CN110681327B - Micro-reaction system and method for continuous synthesis of rubber scorch retarder CTP - Google Patents
Micro-reaction system and method for continuous synthesis of rubber scorch retarder CTP Download PDFInfo
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Abstract
A micro-reaction system and a method for continuous synthesis of rubber scorch retarder CTP are provided, wherein the system is composed of a micro heat exchanger, a chlorination micro reactor, a condensation micro reactor and a stirred tank reactor which are connected in series; the synthesis method comprises the following steps: pre-cooling dicyclohexyl disulfide in a micro heat exchanger, and then continuously reacting the dicyclohexyl disulfide with chlorine in a chlorination microreactor to generate cyclohexyl sulfenyl chloride; and (2) continuously flowing cyclohexyl sulfenyl chloride out of the chlorination microreactor and entering a condensation microreactor to be condensed with the prepared phthalimide salt to generate reaction liquid containing N-Cyclohexyl Thiophthalimide (CTP), entering the reaction liquid into a stirring kettle reactor to perform precipitation or continuously stirring and agglomerating to obtain CTP slurry, and performing water diversion and refining to obtain a CTP product. The invention realizes the continuous synthesis of CTP products widely used in the rubber additive industry; the condensation reaction time in the microchannel reactor is millisecond grade, the settling/stirring time in the stirred tank reactor is shortened to 10-20 minutes, and the total yield of the two-step reaction is up to 96.6%.
Description
Technical Field
The invention belongs to the field of synthesis of additives in the rubber industry, and particularly relates to a micro-reaction system and a method for continuous synthesis of a rubber scorch retarder CTP.
Background
The rubber scorch retarder CTP is an indispensable additive for preventing scorching behavior in the rubber industry at present. The raw rubber is a rubber product which needs to be subjected to a series of processes such as plastication, mixing, calendering, vulcanization and the like, and in a processing procedure before vulcanization, due to the action of heat and high temperature generated during mechanical work, the rubber material is often subjected to early vulcanization (so-called scorching), so that the rubber material is difficult to continue to be vulcanized and crosslinked. The matched anti-scorching agent CTP can realize the sealing and mixing of rubber materials in the rubber production, prolong the scorching time and simultaneously do not hinder the normal exertion of the vulcanization accelerator; when the rubber material is calendered or vulcanized, the system temperature can be increased, so that the rubber processing production efficiency is improved.
The synthesis of CTP mainly comprises two reactions: step one, dicyclohexyl disulfide reacts with chlorine to generate cyclohexyl sulfenyl chloride; and secondly, condensing cyclohexyl sulfenyl chloride and phthalimide to generate CTP. Currently, as for the CTP synthesis method, the two-step reaction of chlorination and condensation is all performed by using a tank reactor.
U.S. Pat. No. 4, 4377700 describes the preparation of N-cyclohexylthiophthalimides from phthalimides and cyclohexylsulfenyl chloride in a stirred vessel in the presence of an aqueous solution of an alkali or alkaline earth metal hydroxide. Chinese patent CN 1022484C discloses a CTP preparation method, which is characterized in that chlorination and condensation reactions are completed in the same stirred reactor, and the yield is only about 85%. Further, the japanese dongli corporation also discloses a CTP synthesis method (CN 1880305a) characterized by synthesizing cyclohexylsulfenyl chloride in a mixed solvent of an aromatic hydrocarbon and a saturated hydrocarbon, and then reacting the cyclohexylsulfenyl chloride with phthalimide in a mixed solvent of an aromatic hydrocarbon and a saturated hydrocarbon to generate CTP, wherein the two-step reaction is carried out by stirring, wherein the chlorination reaction time is 1 to 5 hours, the condensation reaction time is 1 to 5 hours, and the product yield is 89%.
The common characteristics of the above CTP synthesis methods are that all chlorination and condensation in the reaction process are performed by stirring, which can wrap part of phthalimide in the CTP product, resulting in higher concentration of residual imine in the product, and the larger defects are that the time for introducing chlorine gas into dicyclohexyl disulfide is long, the mixing is not uniform, and the generated cyclohexylsulfenyl chloride is unstable under long-term reaction, resulting in low total reaction yield.
Disclosure of Invention
Based on the background technology, aiming at the problems of unstable cyclohexylsulfenyl chloride, high concentration of imine in a product and low total reaction yield in a chlorination and condensation process of a stirring kettle, the invention provides a method for synthesizing the cyclohexylsulfenyl chloride by adopting a microchannel gas-liquid continuous reaction process, and enables an intermediate product to be continuously condensed with an imine solution in a microchannel reactor to synthesize CTP.
The specific scheme is as follows:
the invention provides a micro-reaction system for synthesizing rubber scorch retarder CTP, which comprises at least two micro heat exchangers, at least one chlorination microreactor, a condensation microreactor and a stirred tank reactor; a micro-channel of cold and hot fluid is arranged in the micro heat exchanger, and a chlorine gas distribution channel, a micro-hole and a gas-liquid mixing micro-channel are arranged in at least one chlorination microreactor; a cooling water micro-channel is arranged on the upper side and the lower side of the gas-liquid mixing micro-channel; the condensation microreactor comprises a jet mixing microchannel and a jet outlet; a jet outlet of the condensation microreactor is connected into a stirred tank reactor; the stirred tank reactor is provided with a conventional cooling jacket, and cooling circulating water is filled in the conventional cooling jacket for cooling the stirred tank reactor.
Based on the technical scheme, preferably, the condensation microreactor comprises a plurality of jet mixing microchannels which are arranged in parallel and jet outlets which are arranged in parallel.
Based on the above technical solution, preferably, the condensation microreactor may comprise cooling water channels distributed on upper and lower sides of the jet mixing microchannel.
Based on the above technical solution, preferably, the condensation microreactor is disposed inside the stirred tank reactor, or the jet outlet of the condensation microreactor is disposed inside the stirred tank reactor, and preferably, the condensation microreactor is connected to an open position at the top of the stirred tank, and the jet outlet faces the inside of the stirred tank.
Based on the technical scheme, preferably, the front end of the micro-reactor, in which the chlorine gas distribution channel and the micro-pores are arranged, is connected with at least one micro-heat exchanger for cooling the dicyclohexyl disulfide reaction solution entering the chlorination micro-reactor; at least one micro heat exchanger is connected in front of the condensation microreactor and is used for cooling the phthalimide salt solution fed into the condensation reactor. When the number of the microreactors is at least two, the chlorination microreactor with the chlorine distribution channel and the micropores arranged inside is positioned at the forefront of all the chlorination microreactors and is called a first chlorination microreactor, the rear end of the chlorination microreactor is connected with other chlorination microreactors, and the chlorination microreactors are a second chlorination microreactor and a third chlorination microreactor in sequence. The second chlorination micro-reactor and the third chlorination micro-reactor are internally provided with a gas-liquid mixing micro-channel and a cooling water channel, but do not comprise a chlorine gas distribution channel and a micropore.
Based on the technical scheme, preferably, the hydraulic diameter of the micro-channel of the cold and hot fluid in the micro heat exchanger is 0.1-2 mm; the hydraulic diameters of a chlorine gas distribution channel, micropores and a gas-liquid mixing microchannel in the chlorination microreactor are 0.1-2 mm; the hydraulic diameter of the jet mixing microchannel in the condensation microreactor is 0.1-2 mm; the hydraulic diameter of the cooling water channel in the chlorination microreactor and the condensation microreactor can be any size, and is preferably 0.5-5 mm.
In another aspect of the present invention, there is provided a method for continuously synthesizing a rubber scorch retarder CTP in the micro-reaction system, comprising the steps of:
(1) dissolving dicyclohexyl disulfide in alkane with 6-8 carbon atoms or mixed alkane with 6-8 carbon atoms, preferably 120# solvent oil, and preparing a dicyclohexyl disulfide reaction solution;
(2) mixing water, alkali and phthalimide in sequence, stirring to obtain a phthalimide salt solution, and keeping the phthalimide salt solution at the temperature of-5 ℃ by using a micro heat exchanger;
(3) pre-cooling dicyclohexyl disulfide reaction solution in a micro heat exchanger, and then continuously reacting with chlorine in a first chlorination microreactor and/or a second and a third chlorination microreactors to generate cyclohexyl sulfenyl chloride;
(4) the cyclohexyl sulfenyl chloride continuously flows out of the chlorination microreactor and enters the condensation microreactor, and is mixed with the phthalimide salt solution continuously entering the condensation microreactor at a high speed to generate reaction liquid containing N-Cyclohexyl Thiophthalimide (CTP), the jet flow of the reaction liquid enters a stirred tank reactor, the reaction liquid is precipitated or stirred and agglomerated into a CTP product, and the product is obtained by water diversion and refining.
Based on the technical scheme, preferably, the mass concentration of the dicyclohexyl disulfide reaction solution prepared in the synthesis step (1) is 5-50%; in the step (2), the molar ratio of the alkali (calculated by hydroxyl) to the phthalimide is 1: 1-1.2: 1, the mass concentration of the obtained phthalimide salt solution is 5-30%, wherein the alkali is a sodium hydroxide or potassium hydroxide aqueous solution, preferably industrial liquid alkali-sodium hydroxide, and the mass concentration is 32%.
Based on the technical scheme, preferably, in the process of continuously reacting to generate the cyclohexyl sulfenyl chloride in the step (3), the reaction temperature in the microreactor is-20-15 ℃, and the reaction time is 0.01 second-1.5 minutes; in the step (4), the reaction temperature in the condensation microreactor is-10 ℃, the residence time of materials in the condensation microreactor is 0.005-0.1 second, and preferably 0.02-0.05 second; in the step (4), the reaction temperature in the stirred tank reactor is-10 ℃, and the settling or stirring time is 10-20 minutes.
The method for synthesizing CTP by using the micro-reaction system comprises the following steps of (1) in the chlorination reaction process in the step (3), wherein the molar ratio of a reactant chlorine gas to dicyclohexyl disulfide is 1: 1-1.2: 1; in the condensation reaction in the step (4), the molar ratio of phthalimide to dicyclohexyl disulfide is 2: 1-2.2: 1, preferably 2: 1-2.03: 1.
Advantageous effects
The invention essentially is a continuous synthesis process for generating CTP by continuously chloridizing in a microreactor to form an intermediate product and then introducing the intermediate product into a condensation microreactor to react with an imine solution. Compared with the traditional processes of stirred tank chlorination and stirred tank condensation, the miniaturization technology of the reaction equipment in the whole process of chlorination condensation is remarkable, the chlorination reaction time is shortened from tens of minutes to 0.01-1.5 minutes, the condensation reaction time is shortened from tens of minutes to 0.02-0.05 seconds, and the shortening of the chlorination reaction time ensures that the generated cyclohexyl sulfenyl chloride has high quality and reduces the decomposition chance; the micro-channel jet mixing structure avoids agglomeration and blockage of condensation products, reduces imine residue to a great extent, has high utilization rate of raw material imine, achieves the total yield of 96.6 percent (calculated by disulfide) after the product CTP is purified, has the product CTP purity of more than 97 percent, has the concentration of residual imine of less than 0.5 percent and is 1.0 to 1.5 percent lower than that of the prior art. The adoption of the condensation microreactor reduces the power consumption of a conventional stirred tank.
Drawings
FIG. 1 is a schematic view of the process of the present invention;
FIG. 2 is a schematic structural view of a condensation microreactor according to the present invention;
wherein, 1-raw material preparation micro mixer, 2-micro heat exchanger, 3-chlorination micro reactor, 4-micro heat exchanger, 5-condensation micro reactor, 6-stirred tank reactor, A-dicyclohexyl disulfide, B-alkane or mixed alkane with 6-8 carbon atoms, C-chlorine, D-phthalimide solution, and R-circulating cooling water.
FIGS. 2A and B are schematic structural diagrams of a condensation microreactor according to the present invention, wherein, 5M-condensation microreactor mixing chip, 5-1, 5-2-cyclohexylsulfenyl chloride inlet channel or phthalimide salt solution inlet channel, 5-3-cyclohexylsulfenyl chloride and phthalimide salt solution mixing port, 5-4-jet mixing microchannel, 5-jet outlet, 5-6A, 5-6B-cooling water inlet and outlet channel; 5C-condensation micro-reactor cooling water channel chip, 5-7-cooling water channel.
Detailed Description
The following description of the embodiments of the present invention is provided with reference to the accompanying drawings, but the present invention is not limited to the embodiments described below.
The micro-reaction system for continuous synthesis of rubber scorch retarder CTP, as shown in FIG. 1, comprises the following components: a micro mixer 1 for preparing disulfide solution, a micro heat exchanger 2 for cooling the prepared disulfide solution, a chlorination micro reactor 3 for reacting chlorine with the cooled disulfide solution, a micro heat exchanger 4 for cooling reactant phthalimide solution, a condensation micro reactor 5 for reacting the obtained chlorination product cyclohexylsulfenyl chloride with phthalimide, and a stirred tank reactor 6 for precipitating or stirring and agglomerating the condensation reaction liquid into CTP.
In the micro-reaction system shown in fig. 1, a chlorination microreactor 3 is used as a gas-liquid mixing and reacting device, and a chlorine gas distribution channel and micropores are formed in the chlorination microreactor, and a gas-liquid mixing microchannel is formed in the chlorination microreactor, and cooling water channels are formed on the upper side and the lower side of the gas-liquid mixing microchannel. The chlorination micro-reactor 3 can also be connected with 1-2 micro-reactors in series to further complete the chlorination reaction, and then is connected with the condensation micro-reactor 5, the micro-reactors connected in series do not comprise a chlorine gas distribution channel and a micropore structure for gas-liquid mixing, but are provided with a micro-channel for further gas-liquid mixing and reaction and a cooling water channel.
The micro-channel hydraulic diameter in the micro-mixer, the micro-heat exchanger and the chlorination and condensation micro-reactor is 0.1-2 mm, in the following embodiments, the hydraulic diameter of a chlorine gas distribution channel in the chlorination micro-reactor 3 is gradually reduced from 2 mm to 0.7 mm, the pore diameter of a chlorine gas micropore is 0.7 mm, and the hydraulic diameter of a gas-liquid mixing micro-channel is 0.58 mm. The hydraulic diameter of the jet mixing microchannel in the condensation microreactor 5 is gradually reduced from 2 mm to 0.1 mm, and the total effective volume is 15 microliter.
The CTP process was synthesized using the microreaction system shown in fig. 1: dicyclohexyl disulfide and heptane are conveyed by two pumps and mixed in a certain proportion in a micro mixer 1 to form a disulfide homogeneous phase solution, or solution can be prepared by any other container, the prepared disulfide solution is cooled by a microchannel heat exchanger 2 and then mixed and reacted with chlorine gas C in a chlorination microreactor 3 to generate cyclohexyl sulfenyl chloride, and the cyclohexyl sulfenyl chloride enters a condensation microreactor 5 and is mixed and reacted with phthalimide sodium salt solution continuously entering the microreactor at a high speed to generate a product CTP.
The starting materials for the following examples are all commercially available: dicyclohexyl disulfide purity 95.5% (mass concentration); the purity of the phthalimide is 98.5 percent (mass concentration); the liquid alkali is 32% (mass concentration) sodium hydroxide aqueous solution.
Example 1
The micro-reactor system is shown in FIG. 1, wherein the effective volume of the micro-channel inside the chlorination micro-reactor 3 is 2.7 ml, the volume of the stirred tank reactor is 1L, and the stirring paddle is equipped. Pre-preparing dicyclohexyl disulfide solution, wherein a solvent is normal heptane and isoheptane mixed alkane, the mass concentration of dicyclohexyl disulfide is 11.9%, the dicyclohexyl disulfide is conveyed by a metering pump, the volume flow is 40.0ml/min, the dicyclohexyl disulfide solution enters a micro heat exchanger 2 to be cooled to minus 5 ℃, the dicyclohexyl disulfide solution enters a chlorination microreactor 3 to be mixed with 330ml/min (standard condition) chlorine after being cooled, the reaction temperature in the microreactor 3 is controlled to be minus 15 ℃, the reaction time (calculated by liquid disulfide solution) is 4 seconds, cyclohexyl sulfenyl chloride is generated by reaction, the cyclohexyl sulfenyl chloride enters a condensation microreactor 5 to be mixed with phthalimide sodium salt solution continuously entering the microreactor at a high speed, the molar ratio of alkali to imine in the phthalimide sodium salt solution is 1:1, the mass concentration calculated by imine is 5% (density is 1.027), the freezing point temperature of the solution is kept at 0 ℃, and the mixture is conveyed into a condensation microreactor 5 by a pump, the volume flow of the phthalimide solution is 84.7ml/min (the molar ratio of imine to disulfide is 2:1), the total material receiving time is 5 minutes, and the stirring and agglomeration are continued for 20 minutes after the material receiving is finished. The product was filtered and dried to give 37.1 g of dry product, 97.4% yield based on disulfide, and chromatographed: the purity of the main product CTP is 97.6%, the concentration of the residual phthalimide is 0.48%, so that the purity yield is 95.1% in terms of disulfide and 93.1% in terms of imine.
Example 2
The microreactor system is shown in FIG. 1, wherein the effective volume of the microchannel inside the chlorination microreactor 3 is 0.3 ml (obtained by reducing the number of channels and the number of layers), and the volume of the stirred tank reactor is 2 liters, and the stirred tank reactor is equipped with a stirring paddle. Pre-preparing a dicyclohexyl disulfide solution, wherein a solvent is mixed alkane of n-heptane and iso-heptane, the mass concentration of dicyclohexyl disulfide is 30%, the dicyclohexyl disulfide is delivered by a metering pump, the volume flow is 50.0ml/min, the dicyclohexyl disulfide enters a micro heat exchanger 2 and is cooled to minus 5 ℃, the dicyclohexyl disulfide enters a chlorination microreactor 3 and is mixed with chlorine gas of 1.16L/min (standard condition) after being cooled, the reaction temperature in the microreactor 3 is controlled to be minus 5 ℃, the reaction time (calculated by liquid disulfide solution) is 0.36 second, cyclohexyl sulfenyl chloride is generated by reaction, the cyclohexyl sulfenyl chloride enters a condensation microreactor 5 and is mixed with a phthalimide sodium salt solution continuously entering the microreactor at a high speed, the molar ratio of alkali to imine in the phthalimide sodium salt solution is 1.1:1, the mass concentration calculated by imine is 15% (density is 1.08), the freezing point temperature of the solution is kept at 0 ℃, and the mixture is conveyed into a condensation microreactor 5 by a pump, the volume flow of the phthalimide solution is 92.3ml/min (the molar ratio of imine to disulfide is 2.06:1), the total material receiving time is 4 minutes, and the stirring and agglomeration are continued for 10 minutes after the material receiving is finished. The product was filtered and dried to obtain 101.6 g of dry product, the yield was 99.8% calculated as disulfide, and the chromatographic analysis: the purity of the main product CTP is 96.8%, the concentration of the residual phthalimide is 0.5%, so that the purity yield is 96.6% in terms of disulfide and 92.7% in terms of imine.
Example 3
The micro-reactor system is shown in FIG. 1, wherein the effective volume of the micro-channel inside the chlorination micro-reactor 3 is 2.7 ml, the volume of the stirred tank reactor is 10L, and the stirring paddle is equipped. Dicyclohexyl disulfide is conveyed by a pump 1, the volume flow is 46ml/min, solvent n-heptane and isoheptane mixed alkane is conveyed by a pump 2, the volume flow is 67.1ml/min, dicyclohexyl disulfide solution is formed by mixing in a micro mixer 1 (without heat exchange) at room temperature (the mass concentration of dicyclohexyl disulfide reaction solution can be calculated to be 50%), the dicyclohexyl disulfide solution enters a micro heat exchanger 2 to be cooled to minus 5 ℃, the dicyclohexyl disulfide solution enters a chlorination microreactor 3 to be mixed with chlorine gas of 4.7L/min (standard condition) after being cooled, the reaction temperature in the microreactor 3 is controlled to be minus 5 ℃, the reaction time (measured by liquid disulfide solution) is 1.4 seconds, cyclohexyl sulfenyl chloride is generated, the cyclohexyl sulfenyl chloride enters a condensation microreactor 5 to be mixed with phthalimide sodium salt solution continuously entering the microreactor at high speed, wherein, the molar ratio of alkali to imine in the phthalimide sodium salt solution is 1.2:1, the mass concentration of the phthalimide solution is 30% (density is 1.19), the freezing temperature of the solution is kept at 0 ℃, the solution is conveyed into the condensation microreactor 5 by a pump, the volume flow of the phthalimide solution is 165.0ml/min, the total material receiving time is 7.6 minutes, and after the material receiving is finished, the stirring and agglomeration are continued for 20 minutes. The product was filtered and dried to give 743.1 g of dry product, 94.9% yield based on disulfide and chromatographic analysis: the purity of the main product CTP is 97.5%, the concentration of the residual phthalimide is 1.04%, so that the purity yield is 92.5% in terms of disulfide and 90.8% in terms of imine.
Claims (10)
1. A micro-reaction system for continuous synthesis of rubber scorch retarder CTP is characterized by comprising at least two micro heat exchangers, at least one chlorination microreactor, a condensation microreactor and a stirred tank reactor; the micro heat exchanger is internally provided with a micro channel for cold and hot fluid, and at least one chlorination microreactor is internally provided with a chlorine distribution channel, a micropore and a gas-liquid mixing microchannel; cooling water channels are arranged on the upper side and the lower side of the gas-liquid mixing micro-channel; the condensation microreactor comprises a jet mixing microchannel and a jet outlet; a jet outlet of the condensation microreactor is connected into a stirred tank reactor; the stirred tank reactor is provided with a cooling jacket;
at least one micro heat exchanger is connected in front of the chlorination microreactor with the chlorine distribution channel and the micropores arranged inside; at least one micro heat exchanger is connected in front of the condensation micro reactor.
2. The micro-reaction system of claim 1, wherein when there are at least two chlorination microreactors, the microreactor with the chlorine distribution channel and the micro-pores therein is called a first chlorination microreactor, and the other chlorination microreactors connected in series are a second chlorination microreactor and a third chlorination microreactor in sequence; and a gas-liquid mixing micro-channel and a cooling water channel are arranged in the second chlorination micro-reactor and the third chlorination micro-reactor.
3. The micro-reaction system of claim 2, wherein the condensation microreactor comprises a multi-channel parallel arrangement of fluidic mixing microchannels.
4. The micro-reaction system of claim 3, wherein the jet mixing micro-channel is provided with cooling water channels on the upper and lower sides.
5. The micro-reaction system according to any one of claims 2 to 4, wherein the hydraulic diameter of the micro-channels of the cold and hot fluid in the micro-heat exchanger is 0.1 to 2 mm; the hydraulic diameters of a chlorine gas distribution channel, micropores and a gas-liquid mixing microchannel in the chlorination microreactor are 0.1-2 mm; the hydraulic diameter of the jet mixing microchannel in the condensation microreactor is 0.1-2 mm.
6. A method for synthesizing rubber scorch retarder CTP by using the micro-reaction system as defined in claim 1, comprising the following steps:
(1) dissolving dicyclohexyl disulfide in alkane with 6-8 carbon atoms or mixed alkane with 6-8 carbon atoms to prepare a dicyclohexyl disulfide reaction solution;
(2) mixing water, alkali and phthalimide, stirring to prepare a phthalimide salt solution, and keeping the temperature at-5 ℃;
(3) pre-cooling dicyclohexyl disulfide reaction solution to-15-10 ℃ in a micro heat exchanger, and then reacting the dicyclohexyl disulfide reaction solution with chlorine in a chlorination microreactor to generate cyclohexyl sulfenyl chloride;
(4) and (2) continuously flowing cyclohexyl sulfenyl chloride out of the chlorination microreactor, entering the condensation microreactor, mixing with the phthalimide salt solution continuously entering the condensation microreactor at a high speed to generate reaction liquid containing N-Cyclohexyl Thiophthalimide (CTP), enabling the jet flow of the reaction liquid to enter a stirring kettle reactor, performing sedimentation or stirring agglomeration to obtain a CTP product, and performing water diversion and refining to obtain the rubber scorch retarder CTP.
7. A method for synthesizing rubber scorch retarder CTP by using the micro-reaction system as recited in any one of claims 2-5, which comprises the following steps:
(1) dissolving dicyclohexyl disulfide in alkane with 6-8 carbon atoms or mixed alkane with 6-8 carbon atoms to prepare a dicyclohexyl disulfide reaction solution;
(2) mixing water, alkali and phthalimide, stirring to prepare a phthalimide salt solution, and keeping the temperature at-5 ℃;
(3) pre-cooling dicyclohexyl disulfide reaction solution to-15-10 ℃ in a micro heat exchanger, reacting with chlorine in a first chlorination microreactor, and then sequentially entering other chlorination microreactors for continuous and sufficient reaction to generate cyclohexyl sulfenyl chloride;
(4) and (2) continuously flowing cyclohexyl sulfenyl chloride out of the chlorination microreactor, entering the condensation microreactor, mixing with the phthalimide salt solution continuously entering the condensation microreactor at a high speed to generate reaction liquid containing N-Cyclohexyl Thiophthalimide (CTP), enabling the jet flow of the reaction liquid to enter a stirring kettle reactor, performing sedimentation or stirring agglomeration to obtain a CTP product, and performing water diversion and refining to obtain the rubber scorch retarder CTP.
8. The method as claimed in claim 6 or 7, wherein the mass concentration of the dicyclohexyl disulfide reaction solution in the step (1) is 5% to 50%; in the step (2), the molar ratio of hydroxide ions contained in the alkali to phthalimide is 1: 1-1.2: 1, and the mass concentration of the obtained phthalimide salt solution is 5-30%; the alkali is sodium hydroxide or potassium hydroxide.
9. The method according to claim 6 or 7, wherein in the step (3), the reaction temperature in the chlorination microreactor is-20 to 15 ℃, and the reaction time is 0.01 second to 1.5 minutes; in the step (4), the reaction temperature in the condensation microreactor is-10 ℃, and the material residence time in the condensation microreactor is 0.005-0.1 second; in the step (4), the reaction temperature in the stirred tank reactor is-10 ℃, and the settling or stirring time is 10-20 minutes.
10. The method according to claim 6 or 7, characterized in that, in the chlorination reaction in the step (3), the molar ratio of the chlorine reactant to the dicyclohexyl disulfide is 1: 1-1.2: 1; during the condensation reaction in the step (4), the molar ratio of phthalimide to dicyclohexyl disulfide is 2: 1-2.2: 1.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999054362A1 (en) * | 1998-04-17 | 1999-10-28 | Axiva Gmbh | Method and device for continuous production of polymers |
| CN1880305A (en) * | 2005-06-14 | 2006-12-20 | 东丽精密化学株式会社 | Production method of n-(cyclohixylthio) phthalimide |
| CN104592093A (en) * | 2013-10-31 | 2015-05-06 | 青岛旺裕橡胶制品有限公司 | Synthetic process of rubber scorch retarder CPT |
| CN108610272A (en) * | 2018-06-05 | 2018-10-02 | 蔚林新材料科技股份有限公司 | A kind of micro- reaction method of continuous synthesis tetraalkylthiuram disulfide |
| CN109876746A (en) * | 2019-03-18 | 2019-06-14 | 汤阴永新化学有限责任公司 | A kind of system and method for the micro- reaction synthetic rubber anti-scorching agent CTP of continuous flow |
-
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999054362A1 (en) * | 1998-04-17 | 1999-10-28 | Axiva Gmbh | Method and device for continuous production of polymers |
| CN1880305A (en) * | 2005-06-14 | 2006-12-20 | 东丽精密化学株式会社 | Production method of n-(cyclohixylthio) phthalimide |
| CN104592093A (en) * | 2013-10-31 | 2015-05-06 | 青岛旺裕橡胶制品有限公司 | Synthetic process of rubber scorch retarder CPT |
| CN108610272A (en) * | 2018-06-05 | 2018-10-02 | 蔚林新材料科技股份有限公司 | A kind of micro- reaction method of continuous synthesis tetraalkylthiuram disulfide |
| CN109876746A (en) * | 2019-03-18 | 2019-06-14 | 汤阴永新化学有限责任公司 | A kind of system and method for the micro- reaction synthetic rubber anti-scorching agent CTP of continuous flow |
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