CN118239907B - Synthesis method of rubber vulcanizing agent DTDM - Google Patents
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 40
- 238000001308 synthesis method Methods 0.000 title claims abstract description 4
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims abstract description 108
- 238000006243 chemical reaction Methods 0.000 claims abstract description 50
- 239000002253 acid Substances 0.000 claims abstract description 37
- 239000011230 binding agent Substances 0.000 claims abstract description 37
- 239000002904 solvent Substances 0.000 claims abstract description 30
- PXJJSXABGXMUSU-UHFFFAOYSA-N disulfur dichloride Chemical compound ClSSCl PXJJSXABGXMUSU-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000003756 stirring Methods 0.000 claims abstract description 17
- 230000001276 controlling effect Effects 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- HLBZWYXLQJQBKU-UHFFFAOYSA-N 4-(morpholin-4-yldisulfanyl)morpholine Chemical compound C1COCCN1SSN1CCOCC1 HLBZWYXLQJQBKU-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- 230000001105 regulatory effect Effects 0.000 claims abstract description 8
- 238000010025 steaming Methods 0.000 claims abstract description 8
- 230000001502 supplementing effect Effects 0.000 claims abstract description 8
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 24
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 16
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 16
- 239000002608 ionic liquid Substances 0.000 claims description 15
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 8
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 8
- -1 1-propyl-3-methylimidazole nitrate Chemical compound 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- MKFKRDBGTIMGAC-UHFFFAOYSA-N [N+](=O)(O)[O-].CN1CN(C=C1)C Chemical compound [N+](=O)(O)[O-].CN1CN(C=C1)C MKFKRDBGTIMGAC-UHFFFAOYSA-N 0.000 claims description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 230000002194 synthesizing effect Effects 0.000 claims description 4
- 239000003208 petroleum Substances 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims 1
- 238000010189 synthetic method Methods 0.000 abstract description 20
- 239000002994 raw material Substances 0.000 abstract description 11
- 208000012839 conversion disease Diseases 0.000 abstract description 7
- 238000001914 filtration Methods 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 239000002920 hazardous waste Substances 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 239000012752 auxiliary agent Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000004128 high performance liquid chromatography Methods 0.000 description 8
- 238000001514 detection method Methods 0.000 description 7
- 238000004321 preservation Methods 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000010057 rubber processing Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/22—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with hetero atoms directly attached to ring nitrogen atoms
- C07D295/26—Sulfur atoms
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention discloses a synthetic method of a rubber vulcanizing agent DTDM, which relates to the technical field of rubber auxiliary agent synthesis and comprises the following steps: simultaneously adding raw materials such as a solvent, an acid binding agent, morpholine and the like into a reaction kettle, dropwise adding sulfur monochloride at the temperature of 20-60 ℃ while stirring, continuously preserving heat for reaction after the dropwise adding is finished within 2-6 hours, performing auxiliary treatment on a multi-energy field for 20-30 minutes in the reaction process, and controlling the end point of the reaction by detecting the content of the morpholine and controlling the supplementing amount of the acid binding agent so as to ensure that the added morpholine fully reacts to generate 4, 4-dithiodimorpholine; stopping stirring after reaching the reaction end point, regulating the temperature to room temperature, steaming to recover the solvent, adding water for washing 3-6 times, filtering and drying to obtain the rubber vulcanizing agent DTDM. The synthesis method has high product yield, purity and reaction conversion rate, less hazardous waste production and low working strength.
Description
Technical Field
The invention relates to the technical field of rubber auxiliary agent synthesis, in particular to a method for synthesizing a rubber vulcanizing agent DTDM.
Background
The rubber is widely applied to various industries such as daily life, medical industry, rail transit industry and the like at present, and has irreplaceable function in the life of people. In order to improve the overall properties and stability of the rubber, it is often necessary to add a vulcanizing agent during the rubber processing. The 4,4' -dithiodimorpholine (DTDM) is a common rubber vulcanizing agent, has the advantages of safe operation, no frosting, no color change, no pollution and the like, and is widely applied to the manufacture of high-quality rubber products such as radial tires, engineering tires, inclined rubber tires, butyl inner tubes, rubber seals and the like.
In the existing synthetic method of the rubber vulcanizing agent DTDM, raw materials of morpholine, an acid binding agent and sulfur monochloride are respectively dripped, namely a three-dripping method, the method has the advantages of complex operation process, high working strength, less than 92% of effective conversion rate of main raw materials of morpholine, and higher production cost and three-waste treatment cost of unit products caused by the fact that unreacted raw materials enter a three-waste system. In addition, the acid-binding agent commonly used at present is morpholine or sodium hydroxide, and when morpholine is used as the acid-binding agent, the problem of great waste of morpholine exists, meanwhile, the morpholine recovery process is complex, and the generated wastewater is difficult to treat; when sodium hydroxide is used as an acid binding agent, water is generated in the reaction of sodium hydroxide and hydrochloric acid, and the existence of water can lead to the generation of side reaction of sulfur monochloride decomposition, so that the finally obtained product has low yield and poor quality and hardly meets the index requirements.
In order to solve the problems, the Chinese patent publication No. CN114853695B discloses a preparation method of rubber vulcanizing agent 4,4' -dithiodimorpholine (DTDM), morpholine, organic solvent and acid binding agent are added into a reaction container at the same time, and the thickness ratio and stirring speed of the organic solvent layer and the alkaline solution layer are controlled; adding sulfur monochloride at room temperature-55 deg.c for reaction, maintaining the temperature for 0.5-2 hr to obtain 4,4 '-dithiodimorpholine mixture, separating, water washing and drying to obtain 4,4' -dithiodimorpholine; the conversion rate of morpholine reaches more than 98%, the yield (calculated by morpholine) of DTDM reaches more than 98%, the melting point of the product reaches more than 122 ℃, the purity of HPLC is more than 99%, the product does not need recrystallization, the organic solvent used in the reaction can be directly recycled after being separated from water, the ammonia nitrogen of the produced water is less than 5mg/L, and the salt with higher purity is obtained after concentration. Although the method can reduce the generation of byproducts to a certain extent, water and alkali still exist, and the product yield and the reaction conversion rate still need to be further improved.
Therefore, the synthetic method of the rubber vulcanizing agent DTDM with high product yield, purity and reaction conversion rate, less hazardous waste production and low working strength is developed, meets the market demand, has wide market value and application prospect, and has very important significance for promoting the development of the rubber vulcanizing agent production technology.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a synthetic method of a rubber vulcanizing agent DTDM with high product yield, purity and reaction conversion rate, less hazardous waste production and low working strength.
In order to achieve the above purpose, the invention adopts the following technical scheme: a synthetic method of a rubber vulcanizing agent DTDM comprises the following steps: simultaneously adding a solvent, an acid binding agent and a morpholine raw material into a reaction kettle, dropwise adding sulfur monochloride at the temperature of 20-60 ℃ while stirring, continuously preserving heat for reaction after the dropwise adding is finished within 2-6 hours, performing auxiliary treatment on a multi-energy field for 20-30 minutes in the reaction process, and controlling the end point of the reaction by detecting the morpholine content and controlling the supplementing amount of the acid binding agent to ensure that the added morpholine fully reacts to generate 4, 4-dithiodimorpholine; stopping stirring after reaching the reaction end point, regulating the temperature to room temperature, steaming to recover the solvent, adding water for washing 3-6 times, filtering and drying to obtain the rubber vulcanizing agent DTDM.
Preferably, the solvent is any one of dichloromethane, toluene, benzene, petroleum ether and xylene.
Preferably, the acid binding agent is a mixture formed by mixing triethylamine, pyridine, sodium tert-butoxide and ionic liquid according to the mass ratio of 1 (0.3-0.5) to 0.3 (0.1-0.3).
Preferably, the ionic liquid is at least one of 1-propyl-3-methylimidazole nitrate and 1, 3-dimethylimidazole nitrate.
Preferably, the molar ratio of the morpholine to the sulfur monochloride is 2:1.
Preferably, the mass ratio of the solvent to the acid binding agent to the morpholine is (8-15): 1.5-2): 1.
Preferably, the multi-energy field includes ultrasonic waves, microwaves and magnetic fields; the ultrasonic frequency is 50-100kHz, and the power range is 300-500W; the frequency of the microwave treatment is 2.5-3.0GHz, and the power range is 800-1400W; the magnetic field strength of the magnetic field treatment is 9000-16000Gs.
Due to the application of the technical scheme, the invention has the following beneficial effects:
(1) According to the synthetic method of the rubber vulcanizing agent DTDM, disclosed by the invention, the yield, purity and reaction conversion rate of the reaction product are high, the dangerous waste production is less, and the working strength is low by reasonably selecting reactants and synthetic process parameters.
(2) The invention discloses a synthetic method of a rubber vulcanizing agent DTDM, wherein an acid binding agent is a mixture formed by mixing triethylamine, pyridine, sodium tert-butoxide and ionic liquid according to the mass ratio of 1 (0.3-0.5) to 0.3 (0.1-0.3), so that the problems of low product yield and poor purity caused by the decomposition of sulfur monochloride generated by water are avoided; effectively improves the yield, purity and reaction conversion rate of the product. Meanwhile, the waste of reaction raw materials and the safety, the green and the environmental protection of the reaction process can be reduced.
(3) The invention discloses a synthetic method of a rubber vulcanizing agent DTDM, wherein a multi-energy field is adopted for auxiliary treatment in the reaction process, and the multi-energy field comprises ultrasonic waves, microwaves and a magnetic field; can effectively improve the reaction rate and the reaction conversion rate, and improve the purity and the yield of the product.
Detailed Description
The following description is presented to enable one of ordinary skill in the art to make and use the invention. The preferred embodiments in the following description are by way of example only and other obvious variations will occur to those skilled in the art.
Example 1
A synthetic method of a rubber vulcanizing agent DTDM comprises the following steps: simultaneously adding raw materials such as a solvent, an acid binding agent, morpholine and the like into a reaction kettle, dropwise adding sulfur monochloride at 20 ℃ while stirring, continuously carrying out heat preservation reaction after the dropwise adding is finished within 2 hours, performing multi-energy field auxiliary treatment for 20 minutes in the reaction process, and controlling the reaction end point by detecting the morpholine content and controlling the acid binding agent supplementing amount to ensure that the added morpholine fully reacts to generate 4, 4-dithiodimorpholine; stopping stirring after reaching the reaction end point, regulating the temperature to room temperature, steaming to recover the solvent, adding water for washing for 3 times, filtering, and drying to obtain the rubber vulcanizing agent DTDM.
The solvent is dichloromethane; the acid binding agent is a mixture formed by mixing triethylamine, pyridine, sodium tert-butoxide and ionic liquid according to the mass ratio of 1:0.3:0.3:0.1; the ionic liquid is 1-propyl-3-methylimidazole nitrate; the molar ratio of the morpholine to the sulfur monochloride is 2:1; the mass ratio of the solvent to the acid binding agent to the morpholine is 8:1.5:1.
The multi-energy field includes ultrasonic waves, microwaves and magnetic fields; the ultrasonic frequency is 50kHz, and the power range is 300W; the frequency of the microwave treatment is 2.5GHz, and the power range is 800W; the magnetic field strength of the magnetic field treatment was 9000Gs.
By detection, the yield of DTDM produced by the above-mentioned synthetic method of rubber vulcanizing agent DTDM was found to be 99.38% (calculated as morpholine) and the HPLC purity was found to be 99.76%.
Example 2
A synthetic method of a rubber vulcanizing agent DTDM comprises the following steps: simultaneously adding raw materials such as a solvent, an acid binding agent, morpholine and the like into a reaction kettle, dropwise adding sulfur monochloride at the temperature of 30 ℃ while stirring, continuously carrying out heat preservation reaction after the dropwise adding is finished within 3 hours, performing auxiliary treatment on a multi-energy field during the reaction for 23 minutes, and controlling the end point of the reaction by detecting the content of the morpholine and controlling the supplementing amount of the acid binding agent so as to ensure that the added morpholine fully reacts to generate 4, 4-dithiodimorpholine; stopping stirring after reaching the reaction end point, regulating the temperature to room temperature, steaming to recover the solvent, adding water for washing for 4 times, filtering, and drying to obtain the rubber vulcanizing agent DTDM.
The solvent is toluene; the acid binding agent is a mixture formed by mixing triethylamine, pyridine, sodium tert-butoxide and ionic liquid according to the mass ratio of 1:0.35:0.3:0.15; the ionic liquid is 1, 3-dimethyl imidazole nitrate; the molar ratio of the morpholine to the sulfur monochloride is 2:1; the mass ratio of the solvent to the acid binding agent to the morpholine is 10:1.6:1.
The multi-energy field includes ultrasonic waves, microwaves and magnetic fields; the ultrasonic frequency is 65kHz, and the power range is 350W; the frequency of the microwave treatment is 2.7GHz, and the power range is 1000W; the magnetic field strength of the magnetic field treatment is 11000Gs.
By detection, the yield of DTDM produced by the above-mentioned synthetic method of rubber vulcanizing agent DTDM was found to be 99.65% (calculated as morpholine) and the HPLC purity was found to be 99.82%.
Example 3
A synthetic method of a rubber vulcanizing agent DTDM comprises the following steps: simultaneously adding raw materials such as a solvent, an acid binding agent, morpholine and the like into a reaction kettle, dropwise adding sulfur monochloride at 35 ℃ while stirring, continuously carrying out heat preservation reaction after the dropwise adding is finished within 4 hours, performing auxiliary treatment on a multi-energy field for 25 minutes in the reaction process, and controlling the end point of the reaction by detecting the content of the morpholine and controlling the supplementing amount of the acid binding agent so as to ensure that the added morpholine fully reacts to generate 4, 4-dithiodimorpholine; stopping stirring after reaching the reaction end point, regulating the temperature to room temperature, steaming to recover the solvent, adding water for washing 5 times, filtering and drying to obtain the rubber vulcanizing agent DTDM.
The solvent is petroleum ether; the acid binding agent is a mixture formed by mixing triethylamine, pyridine, sodium tert-butoxide and ionic liquid according to the mass ratio of 1:0.4:0.3:0.2; the ionic liquid is 1-propyl-3-methylimidazole nitrate; the molar ratio of the morpholine to the sulfur monochloride is 2:1; the mass ratio of the solvent to the acid binding agent to the morpholine is 12:1.8:1.
The multi-energy field includes ultrasonic waves, microwaves and magnetic fields; the ultrasonic frequency is 80kHz, and the power range is 400W; the frequency of the microwave treatment is 2.8GHz, and the power range is 1200W; the magnetic field strength of the magnetic field treatment is 13000Gs.
By detection, the yield of DTDM produced by the above-mentioned synthetic method of rubber vulcanizing agent DTDM was found to be 99.71% (calculated as morpholine) and the HPLC purity was found to be 99.89%.
Example 4
A synthetic method of a rubber vulcanizing agent DTDM comprises the following steps: simultaneously adding raw materials such as a solvent, an acid binding agent, morpholine and the like into a reaction kettle, dropwise adding sulfur monochloride at 50 ℃ while stirring, continuously carrying out heat preservation reaction after the dropwise adding is finished within 5 hours, performing multi-energy field auxiliary treatment for 28 minutes in the reaction process, and controlling the reaction end point by detecting the morpholine content and controlling the acid binding agent supplementing amount to ensure that the added morpholine fully reacts to generate 4, 4-dithiodimorpholine; stopping stirring after reaching the reaction end point, regulating the temperature to room temperature, steaming to recover the solvent, adding water for washing 5 times, filtering and drying to obtain the rubber vulcanizing agent DTDM.
The solvent is dimethylbenzene; the acid binding agent is a mixture formed by mixing triethylamine, pyridine, sodium tert-butoxide and ionic liquid according to the mass ratio of 1:0.45:0.3:0.25; the ionic liquid is a mixture formed by mixing 1-propyl-3-methylimidazole nitrate and 1, 3-dimethylimidazole nitrate according to a mass ratio of 3:5; the molar ratio of the morpholine to the sulfur monochloride is 2:1; the mass ratio of the solvent to the acid binding agent to the morpholine is 14:1.9:1.
The multi-energy field includes ultrasonic waves, microwaves and magnetic fields; the ultrasonic frequency is 90kHz, and the power range is 450W; the frequency of the microwave treatment is 2.9GHz, and the power range is 1300W; the magnetic field strength of the magnetic field treatment was 15000Gs.
By detection, the yield of DTDM produced by the above-mentioned synthetic method of rubber vulcanizing agent DTDM was found to be 99.80% (calculated as morpholine) and the HPLC purity was found to be 99.92%.
Example 5
A synthetic method of a rubber vulcanizing agent DTDM comprises the following steps: simultaneously adding raw materials such as a solvent, an acid binding agent, morpholine and the like into a reaction kettle, dropwise adding sulfur monochloride at the temperature of 60 ℃ while stirring, continuously carrying out heat preservation reaction after the dropwise adding is finished within 6 hours, performing auxiliary treatment on a multi-energy field for 30 minutes in the reaction process, and controlling the end point of the reaction by detecting the content of the morpholine and controlling the supplementing amount of the acid binding agent so as to ensure that the added morpholine fully reacts to generate 4, 4-dithiodimorpholine; stopping stirring after reaching the reaction end point, regulating the temperature to room temperature, steaming to recover the solvent, adding water for washing 3-6 times, filtering and drying to obtain the rubber vulcanizing agent DTDM.
The solvent is dichloromethane; the acid binding agent is a mixture formed by mixing triethylamine, pyridine, sodium tert-butoxide and ionic liquid according to the mass ratio of 1:0.5:0.3:0.3; the ionic liquid is 1, 3-dimethyl imidazole nitrate; the molar ratio of the morpholine to the sulfur monochloride is 2:1; the mass ratio of the solvent to the acid binding agent to the morpholine is 15:2:1.
The multi-energy field includes ultrasonic waves, microwaves and magnetic fields; the ultrasonic frequency is 100kHz, and the power range is 500W; the frequency of the microwave treatment is 3.0GHz, and the power range is 1400W; the magnetic field strength of the magnetic field treatment is 16000Gs.
By detection, the yield of DTDM produced by the above-mentioned synthetic method of rubber vulcanizing agent DTDM was found to be 99.85% (calculated as morpholine) and the HPLC purity was found to be 99.95%.
Comparative example 1
The synthesis of the rubber vulcanizing agent DTDM was substantially the same as in example 1, except that no multi-energy field auxiliary treatment was performed.
By detection, the yield of DTDM produced by the above-mentioned synthetic method of rubber vulcanizing agent DTDM was found to be 92.19% (calculated as morpholine) and the HPLC purity was found to be 96.33%.
Comparative example 2
A method for synthesizing a rubber vulcanizing agent DTDM is basically the same as in example 1, except that the acid binding agent is anhydrous trisodium phosphate.
By detection, the yield of DTDM produced by the above-mentioned synthetic method of rubber vulcanizing agent DTDM was found to be 97.32% (calculated as morpholine) and the HPLC purity was found to be 99.21%.
The above embodiments are provided for illustrating the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the present invention and to implement the same, but are not intended to limit the scope of the present invention, and all equivalent changes or modifications according to the spirit of the present invention should be included in the scope of the present invention.
Claims (3)
1. The synthesis method of the rubber vulcanizing agent DTDM is characterized by comprising the following steps: adding solvent, acid binding agent and morpholine into a reaction kettle simultaneously, dropwise adding sulfur monochloride while stirring at 20-60 ℃, continuously preserving heat for reaction after the dropwise adding is finished within 2-6 hours, performing auxiliary treatment on a multi-energy field for 20-30 minutes in the reaction process, and controlling the end point of the reaction by detecting the content of the morpholine and controlling the supplementing amount of the acid binding agent so as to ensure that the added morpholine fully reacts to generate 4, 4-dithiodimorpholine; stopping stirring after reaching the reaction end point, regulating the temperature to room temperature, rotationally steaming to recover the solvent, adding water for washing 3-6 times, and drying after suction filtration to obtain the rubber vulcanizing agent DTDM; the acid binding agent is a mixture formed by mixing triethylamine, pyridine, sodium tert-butoxide and ionic liquid according to the mass ratio of 1 (0.3-0.5) to 0.3 (0.1-0.3); the multi-energy field includes ultrasonic waves, microwaves and magnetic fields; the ultrasonic frequency is 50-100kHz, and the power range is 300-500W; the frequency of the microwave treatment is 2.5-3.0GHz, and the power range is 800-1400W; the magnetic field intensity of the magnetic field treatment is 9000-16000Gs; the ionic liquid is at least one of 1-propyl-3-methylimidazole nitrate and 1, 3-dimethylimidazole nitrate; the molar ratio of the morpholine to the sulfur monochloride is 2:1.
2. The method for synthesizing rubber vulcanizing agent DTDM according to claim 1, wherein the solvent is any one of dichloromethane, toluene, benzene, petroleum ether and xylene.
3. The method for synthesizing the rubber vulcanizing agent DTDM according to claim 1, wherein the mass ratio of the solvent, the acid-binding agent and the morpholine is (8-15): (1.5-2): 1.
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| CN110330468A (en) * | 2019-08-05 | 2019-10-15 | 山东阳谷华泰化工股份有限公司 | A kind of synthetic method of 4,4 '-dithio morpholines |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US4042642A (en) * | 1972-06-26 | 1977-08-16 | The Goodyear Tire & Rubber Company | Urea additives for sulfur vulcanizable polymers |
| TWI357901B (en) * | 2004-03-12 | 2012-02-11 | Lundbeck & Co As H | Substituted morpholine and thiomorpholine derivati |
| CN108658864B (en) * | 2018-04-30 | 2020-11-13 | 杭州布朗生物医药科技有限公司 | A kind of preparation method of rubber vulcanizing agent 1,1'-dithiobiscaprolactam |
| CN113248439B (en) * | 2021-06-09 | 2024-06-14 | 顺毅南通化工有限公司 | Synthesis method of pyrazole disulfide |
| CN114853695B (en) * | 2022-05-07 | 2023-03-10 | 河南易交联新材料研究院有限公司 | Preparation method of rubber vulcanizing agent 4,4' -dithiodimorpholine |
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| CN110330468A (en) * | 2019-08-05 | 2019-10-15 | 山东阳谷华泰化工股份有限公司 | A kind of synthetic method of 4,4 '-dithio morpholines |
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