 14, wherein: the content of the tert-butyl peroxyneodecanoate is more than or equal to 92 percent.
17. The continuous-flow synthesis process of claim 1, wherein: the temperature of the alkalization reaction is 5-35 ℃.
18. The continuous-flow synthesis process of claim 17, wherein: the temperature of the alkalization reaction is 5-30 ℃.
19. The continuous-flow synthesis process of claim 17, wherein: the temperature of the alkalization reaction is 5-20 ℃.
20. The continuous-flow synthesis process of claim 17, wherein: the temperature of the alkalization reaction is 5-18 ℃.
21. The continuous-flow synthesis process of claim 17, wherein: the temperature of the alkalization reaction is 5-13 ℃.
22. The continuous-flow synthesis process of claim 17, wherein: the temperature of the alkalization reaction is 6-11 ℃.
23. The continuous-flow synthesis process of claim 17, wherein: the temperature of the alkalization reaction is 7-9 ℃.
24. The continuous-flow synthesis process of claim 1, wherein: the temperature of the esterification reaction is 15-65 ℃.
25. The continuous-flow synthesis process of claim 24, wherein: the temperature of the esterification reaction is 35-60 ℃.
26. The continuous-flow synthesis process of claim 24, wherein: the temperature of the esterification reaction is 35-55 ℃.
27. The continuous-flow synthesis process of claim 24, wherein: the temperature of the esterification reaction is 35-45 ℃.
28. The continuous-flow synthesis process of claim 24, wherein: the temperature of the esterification reaction is 50-60 ℃.
29. The continuous-flow synthesis process of claim 1, wherein: the temperature of the quenching step is 5-35 ℃.
30. The continuous-flow synthesis process of claim 29, wherein: the temperature of the quenching step is 10-30 ℃.
31. The continuous-flow synthesis process of claim 1, wherein: the alkali liquor is selected from aqueous solution of potassium hydroxide or sodium hydroxide.
32. The continuous-flow synthesis process of claim 1, wherein: the concentration of the alkali liquor is 5-45%.
33. The continuous-flow synthesis process of claim 32, wherein: the concentration of the alkali liquor is 15-35%.
34. The continuous-flow synthesis process of claim 32, wherein: the concentration of the alkali liquor is 20-30%.
35. The continuous-flow synthesis process of claim 1, wherein: the concentration of the tert-butyl peroxide is 60-85%.
36. The continuous-flow synthesis process of claim 35, wherein: the concentration of the tert-butyl peroxide is 65-80%.
37. The continuous-flow synthesis process of claim 35, wherein: the concentration of the tert-butyl peroxide is 70-75%.
38. The continuous-flow synthesis process of claim 1, wherein: the molar ratio of the alkali to the tert-butyl peroxide is 1.0-1.5: 1.
39. The continuous-flow synthesis process of claim 38, wherein: the molar ratio of the alkali to the tert-butyl peroxide is 1.10-1.25: 1.
40. The continuous-flow synthesis process of claim 38, wherein: the molar ratio of the base to t-butanol peroxide was 1.18: 1.
41. The continuous-flow synthesis process of claim 1, wherein: the molar ratio of the neodecanoyl chloride to the tert-butyl peroxide is 0.6-1.1: 1.
42. The continuous-flow synthesis process of claim 41, wherein: the molar ratio of the neodecanoyl chloride to the tert-butyl peroxide is 0.7-0.9: 1.
43. The continuous-flow synthesis process of claim 41, wherein: the molar ratio of neodecanoyl chloride to t-butanol peroxide was 0.75: 1.
44. The continuous-flow synthesis process according to any one of claims 1 to 43, wherein: the temperature of the alkalization unit is 5-30 ℃.
45. The continuous-flow synthesis process according to any one of claims 1 to 43, wherein: the temperature of the alkalization unit is 5-20 ℃.
46. The continuous-flow synthesis process according to any one of claims 1 to 43, wherein: the temperature of the alkalization unit is 5-18 ℃.
47. The continuous-flow synthesis process according to any one of claims 1 to 43, wherein: the temperature of the alkalization unit is 5-13 ℃.
48. The continuous-flow synthesis process according to any one of claims 1 to 43, wherein: the temperature of the alkalization unit is 6-11 ℃.
49. The continuous-flow synthesis process according to any one of claims 1 to 43, wherein: the temperature of the alkalization unit is 7-9 ℃.
50. The continuous-flow synthesis process according to any one of claims 1 to 43, wherein: the temperature of the esterification unit is 35-60 ℃.
51. The continuous-flow synthesis process according to any one of claims 1 to 43, wherein: the temperature of the esterification unit is 35-55 ℃.
52. The continuous-flow synthesis process according to any one of claims 1 to 43, wherein: the temperature of the esterification unit is 35-45 ℃.
53. The continuous-flow synthesis process according to any one of claims 1 to 43, wherein: the temperature of the esterification unit is 50-60 ℃.
54. The continuous-flow synthesis process according to any one of claims 1 to 43, wherein: the temperature of the quenching unit is 10-30 ℃.
55. The continuous-flow synthesis process according to any one of claims 1 to 43, wherein: the integrated continuous flow reactor adopts a unitized structure, each unit independently comprises more than one reactor module or reactor module group, wherein the reactor module group is formed by connecting a plurality of reactor modules in series or in parallel, and the units are connected in series.
56. The continuous-flow synthesis process according to any one of claims 1 to 43, wherein: the integrated continuous flow reactor adopts a unitized structure, each unit corresponds to at least one temperature zone, each temperature zone independently comprises more than one reactor module or reactor module group, the reactor module group is formed by connecting a plurality of reactor modules in series or in parallel, and the temperature zones are mutually connected in series.
57. The continuous-flow synthesis process according to any one of claims 1 to 43, wherein: the units further comprise buffers.
58. The continuous-flow synthesis process according to any one of claims 1 to 43, wherein: the number of the feeding ports of the integrated continuous flow reactor is 1 or more, and the number of the discharging ports of the integrated continuous flow reactor is 1 or more.
59. The continuous-flow synthesis process according to claim 55 or 56 or 57 or 58, wherein: the reactor module is any reactor capable of realizing continuous flow process, and the reactor is selected from one or more of microreactor, serial-connected coil reactor and tubular reactor.
60. The continuous-flow synthesis process of claim 59, wherein: the number of the reactors can be one or more.
61. The continuous-flow synthesis process of claim 59, wherein: the material of the reactor channel is monocrystalline silicon, special glass, ceramic, stainless steel or metal alloy coated with a corrosion-resistant coating, and polytetrafluoroethylene.
62. The continuous-flow synthesis process according to claim 55 or 56 or 57 or 58, wherein: the reactor modules, the reactor module groups and the reactor modules and the reactor module groups are respectively connected in series or in parallel.
63. The continuous-flow synthesis process according to any one of claims 1 to 43, wherein: the continuous flow synthesis process is carried out in an integrated continuous flow reactor comprising 3 temperature zones.
64. The continuous-flow synthesis process of claim 63, wherein: the alkalization unit corresponds to a temperature area 1, the esterification unit corresponds to a temperature area 2, and the quenching unit corresponds to a temperature area 3.
65. The continuous-flow synthesis process of claim 63 or 64, wherein: the continuous flow synthesis process comprises the following steps:
(a) delivering tert-butyl peroxide and alkali liquor into a temperature region 1, and reacting through the temperature region 1 to generate an intermediate tert-butyl peroxygenated salt;
(b) the reaction liquid flowing out of the temperature zone 1 is mixed with neodecanoyl chloride, enters the temperature zone 2 and flows through the temperature zone 2 until the reaction is complete;
(c) the reaction liquid flowing out of the temperature zone 2 enters the temperature zone 3 to be cooled to quench the reaction, and reaction mother liquid containing tert-butyl peroxyneodecanoate is output.
66. The continuous-flow synthesis process of claim 65, wherein: the temperature of the temperature zone 1 is 5-35 ℃.
67. The continuous-flow synthesis process of claim 65, wherein: the temperature of the temperature zone 1 is 5-30 ℃.
68. The continuous-flow synthesis process of claim 65, wherein: the temperature of the temperature zone 1 is 5-20 ℃.
69. The continuous-flow synthesis process of claim 65, wherein: the temperature of the temperature zone 1 is 5-18 ℃.
70. The continuous-flow synthesis process of claim 65, wherein: the temperature of the temperature zone 1 is 5-13 ℃.
71. The continuous-flow synthesis process of claim 65, wherein: the temperature of the temperature zone 1 is 6-11 ℃.
72. The continuous-flow synthesis process of claim 65, wherein: the temperature of the temperature zone 1 is 7-9 ℃.
73. The continuous-flow synthesis process of claim 65, wherein: the temperature of the temperature zone 2 is 15-65 ℃.
74. The continuous-flow synthesis process of claim 65, wherein: the temperature of the temperature zone 2 is 35-60 ℃.
75. The continuous-flow synthesis process of claim 65, wherein: the temperature of the temperature zone 2 is 35-55 ℃.
76. The continuous-flow synthesis process of claim 65, wherein: the temperature of the temperature zone 2 is 35-45 ℃.
77. The continuous-flow synthesis process of claim 65, wherein: the temperature of the temperature zone 2 is 50-60 ℃.
78. The continuous-flow synthesis process of claim 65, wherein: the temperature of the warm zone 3 is 5-35 ℃.
79. The continuous-flow synthesis process of claim 65, wherein: the temperature of the temperature zone 3 is 10-30 ℃.
80. The continuous-flow synthesis process of claim 65, wherein: the alkali liquor in the step (a) is selected from an aqueous solution of potassium hydroxide or sodium hydroxide.
81. The continuous-flow synthesis process of claim 65, wherein: the concentration of the alkali liquor is 5-45%.
82. The continuous-flow synthesis process of claim 65, wherein: the concentration of the alkali liquor is 15-35%.
83. The continuous-flow synthesis process of claim 65, wherein: the concentration of the alkali liquor is 20-30%.
84. The continuous-flow synthesis process of claim 65, wherein: the concentration of the tert-butyl peroxide in the step (a) is 60-85%.
85. The continuous-flow synthesis process of claim 65, wherein: the concentration of the tert-butyl peroxide in the step (a) is 65-80%.
86. The continuous-flow synthesis process of claim 65, wherein: the concentration of the tert-butyl peroxide in the step (a) is 70-75%.
87. The continuous-flow synthesis process of claim 65, wherein: the molar ratio of the alkali to the tert-butyl peroxide is 1.0-1.5: 1.
88. The continuous-flow synthesis process of claim 65, wherein: the molar ratio of the alkali to the tert-butyl peroxide is 1.10-1.25: 1.
89. The continuous-flow synthesis process of claim 65, wherein: the molar ratio of base to t-butanol peroxide was 1.18: 1.
90. The continuous-flow synthesis process of claim 65, wherein: the molar ratio of the neodecanoyl chloride to the tert-butyl peroxide is 0.6-1.1: 1.
91. The continuous-flow synthesis process of claim 65, wherein: the molar ratio of the neodecanoyl chloride to the tert-butyl peroxide is 0.7-0.9: 1.
92. The continuous-flow synthesis process of claim 65, wherein: the molar ratio of neodecanoyl chloride to t-butanol peroxide was 0.75: 1.
93. The continuous-flow synthesis process of claim 65, wherein: the yield of the tert-butyl peroxyneodecanoate is more than or equal to 98 percent.
94. The continuous-flow synthesis process of claim 65, wherein: the yield of the tert-butyl peroxyneodecanoate is more than or equal to 99 percent.
95. The continuous-flow synthesis process of claim 65, wherein: the yield of the tert-butyl peroxyneodecanoate is more than or equal to 99.5 percent.
96. The continuous-flow synthesis process of claim 65, wherein: the content of the tert-butyl peroxyneodecanoate is more than or equal to 89.4 percent.
97. The continuous-flow synthesis process of claim 65, wherein: the content of the tert-butyl peroxyneodecanoate is more than or equal to 90 percent.
98. The continuous-flow synthesis process of claim 65, wherein: the content of the tert-butyl peroxyneodecanoate is more than or equal to 92 percent.
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