CN101724174A - Method for preparing anti-aging agent RD - Google Patents
Method for preparing anti-aging agent RD Download PDFInfo
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- CN101724174A CN101724174A CN200810155870A CN200810155870A CN101724174A CN 101724174 A CN101724174 A CN 101724174A CN 200810155870 A CN200810155870 A CN 200810155870A CN 200810155870 A CN200810155870 A CN 200810155870A CN 101724174 A CN101724174 A CN 101724174A
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Abstract
The invention belongs to the technical field of fine chemical engineering, and relates to a method for preparing anti-aging agent RD. The method comprises: under the condition of existence of resin acid catalyst, taking phenylamine and acetone as reaction raw materials for condensation reaction, and obtaining reaction mixture containing 2, 2, 4-trimethyl-1, 2-dihydro-quinoline monomer; and removing unreacted phenylamine for recovery and mechanical application. By using the resin acid catalyst for condensation, the method avoids the liquid acid corroding equipment, reduces the consumption of acid and alkali, decreases waste water quantity and relieves the environmental pollution.
Description
Technical field: the invention belongs to the fine chemical technology field, be specifically related to a kind of method for preparing anti-aging agent RD.
Background technology: anti-aging agent RD excellent property, low toxicity, do not contain carcinogenic substance, heat and oxygen aging had splendid protection effect.This product has higher restraining effect to metal catalytic oxidation, is applicable to natural rubber and various synthetic rubber and partly plastic goods, is mainly used in various tires and the cable goods that use plane tyre, high speed tire, tank track pad and torrid areas.Especially be difficult for bloom in vulcanized rubber article, volatility is low, and intermiscibility is good, and pollution level is little, and appearance luster is more shallow.In recent years, along with China's automobile and tire industry development, the demand of anti-aging agent RD is presented the trend of quick growth.
2,2,4-trimethylammonium-1,2-dihyaroquinoline are the monomers of synthetic anti-aging agent RD, two, three, the tetramer is the active princlple of anti-aging agent RD, the quality of three kinds of content sums reflection anti-aging agent RD quality producies.Present 2,2,4-trimethylammonium-1, the synthetic method of 2-dihyaroquinoline mainly is that aniline and condensation of acetone reaction make in the presence of an acidic catalyst, wherein an acidic catalyst has liquid acid catalyst and solid acid catalyst.2,2,4-trimethylammonium-1, the main production method of 2-dihyaroquinoline and polymkeric substance thereof has following several.
CN1344753A is raw material single stage method solvent-free polycondensation Synthetic 2 as catalyzer with industrial aniline and acetone with hydrochloric acid, 2, and 4-trimethylammonium-1,2-dihyaroquinoline polymer.
CN1730511A two step method Synthetic 2,2,4-trimethylammonium-1,2-dihyaroquinoline polymer.Patent is mainly introduced monomer and is purified, and is that raw material condensation reaction must comprise 2,2 as catalyzer with aniline and acetone with hydrochloric acid earlier, 4-trimethylammonium-1, the monomeric reaction mixture of 2-dihyaroquinoline, under the high-temperature low-pressure condition in the hydro carbons inert solvent neutralization and the washing reaction mixture to purify 2,2,4-trimethylammonium-1,2-dihyaroquinoline monomer makes 2,2 of purification then in the presence of acid catalyst, 4-trimethylammonium-1,2-dihyaroquinoline monomer polymerization reaction take place.
As catalyzer, the water of taking away aniline and condensation of acetone reaction generation with toluene class organic solvent prepares anti-aging agent RD to CN86100665A with hydrochloric acid.
JP56014516 is a catalyzer with tosic acid, hydrochloric acid and zinc chloride, toluene is solvent, aniline and acetone are that raw material is synthetic, concrete grammar is: add 27.9 gram aniline in reactor, 4 gram tosic acid, 2 gram zinc chloride and 6 milliliters of toluene add acetone during to 140 ℃, added acetone 34.8 grams in 5.5 hours.With 6.6 grams, 28% combined, temperature is 90 ℃, reacts 3 hours then, react 2,2,4-trimethylammonium-1,2-dihyaroquinoline dimer and trimerical weight percentage are 58%.After the catalyzer tosic acid that advantage anti-aging agent RD active princlple content height, shortcoming use, hydrochloric acid and zinc chloride consume, can not regenerate and recycle, waste liquid is many, seriously corroded, toluene toxicity are big.
JP58088363 is catalyzer with the cupric chloride, and in the presence of normal hexane, toluene, aniline and acetone are that reaction raw materials is synthetic: add 93.0 gram aniline in the reactor, 8.5 gram copper chloride dihydrate, 3.0 the gram normal hexane is heated to 85 ℃, adds 174 gram acetone then, temperature of reaction maintains 70～90 ℃, add the aqueous sodium hydroxide solution that adds 5 grams 28% behind the acetone again, 100 ml waters and 100 milliliters of toluene are by removing by filter catalyzer, the filtrate oil reservoir gets 75.9 gram polycondensates, contains dimer 48%.
As catalyzer condensation aniline and acetone, temperature of reaction is lower than 120 ℃ to JP5602026, uses concentrated hydrochloric acid as the polymerization catalyst condensated liquid again with tosic acid.Reaction finishes back dilution with toluene reaction soln, the neutralization of hydro-oxidation sodium solution.Be divided into water layer and oil reservoir after stopping to stir, branch vibration layer, oil reservoir washes with water several times.Distillation then, toluene at first steams from oil reservoir, steams low-boiling-point substance again, and residuum is the RD polymkeric substance.
US4897482 earlier makes catalyzer with tosic acid or hydrochloric acid, with aniline and acetone in toluene solvant, heating reflux reaction, reaction water and methylbenzene azeotropic are taken out of, condensation product minute removes toluene, acetone through distillation, obtains the RD monomer.Use oxalic acid, succsinic acid or other aliphatic dicarboxylic acid as catalyst again, with the monomer reacting by heating, polymerisate is removed unreacted monomer through distillation, can obtain dimer content and be 50～60% anti-aging agent RD, and yield is about 60%.This method catalyzer is not easy to obtain, and can not reclaim and apply mechanically.
At present both at home and abroad the production method of anti-aging agent RD mainly is as catalyzer aniline and acetone to be carried out polycondensation with hydrochloric acid, and except that a small amount of enterprise not the solubilizing agent, most of enterprise takes away condensation reaction water with toluene.Its principal feature is that synthetic method is simple, and flow process is short, technical maturity.Shortcoming is that wastewater flow rate is big, temperature of reaction is high, serious to equipment corrosion.
Summary of the invention: the objective of the invention is the shortcoming at above-mentioned processing method, a kind of method for preparing anti-aging agent RD of proposition can effectively solve the problem that existing processing method exists.
The inventive method is 2 of a kind of environmental protection, 2,4-trimethylammonium-1, the condensation prepared technology of 2-dihyaroquinoline polymer (anti-aging agent RD), utilize the resinous acid catalyzer to substitute liquid acid catalyst, can reduce acid, alkali that promotor RD N-process is consumed, thereby cut down the consumption of raw materials, reduce the wastewater flow rate in the reaction process.
The inventive method is achieved like this: with aniline and acetone is raw material, carries out condensation reaction in the presence of the resinous acid catalyzer, carries out as follows:
1) resinous acid catalyzer and aniline are joined in the reactor, be warming up to 110～160 ℃, the resinous acid catalyst consumption is 20～100% of an aniline weight; 2) add acetone continuously at 110～160 ℃, the mol ratio of aniline and acetone is 1: 5～20, and the control joining day is 8～24 hours; 3) condensation reaction solution is removed from reactor, added hydrochloric acid and carry out polymerization, polymerization temperature is controlled at 90～150 ℃, and polymerization time was controlled at 4～10 hours; 4) add after the polymerization alkaline solution carry out in and polymer fluid, separate and remove water and get organic phase, distill and make finished product.Further technical scheme is at first the resinous acid catalyzer to be soaked with aniline, immersion can be carried out in reactor, also can outside reactor, carry out, what the resinous acid catalyst consumption was preferably aniline weight is 30～70%, the preferable time of soaking is 0.5-1 hour, and other step is the same.
The used resinous acid catalyzer of the present invention usually is the strongly-acid exchange resin; Used strongly-acid exchange resin is the macroporous type strong-acid ion exchange resin; The used macroporous type strong-acid ion exchange resin product that to be fragrant olefines obtain through sulfonation and high temperature resistant processing; Used resinous acid catalyzer also can be macropore fragrance olefines storng-acid cation exchange resin; The fragrance olefines is polystyrene, divinyl benzene series.
The resinous acid catalyzer is reusable; The mol ratio of reaction raw materials aniline and acetone is 1: 5～20, best 1: 8～15; Setting-up point is 110～160 ℃, best 120～140 ℃; Condensation reaction time is 8～24 hours, best 10～18 hours; Polymerization temperature is 90～150 ℃, best 100～115 ℃; Polymerization time is 4～10 hours, best 5～6 hours.
According to processing method synthetic anti-aging agent RD of the present invention, active princlple 2,2,4-trimethylammonium-1,2-dihyaroquinoline two, three, tetramer content are greater than 50%, and oxious component IBA (isopropyl diphenyl amine) is less than 0.3%.Domestic manufacturer's anti-aging agent RD is the best in quality at present is active princlple 2,2,4-trimethylammonium-1, and 2-dihyaroquinoline two, three, tetramer content 48%, synthetic anti-aging agent RD of the present invention are better than present domestic anti-aging agent RD quality product.
Compared with prior art, the present invention has following advantage:
1) be condensation catalyst with respect to hydrochloric acid and tosic acid, the present invention has avoided the corrosion of catalyzer to condensation equipment, has reduced the wastewater flow rate of producing anti-aging agent RD;
2) be condensation catalyst with respect to cupric chloride, the present invention reduces catalyst removal step;
3) with respect to condensation catalysts such as hydrochloric acid, tosic acid, cupric chlorides, catalyzer of the present invention can be applied mechanically continuously;
4) the present invention does not use plus solvent, has reduced the solvent recuperation process;
5) the synthetic anti-aging agent RD quality product of the inventive method is better, and active princlple can reach 2,2,4-trimethylammonium-1, and 2-dihyaroquinoline two, three, tetramer content are greater than 50%.
Embodiment: the present invention is described in detail below in conjunction with embodiment.
Embodiment 1: having thermometer, add 100 gram aniline in the condensation reactor of reflux exchanger and soak 70 gram resinous acid catalyzer, add 100 gram aniline again and be warming up to 130 ℃, continuous speed with 100 milliliters/hour adds acetone, reaction was kept 10 hours, water generation reaction is taken away by acetone, after finishing, reaction gets 145 gram condensated liquids, add 9 grams, 30% hydrochloric acid 105 ℃ of polymerizations 5 hours, sodium hydroxide solution neutralization with 10 grams 15%, after anhydrating mutually, branch carries out vacuum distilling, remove 50 gram foreshots and get 93 gram anti-aging agent RD finished products, yield is 97.89%, active princlple 2,2,4-trimethylammonium-1,2-dihyaroquinoline two, three, tetramer content 51.3%, oxious component IBA (isopropyl diphenyl amine) 0.28%.The foreshot recovery set is used for condensation reaction.
Embodiment 2: operational condition is with embodiment 1, but hold time in reaction is 12 hours, after finishing, reaction gets 162 gram condensated liquids, add 10 grams, 30% hydrochloric acid 105 ℃ of polymerizations 5 hours, sodium hydroxide solution neutralization with 11.1 grams 15%, after anhydrating mutually, branch carries out vacuum distilling, remove 49 gram foreshots and get 111 gram anti-aging agent RD finished products, yield is 98.23%, active princlple 2,2,4-trimethylammonium-1,2-dihyaroquinoline two, three, tetramer content 55.8%, oxious component IBA (isopropyl diphenyl amine) 0.28%.The foreshot recovery set is used for condensation reaction.
Embodiment 3: operational condition is with embodiment 1, but hold time in reaction is 16 hours, after finishing, reaction gets 170 gram condensated liquids, add 10.5 grams, 30% hydrochloric acid 105 ℃ of polymerizations 5 hours, sodium hydroxide solution neutralization with 11.7 grams 15%, after anhydrating mutually, branch carries out vacuum distilling, remove 49 gram foreshots and get 119 gram anti-aging agent RD finished products, yield is 98.34%, active princlple 2,2,4-trimethylammonium-1,2-dihyaroquinoline two, three, tetramer content 53.2%, oxious component IBA (isopropyl diphenyl amine) 0.27%.The foreshot recovery set is used for condensation reaction.
Embodiment 4: operational condition is with embodiment 1, but add acetone with 80 milliliters/hour speed, after finishing, reaction gets 138 gram condensated liquids, add 9 grams, 30% hydrochloric acid 105 ℃ of polymerizations 5 hours, sodium hydroxide solution neutralization with 10 grams 15%, after anhydrating mutually, branch carries out vacuum distilling, remove 54 gram foreshots and get 82 gram anti-aging agent RD finished products, yield is 97.62%, active princlple 2,2,4-trimethylammonium-1,2-dihyaroquinoline two, three, tetramer content 54.1%, oxious component IBA (isopropyl diphenyl amine) 0.20%.The foreshot recovery set is used for condensation reaction.
Embodiment 5: operational condition is with embodiment 1, but add acetone with 120 milliliters/hour speed, after finishing, reaction gets 152 gram condensated liquids, add 9.5 grams, 30% hydrochloric acid 105 ℃ of polymerizations 5 hours, sodium hydroxide solution neutralization with 10.4 grams 15%, after anhydrating mutually, branch carries out vacuum distilling, remove 49 gram foreshots and get 101 gram anti-aging agent RD finished products, yield is 98.06%, active princlple 2,2,4-trimethylammonium-1,2-dihyaroquinoline two, three, tetramer content 52.7%, oxious component IBA (isopropyl diphenyl amine) 0.29%.The foreshot recovery set is used for condensation reaction.
Claims (10)
1. method for preparing anti-aging agent RD, with aniline and acetone is raw material, it is characterized in that in the presence of the resinous acid catalyzer, carrying out condensation reaction, carry out as follows: 1) resinous acid catalyzer and aniline are joined in the reactor, be warming up to 110～160 ℃, the resinous acid catalyst consumption is 20～100% of an aniline weight; 2) add acetone continuously at 110～160 ℃, the mol ratio of aniline and acetone is 1: 5～20, and the control joining day is 8～24 hours; 3) condensation reaction solution is removed from reactor, added hydrochloric acid and carry out polymerization, polymerization temperature is controlled at 90～150 ℃, and polymerization time was controlled at 4～10 hours; 4) add after the polymerization alkaline solution carry out in and polymer fluid, separate and remove water and get organic phase, distill and make finished product.
2. method according to claim 1 is characterized in that the resinous acid catalyzer is soaked with aniline earlier, adds in the reactor then.
3. method according to claim 1 is characterized in that the resinous acid catalyzer is soaked with aniline in reactor.
4. method according to claim 1 is characterized in that the resinous acid catalyzer is the macroporous type strong-acid ion exchange resin.
5. method according to claim 1 is characterized in that used resinous acid catalyzer is a macropore fragrance olefines storng-acid cation exchange resin.
6. according to claim 4 or 5 described methods, it is characterized in that fragrant olefines is polystyrene, divinyl benzene series.
7. method according to claim 1 is characterized in that the repeated use of resinous acid catalyzer.
8. method according to claim 1, the mol ratio of its characteristic reaction raw material aniline and acetone be preferably 1: 8～and 15.
9. method according to claim 1 is characterized in that the resinous acid catalyst consumption is 30～70% of an aniline charge weight.
10. method according to claim 1 is characterized in that 120～140 ℃ of setting-up point; Condensation reaction time 10～18 hours; Polymerization temperature is 100～115 ℃, and polymerization time is 5～6 hours.
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| CN200810155870A CN101724174A (en) | 2008-10-17 | 2008-10-17 | Method for preparing anti-aging agent RD |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102584696A (en) * | 2012-02-28 | 2012-07-18 | 徐州工业职业技术学院 | Catalytic synthesis method for rubber antioxidant RD |
| CN105348189A (en) * | 2014-08-20 | 2016-02-24 | 中国石油化工股份有限公司 | Continuous 2,2,4-trimethyl-1,2-dihydroquinoline preparation method |
| CN110590657A (en) * | 2019-09-16 | 2019-12-20 | 山东尚舜化工有限公司 | Equipment and process for full-automatic continuous production of antioxidant RD |
| CN111039865A (en) * | 2018-10-15 | 2020-04-21 | 中国石油化工股份有限公司 | Preparation method of anti-aging agent TMQ |
| CN112657488A (en) * | 2019-10-15 | 2021-04-16 | 中石化南京化工研究院有限公司 | Polyacid type solid catalyst |
| CN114315712A (en) * | 2020-09-27 | 2022-04-12 | 中石化南京化工研究院有限公司 | Method for purifying 2,2, 4-trimethyl-1, 2-dihydroquinoline polymer |
| CN114773264A (en) * | 2022-06-20 | 2022-07-22 | 科迈(天津)建设工程股份有限公司 | Preparation device and preparation method of rubber antioxidant TMQ |
-
2008
- 2008-10-17 CN CN200810155870A patent/CN101724174A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102584696A (en) * | 2012-02-28 | 2012-07-18 | 徐州工业职业技术学院 | Catalytic synthesis method for rubber antioxidant RD |
| CN102584696B (en) * | 2012-02-28 | 2013-11-06 | 徐州工业职业技术学院 | Catalytic synthesis method for rubber antioxidant RD |
| CN105348189A (en) * | 2014-08-20 | 2016-02-24 | 中国石油化工股份有限公司 | Continuous 2,2,4-trimethyl-1,2-dihydroquinoline preparation method |
| CN111039865A (en) * | 2018-10-15 | 2020-04-21 | 中国石油化工股份有限公司 | Preparation method of anti-aging agent TMQ |
| CN110590657A (en) * | 2019-09-16 | 2019-12-20 | 山东尚舜化工有限公司 | Equipment and process for full-automatic continuous production of antioxidant RD |
| CN112657488A (en) * | 2019-10-15 | 2021-04-16 | 中石化南京化工研究院有限公司 | Polyacid type solid catalyst |
| CN114315712A (en) * | 2020-09-27 | 2022-04-12 | 中石化南京化工研究院有限公司 | Method for purifying 2,2, 4-trimethyl-1, 2-dihydroquinoline polymer |
| CN114773264A (en) * | 2022-06-20 | 2022-07-22 | 科迈(天津)建设工程股份有限公司 | Preparation device and preparation method of rubber antioxidant TMQ |
| CN114773264B (en) * | 2022-06-20 | 2022-09-30 | 科迈化工股份有限公司 | Preparation device and preparation method of rubber antioxidant TMQ |
| WO2023245776A1 (en) * | 2022-06-20 | 2023-12-28 | 科迈化工股份有限公司 | Apparatus and method for preparing rubber antioxidant tmq |
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Application publication date: 20100609 |