CN1344753A - Solventless one-step process of synthesizing 2,2,4-trimethyl-1,2-dihydroquinoline polymer - Google Patents
Solventless one-step process of synthesizing 2,2,4-trimethyl-1,2-dihydroquinoline polymer Download PDFInfo
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- CN1344753A CN1344753A CN 01134117 CN01134117A CN1344753A CN 1344753 A CN1344753 A CN 1344753A CN 01134117 CN01134117 CN 01134117 CN 01134117 A CN01134117 A CN 01134117A CN 1344753 A CN1344753 A CN 1344753A
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- aniline
- acetone
- hydrochloric acid
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- dihyaroquinoline
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Abstract
The present invention relates to the synthesis of one kind of antiagers for rubber and plastic. The synthesis utilizes industrial aniline and acetone as material and hydrochloric acid as catalyst and includes the processes of addition of aniline and hydrochloric acid in the molar ratio of 0.15-0.60 in a reactor, dropping acetone in 2-12 times molar weight of aniline at 85-180 deg.c, continuous stirring for 10-12 hr to complete condensation polymerization in one step, adding liquid alkali to neutralize the product, separating to eliminate water phase, distillation, cooling and shaping so as to get finished product.
Description
One, technical field
The present invention is a kind of synthetic method that is mainly used in the anti-aging agent of rubber and plastics, especially a kind of solventless one-step Synthetic 2,2,4-trimethylammonium-1, the polymeric method of 2-dihyaroquinoline.
Two, background technology
2,2,4-trimethylammonium-1,2-dihyaroquinoline polymer is commonly called as anti-aging agent RD (Antioxidant RD), mainly as rubber antioxidant, aging stronger restraining effect is arranged to what heat and oxygen caused, is widely used in industries such as rubber, plastics.
The anti-aging agent RD synthesis route has multiple, normally in the presence of solvent, is raw material with aniline and acetone, under the effect of an acidic catalyst, forms through polycondensation.On technology, previous employing so-called " two-step synthesis ", promptly on flow process condensation reaction and polyreaction be divided into two the step carry out, condensation reaction herein means that aniline and acetone dehydrating condensation generate 2,2,4-trimethylammonium-1,2-dihyaroquinoline monomer (hereinafter to be referred as " hydrogenated quinoline monomer "), polyreaction means that the further polymerization of hydrogenated quinoline monomer generates polymer.In recent years, progressively adopt both at home and abroad " one-step synthesis ", promptly above-mentioned two processes are once finished in reactor, and the centre need not to prepare the hydrogenated quinoline monomer earlier and reacts the method that makes target compound again.Comparatively speaking, it is simple that " single stage method " has synthetic method, and flow process is short, yield height, advantage such as the three wastes are few.The early 1990s, the synthesis technique of Research Inst., of Applied Chemistry, Shanxi Prov.'s exploitation (is seen " research of anti-aging agent RD novel process ", " Shanxi chemical industry " 1994.1 phases), be to be catalyzer with hydrochloric acid, raw material aniline, acetone and solvent toluene are at first carried out polycondensation in reactor, reaction is finished after neutralize, wash, and redistillation removal toluene, unreacted aniline and hydrogenated quinoline monomer can get part anti-aging agent RD finished product; The hydrogenated quinoline monomer that steams through processes such as polymerization, neutralization, washings, can obtain another part anti-aging agent RD finished product again, and two portions total yield of products can reach about 90%.People such as the king of Northeast Normal University grace ripple adopt heteropoly acid catalysis single stage method production anti-aging agent RD (to see " being that the catalyzer single stage method is produced the anti-aging agent RD interim test with the heteropolyacid ", CSTAD), condensation reaction in the presence of heteropolyacid catalyst generates the hydrogenated quinoline monomer by aniline and acetone in system, monomer polymerization becomes the polymer of n=2-4 simultaneously, after the neutralization washing, steam solvent and get product.This process using heteropoly acid catalysis is though catalytic activity is higher, more expensive than industrial hydrochloric acid price commonly used.
In " single stage method " synthetic anti-aging agent RD technology, introduce plus solvent such as toluene etc., be considered to one of significant improvement of anti-aging agent RD synthesis technique, reason is that plus solvent can play multiple effect: the one, add solvent, by the water that component distillation is constantly taken reaction out of and generated, can make reaction continue to carry out; The 2nd, reaction later stage material viscosity increases, and adds solvent and can improve material fluidity, helps operations such as neutralization, washing thereafter.But the introducing of plus solvent makes that this operation link of solvent recuperation is essential, has both increased equipment and the pipeline in the production equipment, the consumption that brings solvent again inevitably, and this just makes this technology material consumption, energy consumption increase the increase that brings product cost.The increase of operation link also makes Production Flow Chart comparatively complicated.
Three, summary of the invention
(1) goal of the invention
Purpose of the present invention just provides a kind of with aniline, acetone direct condensation generation anti-aging agent RD, need not to add in addition the solventless one-step Synthetic 2 of solvent toluene, and 2,4-trimethylammonium-1, the polymeric method of 2-dihyaroquinoline.
(2) technical scheme
Solventless one-step Synthetic 2 of the present invention, 2,4-trimethylammonium-1, the polymeric method of 2-dihyaroquinoline is to be raw material with industrial aniline and acetone, with hydrochloric acid is catalyzer, under the normal pressure, add the hydrochloric acid of aniline and 30% in the reactor, hydrochloric acid: aniline=0.15～0.60: 1 (mol ratio), in being 85～180 ℃ of scopes, temperature drips acetone, acetone: aniline=2～12: 1 (mol ratio), continuously stirring 10～12 hours, a step is finished polycondensation in reactor, add in the liquid caustic soda and above-mentioned reaction product, after water is removed in separation, carry out the finished product distillation, the gained reaction mass is through cooling in the still, shaping can make finished product.The temperature of polycondensation is that the liquid caustic soda of 140 ℃～160 ℃ usefulness that are used to neutralize is 12～18% aqueous sodium hydroxide solution.
Principal reaction equation of the present invention is:
(1) condensation reaction
(2) polyreaction
Following mask body association reaction condition, proportioning raw materials, it is as follows by following four key steps in detail technical process to be described in detail:
The first step: polycondensation
Under the normal pressure, the hydrochloric acid that in reactor, adds a certain amount of aniline and 30%, hydrochloric acid: aniline=0.15-0.60: 1 (best 0.30-0.40: 1) (mol ratio), be warming up to 85～180 ℃ (best 140～160 ℃), under this temperature, drip acetone continuously, acetone: aniline=2-12: 1 (best 5-7: 1) (mol ratio), aniline and acetone are carried out polycondensation under the hydrochloric acid catalysis effect, lasting 10～12 hours of reaction.Water that reaction generates and excessive acetone steam in the lump, are collected in after condensation in the basin, treat the 4th step recovery raw material aniline and acetone wherein, apply mechanically to this step in next pot again.
Second step: neutralization
The aqueous sodium hydroxide solution of above-mentioned reaction product adding 15% carries out neutralization reaction.After reaction is finished, separate and to remove water, what obtain organicly treats each other next step processing.
The 3rd step: finished product distillation
With the organic phase of the second step gained, under vacuum condition, distill.Receiving with basin after the lower component condensation of the boiling point that steams, is to be foreshot, mainly comprises unreacted raw material aniline and a small amount of hydrogenated quinoline monomer, and foreshot is applied mechanically to abovementioned steps one in next pot.
After foreshot is removed in distillation, be the anti-aging agent RD finished product in the still.
The 4th step: acetone reclaims
The aforementioned the first step collected condensation product in reaction process is mainly the water that is generated in unreacted raw material acetone, minor amounts of aniline and the reaction, and wherein raw material need give recovery.Acetone reclaims the atmospheric distillation method that adopts.Acetone is accepted with basin through condensation, can be used as raw materials for production and applies mechanically to next pot time step 1.Be divided into two layers after the resistates cooling in the still, lower floor's water, upper oil phase is mainly unreacted raw material aniline.Above-mentioned two-phase is after separating, and oil phase aniline is applied mechanically to next pot time step 1.
(3) technique effect
The invention has the advantages that:
The present invention adopts be easy to get industrial raw material aniline and acetone, is catalyzer with the technical hydrochloric acid, and an one-step polycondensation synthesizes anti-aging agent RD, has advantages such as synthetic method is simple, flow process is short, yield is high, the three wastes are few.Than prior art, owing in technical process, got rid of the use of plus solvent toluene, reduced the toluene removal process, therefore flow process is simplified, and material consumption reduces, and is easy and simple to handle, and the products production cost reduces.Than existing technology, wastewater flow rate also has minimizing.In specific words, the present invention is than existing anti-aging agent RD synthesis technique, advantage be mainly reflected in following some:
The first, this technology need not to use plus solvent toluene by changing proportioning raw materials and processing condition in technical process, reduced toluene thus in the flow arrangement and reclaimed this link, makes process simplification, operates easier; And material consumption, energy consumption descend to some extent, reduced product cost.
The second, processing arrangement of the present invention is after polycondensation is finished, reaction product in adding liquid caustic soda and after, must can directly not carry out the finished product distillation again through washing, final product quality is not brought any disadvantageous effect, therefore compare existing synthesis technique, wastewater flow rate reduces to some extent.
The 3rd, because the change of processing condition, the soda acid consumption that uses in the technological process of the present invention reduces.
The 4th, the synthetic anti-aging agent RD product yield of the inventive method is higher, can reach 98%; And quality product increases.
The 5th, because of having saved washing in the technical process and having reclaimed the toluene two procedures, shorten when finishing the platform of whole process flow; And reaction conditions relaxes, smooth operation.
The 6th, on industrial application because the simplification of technical process, than prior art, the present invention will save equipment component, reduce investment and expense that whole device moves.
With method synthetic anti-aging agent RD of the present invention, product yield can reach 98%, and quality is compared with existing synthetic technology and increased.
Four, embodiment
Embodiment of the present invention are as follows:
In the four-hole bottle that the 500mL band stirs, adding 64 gram aniline, 56 gram foreshots and 42 gram concentration are 30% hydrochloric acid, stir and be warming up to 140-150 ℃, drip 348 gram acetone (comprising recovery set acetone) continuously.Carry out polycondensation with this understanding, keep 12 hours reaction times.Water that reaction generates and excessive acetone steam in the lump, after condensation, collect 312 grams.After reaction was finished, adding 60 gram concentration were 15% aqueous sodium hydroxide solution, keep 90-100 ℃, continuously stirring 1.5 hours.To carry out vacuum distilling behind the above-mentioned material branch vibration layer, temperature≤135 ℃ following foreshot 56 grams of collecting.After removing foreshot, promptly get the anti-aging agent RD finished product in the still.Get finished product 117.5 grams, yield 99.27%.88.2 ℃ of finished product softening temperatures.
Claims (5)
1. solventless one-step Synthetic 2,2,4-trimethylammonium-1, the polymeric method of 2-dihyaroquinoline, it is characterized in that with industrial aniline and acetone be raw material, is catalyzer with hydrochloric acid, under the normal pressure, the hydrochloric acid that adds aniline and 30% in the reactor, hydrochloric acid: aniline=0.15～0.60: 1 (mol ratio) drips acetone, acetone: aniline=2～12 in temperature is 85～180 ℃ of scopes: 1 (mol ratio), continuously stirring 10～12 hours, a step is finished polycondensation in reactor, adds in the liquid caustic soda and above-mentioned reaction product, after water is removed in separation, carry out the finished product distillation, the gained reaction mass is through cooling in the still, shaping can make finished product.
2. a kind of solventless one-step Synthetic 2 according to claim 1,2,4-trimethylammonium-1, the polymeric method of 2-dihyaroquinoline, it is characterized in that aniline in reactor and 30% hydrochloric acid ratio are hydrochloric acid: aniline=0.30～0.40: 1 (mol ratio), the ratio of acetone and aniline are acetone: aniline=5～7: 1 (mol ratio).
3. a kind of solventless one-step Synthetic 2 according to claim 1 and 2,2,4-trimethylammonium-1, the polymeric method of 2-dihyaroquinoline, the temperature that it is characterized in that polycondensation are 140 ℃～160 ℃.
4. a kind of solventless one-step Synthetic 2 according to claim 1 and 2,2,4-trimethylammonium-1, the polymeric method of 2-dihyaroquinoline, the liquid caustic soda of the usefulness that it is characterized in that being used to neutralizing is 12～18% aqueous sodium hydroxide solution.
5. a kind of solventless one-step Synthetic 2 according to claim 1 and 2,2,4-trimethylammonium-1, the polymeric method of 2-dihyaroquinoline is characterized in that finished product distillation carries out under vacuum condition.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011341173A CN1157429C (en) | 2001-10-30 | 2001-10-30 | Solventless one-step process of synthesizing 2,2,4-trimethyl-1,2-dihydroquinoline polymer |
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| CNB011341173A CN1157429C (en) | 2001-10-30 | 2001-10-30 | Solventless one-step process of synthesizing 2,2,4-trimethyl-1,2-dihydroquinoline polymer |
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| CN1344753A true CN1344753A (en) | 2002-04-17 |
| CN1157429C CN1157429C (en) | 2004-07-14 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101353447B (en) * | 2008-08-27 | 2011-09-28 | 河南省开仑化工有限责任公司 | Synthetic process of rubber antiager RD |
| CN103214640A (en) * | 2013-03-27 | 2013-07-24 | 科迈化工股份有限公司 | Production method of rubber antioxidant TMQ |
| CN109665991A (en) * | 2017-10-16 | 2019-04-23 | 中国石油化工股份有限公司 | A kind of preparation method of anti-aging agent TMQ |
| CN110747241A (en) * | 2018-07-24 | 2020-02-04 | 中国石油化工股份有限公司 | Preparation method of 2,2, 4-trimethyl-1, 2-dihydroquinoline |
| CN111039864A (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 |
| CN114315713A (en) * | 2020-10-10 | 2022-04-12 | 中石化南京化工研究院有限公司 | Preparation method of low primary amine TMQ (tetramethylammonium terephthalate) antioxidant |
-
2001
- 2001-10-30 CN CNB011341173A patent/CN1157429C/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101353447B (en) * | 2008-08-27 | 2011-09-28 | 河南省开仑化工有限责任公司 | Synthetic process of rubber antiager RD |
| CN103214640A (en) * | 2013-03-27 | 2013-07-24 | 科迈化工股份有限公司 | Production method of rubber antioxidant TMQ |
| CN109665991A (en) * | 2017-10-16 | 2019-04-23 | 中国石油化工股份有限公司 | A kind of preparation method of anti-aging agent TMQ |
| CN109665991B (en) * | 2017-10-16 | 2022-08-23 | 中国石油化工股份有限公司 | Preparation method of anti-aging agent TMQ |
| CN110747241A (en) * | 2018-07-24 | 2020-02-04 | 中国石油化工股份有限公司 | Preparation method of 2,2, 4-trimethyl-1, 2-dihydroquinoline |
| CN110747241B (en) * | 2018-07-24 | 2023-05-02 | 中国石油化工股份有限公司 | Preparation method of 2, 4-trimethyl-1, 2-dihydroquinoline |
| CN111039864A (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 |
| CN111039864B (en) * | 2018-10-15 | 2022-10-18 | 中国石油化工股份有限公司 | Preparation method of anti-aging agent |
| CN114315713A (en) * | 2020-10-10 | 2022-04-12 | 中石化南京化工研究院有限公司 | Preparation method of low primary amine TMQ (tetramethylammonium terephthalate) antioxidant |
| CN114315713B (en) * | 2020-10-10 | 2024-01-30 | 中石化南京化工研究院有限公司 | Preparation method of low primary amine TMQ (TMQ) anti-aging agent |
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| CN1157429C (en) | 2004-07-14 |
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