CN108003095A - A kind of antioxidant TMQ and preparation method thereof - Google Patents

A kind of antioxidant TMQ and preparation method thereof Download PDF

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Publication number
CN108003095A
CN108003095A CN201610967017.3A CN201610967017A CN108003095A CN 108003095 A CN108003095 A CN 108003095A CN 201610967017 A CN201610967017 A CN 201610967017A CN 108003095 A CN108003095 A CN 108003095A
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acetone
tmq
reaction
aniline
preparation
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刘建
韦志强
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China Petroleum and Chemical Corp
Research Institute of Sinopec Nanjing Chemical Industry Co Ltd
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China Petroleum and Chemical Corp
Research Institute of Nanjing Chemical Industry Group Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/04—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms
    • C07D215/06—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms having only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, attached to the ring nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3432—Six-membered rings
    • C08K5/3437—Six-membered rings condensed with carbocyclic rings

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

A kind of antioxidant TMQ of the present invention and preparation method thereof.With aniline and acetone（Or isopropylidene acetone）For raw material, one-step method prepares rubber antioxidant TMQ under the action of catalyst, and catalyst includes titanate ester catalyst.Rubber antioxidant TMQ is the antioxidant that the above method is prepared.The present invention can use intermittent or continous way production technology.Its conversion per pass can reach more than 80% in terms of aniline, the effective body contents of product TMQ (two, three, the tetramer) are up to 65 75%, compared with prior art, rubber antioxidant TMQ is prepared using titanate catalyst, with it is easy to operate, catalyst consumption is low, the greenization technique that cost is relatively low, effective body content is higher.

Description

A kind of antioxidant TMQ and preparation method thereof
Technical field
The invention belongs to technical field of fine, is related to a kind of preparation method of antioxidant TMQ, is a kind of environmentally protective Preparation process.
Background technology
Antioxidant TMQ is two, three, four condensates of 2,2,4- trimethyl -1,2- dihyaroquinolines, also known as anti-aging agent RD, It is a kind of ketone amines antioxidants, moors coloured particles or thin slice to ruins to be faint yellow, be mainly used as rubber antioxidant, be domestic and international market On one of the rubber antioxidant product that has the call.
Its raw material of the synthesis of antioxidant TMQ is mainly aniline and acetone（Or derivatives thereof）, technique can substantially be divided into " a step Method " or two kinds of " two-step method "." one-step method " is：Condensation, polymerisation occur under catalyst action for aniline, acetone, directly To two containing 2,2,4- trimethyl -1,2- dihyaroquinolines, three, four polymeric antioxidant TMQ polycondensation liquid, TMQ polycondensations liquid warp Liquid caustic soda neutralizes, divides water, distillation etc. to obtain TMQ." two-step method " is aniline, acetone condensation reaction under catalyst action, reaction solution Or the reaction solution after neutralizing obtains 2,2,4- trimethyl -1,2- dihyaroquinolines, that is, TMQ monomers by distillation or rectifying, afterwards The polymerisation under catalyst action, obtain 2,2,4- trimethyl -1,2- dihyaroquinolines two, three, four polymerize TMQ monomers again Body, then it is neutralized, divide water, distillation obtain antioxidant TMQ.Sometimes for accelerate reaction process, and can add in the reaction toluene, Dimethylbenzene, hexamethylene equal solvent, therefore TMQ synthetic methods can be divided into " solvent method " or " solventless method " etc. again.Used acidity Catalyst, to reach ideal reaction effect, generally require needs to select not in the different phase that monomer is condensed and is polymerize Same catalyst, the catalyst are difficult recycling.
Japan Patent JP58088363, which is disclosed, to be reported using salt acid as catalyst to prepare antioxidant TMQ, it is post-processed When need to use in substantial amounts of sodium hydroxide and hydrochloric acid, and hydrochloric also outstanding method recycling Ran Liyong.In addition, exist in hydrochloric acid Under, aniline conversion can be caused relatively low, poor product quality, one is useless seriously polluted, while pair sets and each to require high, production cycle length. CN1730511A hydrochloric acid methods synthesize 2,2,4- trimethyl -1,2- dihyaroquinoline monomers.Patent is catalyst with hydrochloric acid, aniline and Acetone carries out condensation reaction for raw material and obtains the reaction mixture containing 2,2,4- trimethyl -1,2- dihyaroquinoline monomers, in height Under warm lower pressure in hydro carbons atent solvent in and and washing reaction mixture to purify 2,2,4- trimethyl -1,2- dihydros Quinoline monomer.For JP56014516 using p-methyl benzenesulfonic acid and zinc chloride as catalyst, toluene is that solvent, aniline and acetone close for raw material Into 2,2,4- trimethyl -1,2- dihyaroquinoline monomers.This method is disadvantageous in that the catalyst p-methyl benzenesulfonic acid used After being consumed with zinc chloride, it is impossible to which regeneration and recycling, produce more waste liquid, etching apparatus.JP56020026 is with to first For benzene sulfonic acid as catalyst, aniline and acetone are raw material, synthesize 2,2,4- trimethyl -1,2- dihyaroquinolines.JP58088363 It is that JP5602026 is improved, adds n-hexane, n-hexane azeotrope with water takes away reaction water.JP61015873 is with HF-BF3 For catalyst, in solvent（CH3）2C（OH）CH2COCH3And CH3COCH=C（CH3）2In the presence of, aniline and acetone carry out for raw material Condensation reaction, solvent and catalyst are all more special, are difficult to obtain.JP58136625 using copper chloride as catalyst, aniline and Acetone is reaction raw materials, and catalyst amount is the 5% of aniline（Molar ratio）.It is difficult to layering in the method and when washing and is difficult to filter Remove catalyst.JP57011967 and EP01893834 are with BF3Aniline is condensed for catalyst and acetone, aniline conversion are low.Make Boron trifluoride for catalyst is difficult not only obtained and expensive, and toxicity is big, makes after boron trifluoride and its decomposition product in addition Into water pollution.CN200810141134 is catalyst with oxide type solid strong acid, and 2,2,4- must be contained by being condensed aniline and acetone The reaction solution of trimethyl -1,2- dihyaroquinoline.Catalyst needs filtration washing, and reaction temperature is high, big energy-consuming.CN102153511 Disclose one kind and prepare 2,2,4- trimethyl -1,2- dihyaroquinoline condensates（Antioxidant TMQ）Method, this method is by aniline With acetone to continuously enter the reaction tower equipped with solid acid catalyst, reactant is condensed again, and this method is easy to operate, waste water Measure small, but solid acid catalyst is difficult to use in the industrialized production of this technique.
In the synthetic method of traditional antioxidant TMQ, either one-step method or two-step method, use acid to be deposited for catalyst Big using hydrochloric acid, sulfuric acid, ferric trichloride, benzene sulfonic acid, the quantity of three wastes such as p-methyl benzenesulfonic acid, the problem of seriously corroded, using negative Load type acid catalyst constrains the security of TMQ productions and can hold there is expensive, toxicity is big or unrenewable problem Continuous property.
The content of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide one kind raising stability, change The preparation method of the pollution of corrosion and environment of the catalyst to equipment is used in kind antioxidant TMQ production processes.
The present invention provides a kind of preparation method of antioxidant TMQ.The preparation method is included with aniline and acetone（Or isopropylidene Acetone）For raw material, one-step method prepares rubber antioxidant TMQ under the action of catalyst, and catalyst includes titanate ester catalyst.
Usually, the titanate ester catalyst is tetraisopropyl titanate, isopropyl titanate, tetrabutyl titanate, titanium One kind in sour diisopropyl ester, tetra-n-butyl titanate, metatitanic acid di-isooctyl.
The reaction temperature that the one-step method prepares rubber antioxidant TMQ is 90 ~ 150 DEG C, and the reaction time is small for 1 ~ 10 When.
Further, the reaction temperature that the one-step method prepares rubber antioxidant TMQ is 110 ~ 130 DEG C, the reaction time For 4 ~ 6 it is small when.
The aniline and the weight ratio of acetone are 1:1 ~ 6, the weight ratio of titanate esters and aniline is 0.0005 ~ 0.05:1.
Further, the weight ratio of the aniline and acetone is 1:1.5~4；Titanate esters and the weight ratio of aniline are 1: 0.002~0.01。
The one-step method prepares rubber antioxidant TMQ and uses intermittent or continous way production technology.
When using batch tank catalytic reaction mode, raw material aniline and titanate esters are disposably put into kettle, acetone is adopted Fed with continuous dropwise addition mode, the charging reaction time be generally 2 ~ 7 it is small when, be preferably 4 ~ 5 it is small when.Under normal pressure, control reaction Temperature is 90 ~ 150 DEG C, is preferably 110 ~ 130 DEG C, and recycling acetone is directly separated by the fractionating column on reaction kettle, then by acetone Set is used in raw material storage tank.
When using continuous tower-type catalytic reaction (also known as fixed bed or trickle bed reaction) mode, by aniline, titanate esters from Tower top continuous feed, acetone, from bottom of towe gas-phase feed, carry out successive reaction after vaporization in tower.Under normal pressure, control reaction Temperature is 90 ~ 150 DEG C, is preferably 110 ~ 130 DEG C.When material residence time in tower is 3 ~ 7 small, when being preferably 4 ~ 6 small.Will Acetone steams at the same time with the water produced in reaction process, after recycling acetone is directly separated by fractionating column, simultaneous reactions generation Antioxidant TMQ polycondensation reaction liquid etc. continuously flows into bottom of towe receiving slit.
TMQ polycondensations liquid in reaction kettle or dump tank is added liquid caustic soda to neutralize, stratification, oil phase is true in -0.098MPa Under sky, 180-260 DEG C of material temperature is controlled, is preferably 200 ~ 230 DEG C, it is mono- to be distilled to recover unreacted raw material aniline, unpolymerized TMQ Body set is used in reacting.After the cooling of kettle material, antioxidant TMQ finished products are made through being granulated, effectively body TMQ bis-, three, four is poly- in its product Body content reaches 60 ~ 75 %.
Beneficial effect：
1st, using aniline and acetone as raw material, in the presence of titanate catalyst, one-step method is solvent-free to prepare antioxidant TMQ, with benzene Its conversion per pass of amine meter can reach more than 80%, and the effective body contents of product TMQ (two, three, the tetramer) are up to 65 ~ 75%.
2nd, compared with prior art, rubber antioxidant TMQ is prepared using titanate catalyst, have it is easy to operate, urge Agent consumption is low, the green preparation process that cost is relatively low, effective body content is higher.
3rd, the titanate ester catalyst in the present invention can be used for intermittent reaction or autoclave is continuous, tower numerous reactions such as continuous In form, so production capacity does not limit, larger with production capacity so as to realize continuous production, energy consumption, consumption are relatively low, raw Produce the more low advantage of cost.
Embodiment
The detailed content of the present invention is further illustrated below in conjunction with embodiment.
Embodiment 1
Batch tank reactive mode:The aniline of 250g and 5g metatitanic acid diisopropyl esters are put into 1000m1 with blender, temperature In the four-hole boiling flask of meter and discharging pipeline (being connected to a fractionating column, make the water that acetone is produced with reaction enter fractionating column). Under normal pressure, 1500g acetone is fed by the way of metering pump continuous charging, when the charging reaction time is 6 small, control reaction temperature Spend for 130 DEG C, antioxidant TMQ feed liquids are made.Water caused by reaction, by fractionating column, can recycle at the same time with excessive acetone Acetone, and the water that reaction produces is separated, aniline conversion per pass can reach 80% in reaction.Afterwards by antioxidant TMQ feed liquids, add 3g liquid caustic soda neutralizes, static layering, and lower floor waste water carried out waste water treatment system, under the feed liquid process -0.098MPa vacuum of upper strata, is subtracted After pressure is distilled to recover unreacted aniline, unpolymerized TMQ monomers are further distilled to recover, control 220 DEG C of material temperature, the aniline of recycling Continue set with monomer to be used in reacting.After the cooling of kettle material, 340g antioxidant TMQ finished products are made through being granulated, once through yield 81.8%, Effective body (two, three, the tetramer) content reaches 70.2%, aniline and monomer set for be condensed and polymerisation after, product TMQ's Effective yield 98.2%.
Embodiment 2
Continuous tower-type reactive mode:The feed weight ratio for controlling metatitanic acid tetra isopropyl ester, aniline and acetone is 1:450:1100.Benzene For amine from tower top continuous feed, acetone from bottom of towe gas-phase feed, carries out successive reaction, reaction pressure is normal after vaporization in tower Pressure, reaction temperature are 120 DEG C, and when material residence time in tower is 5 small, the water that excessive acetone is produced with reaction passes through company The fractionating column of reaction tower top is connected on, while recycles acetone and the water of separation reaction generation, reacts the polycondensation of the antioxidant TMQ of generation Liquid continuously flows into bottom of towe receiving slit, and the wherein conversion ratio of aniline is 80.4%.Afterwards by antioxidant TMQ polycondensation liquid, add 5% sodium hydroxide 3g, is neutralized to alkalescent, stratification, and under -0. 098MPa vacuum of upper oil phase process, unreacted benzene is recycled in vacuum distillation After amine, unpolymerized TMQ monomers, control 230 DEG C of material temperature（The aniline of recycling continues set with monomer and is used in reacting）, kettle liquid is through being granulated Obtained antioxidant TMQ finished products, the once through yield 83.2% of continuous process, wherein, the effective body contents 74.2% of antioxidant TMQ；Benzene Amine is used to react with monomer set, product TMQ effective yields 99.6%.
Embodiment 3
Batch tank reactive mode：250g aniline and 2g tetra-n-butyl titanates catalyst are disposably put into 1000m1 with stirring Four mouthfuls of burnings of device, thermometer and discharging pipeline (being connected to a fractionating column, make the water that acetone is produced with reaction enter fractionating column) In bottle, 1600g acetone is fed by the way of metering pump continuous charging, when the charging reaction time is 4 small.Under normal pressure, control Reaction temperature processed is 140 DEG C, and reaction water is recycled acetone with excessive acetone and separates reaction water, kettle liquid at the same time by fractionating column For TMQ polycondensation liquid, aniline conversion per pass can reach 81.5% in reaction.Add 25% sodium acid carbonate 1g, be neutralized to alkalescent, it is quiet Put layering, under upper oil phase process -0.098MPa vacuum, aniline, the TMQ monomers of vacuum distillation recycling end reaction, control material temperature 210 DEG C, antioxidant TMQ finished products are made through being granulated, once through yield 85.2%, wherein, effective body in antioxidant TMQ finished products (two, 3rd, the tetramer) content can reach 73.2%, aniline and monomer set be used to be condensed and polymerisation after, product TMQ's effectively receives 98.2 % of rate.
Embodiment 4
Continuous tower-type reactive mode：The feed weight ratio for controlling metatitanic acid diisopropyl ester, aniline and acetone is 1:300:1000., For aniline from tower top continuous feed, acetone from bottom of towe gas-phase feed, carries out successive reaction, reaction pressure is after vaporization in tower Normal pressure, reaction temperature are 120 ~ 130 DEG C, and when adjusting material residence time in tower is 3 small, excessive acetone and reaction water pass through Fractionating column recycles acetone and separation reaction water at the same time, and the polycondensation liquid of obtained antioxidant TMQ continuously flows into bottom of towe receiving slit, aniline Conversion ratio be 84.9%, add 10% disodium phosphate soln 2g, be neutralized to alkalescent, stratification, upper oil phase process- Under 0.098MPa vacuum, vacuum distillation, controls 200 ~ 210 DEG C of material temperature, cooling, is granulated and antioxidant TMQ finished products, the catalysis is made Agent continuous process once through yield 84.4%, the effective body contents of TMQ can reach 68.2%.
Embodiment 5-18
Using the catalyst and experimental method of embodiment 1.In the case where other conditions are constant, by varying aniline when reacting With the ratio of acetone, the ratio of aniline and catalyst, different reaction temperatures and reaction time, reaction formation investigate the list of reaction Journey conversion ratio and the effective body content of product, the results are shown in Table 1 for it:
Table 1：
Embodiment Aniline/acetone weight ratio Catalyst/aniline weight ratio Reaction temperature（℃） Reaction time（h） Vapo(u)rizing temperature（℃） Effective body content（%） Once through yield（%）
5 1/1 0.0005/1 110 4 180 72.1 40.0
6 1/1.5 0.05/1 110 6 210 68.3 80.1
7 1/4 0.01/1 150 4 230 71.4 78.4
8 1/6 0.002/1 110 4 200 71.0 73.2
9 1/4 0.05/1 110 4 210 60.2 85.4
10 1/4 0.01/1 130 4 210 69.2 75.9
11 1/4 0.05/1 150 4 210 66.4 84.4
12 1/4 0.01/1 90 4 200 72.0 78.6
13 1/4 0.0005/1 120 4 200 74.2 36.8
14 1/4 0.01/1 120 6 200 72.2 77.9
15 1/4 0.01/1 100 8 200 67.3 78.5
16 1/4 0.01/1 120 4 260 73.5 74.7
17 1/4 0.01/1 120 1 200 70.6 80.2
18 1/4 0.01/1 100 10 230 54.2 88.5
Embodiment 19-32
Using the experimental method of embodiment 2.In the case where other conditions are constant, by varying catalyst, aniline during reaction With the ratio of acetone, the ratio of aniline and catalyst, different reaction temperatures and reaction time, reaction formation investigate the list of reaction Journey conversion ratio and the effective body content of product, the results are shown in Table 2 for it:
Table 2：
Embodiment Aniline/acetone weight ratio Catalyst Catalyst/aniline weight ratio Reaction temperature（℃） Residence time（h） Vapo(u)rizing temperature（℃） Effective body content（%） Once through yield（%）
19 1/4 Metatitanic acid tetra isopropyl ester 0.05/1 130 6 200 71.2 77.0
20 1/4 Metatitanic acid tetra isopropyl ester 0.02/1 130 4 200 74.3 66.1
21 1/4 Metatitanic acid tetra isopropyl ester 0.05/1 130 4 230 71.9 78.2
22 1/6 Metatitanic acid tetra isopropyl ester 0.05/1 110 4 200 71.4 73.1
23 1/1.5 Metatitanic acid diisopropyl ester 0.05/1 110 3 180 67.5 70.0
24 1/1 Metatitanic acid diisopropyl ester 0.01/1 130 4 210 63.2 55.9
25 1/4 Metatitanic acid diisopropyl ester 0.05/1 150 4 210 60.4 84.2
26 1/4 Metatitanic acid diisopropyl ester 0.01/1 90 4 200 74.0 53.6
27 1/4 Isopropyl titanate 0.0005/1 120 4 200 74.7 33.8
28 1/4 Tetrabutyl titanate 0.002/1 120 6 200 72.1 47.6
29 1/4 Tetra-n-butyl titanate 0.01/1 100 8 260 66.5 77.4
30 1/4 Metatitanic acid di-isooctyl 0.01/1 120 1 210 73.4 34.7
31 1/4 Metatitanic acid di-isooctyl 0.01/1 120 10 200 71.2 85.3
32 1/4 Metatitanic acid di-isooctyl 0.01/1 100 7 230 73.3 82.6
The foregoing is only a preferred embodiment of the present invention, is not intended to limit the invention, for those skilled in the art For member, the invention may be variously modified and varied.Within the spirit and principles of the invention, made any is waited to repair Change, equivalent substitution, improvement etc.（Such as use acetone derivatives, anil, aniline and acetone reaction intermediates）, should all wrap It is contained within protection scope of the present invention.

Claims (10)

  1. A kind of 1. preparation method of antioxidant TMQ, using aniline, acetone or isopropylidene acetone as raw material, in the effect of catalyst It is lower that rubber antioxidant TMQ is prepared using one-step method, it is characterised in that the catalyst includes titanate ester catalyst.
  2. 2. preparation method according to claim 1, it is characterised in that the titanate ester catalyst is four isopropyl of metatitanic acid One kind in ester, isopropyl titanate, tetrabutyl titanate, metatitanic acid diisopropyl ester, tetra-n-butyl titanate, metatitanic acid di-isooctyl.
  3. 3. preparation method according to claim 1, it is characterised in that the one-step method prepares rubber antioxidant TMQ's Reaction temperature is 90 ~ 150 DEG C, when the reaction time is 1 ~ 10 small.
  4. 4. preparation method according to claim 4, it is characterised in that the one-step method prepares rubber antioxidant TMQ's Reaction temperature is 110 ~ 130 DEG C, when the reaction time is 4 ~ 6 small.
  5. 5. preparation method according to claim 1, it is characterised in that the aniline and acetone or isopropylidene acetone Weight ratio is 1:The weight ratio of 1-6, the titanate esters and aniline is 0.0005 ~ 0.05:1.
  6. 6. the preparation method stated according to claim 5, it is characterised in that the aniline and acetone or the weight of isopropylidene acetone Amount is than being 1:1.5~4；Titanate esters and the weight ratio of aniline are 0.002 ~ 0.01:1.
  7. 7. preparation method according to claim 1, it is characterised in that the one-step method prepares rubber antioxidant TMQ and adopts With intermittent or continous way production technology.
  8. 8. preparation method according to claim 7, it is characterised in that the batch production technique is：By benzene feedstock Amine is disposably put into kettle with titanate esters, and acetone is fed using continuous dropwise addition mode, and controlling reaction temperature and time for adding, pass through Fractionating column on reaction kettle is directly separated recycling acetone, then acetone set is used in raw material storage tank, and reaction solution is neutralized with lye, Divide water, oil phase distills to obtain TMQ.
  9. 9. preparation method according to claim 7, it is characterised in that the continous way production technology is：By aniline, titanium For acid esters from tower top continuous feed, acetone, from bottom of towe gas-phase feed, carries out successive reaction, control reaction temperature after vaporization in tower Spend for 90 ~ 150 DEG C, when material residence time in tower is 3 ~ 7 small；Acetone is steamed at the same time with the water produced in reaction process, Recycling acetone is directly separated by fractionating column afterwards, the antioxidant TMA polycondensation reaction liquid of simultaneous reactions generation continuously flows into bottom of towe and connects Receive groove；TMQ reaction solutions in dump tank are neutralized with lye, divide water, oil phase distills to obtain TMQ.
  10. 10. a kind of antioxidant TMQ, it is characterised in that prepared using preparation method as claimed in any one of claims 1-9 wherein Obtain, TMQ bis-, three, tetramer content are 65 ~ 75%.
CN201610967017.3A 2016-10-28 2016-10-28 A kind of antioxidant TMQ and preparation method thereof Pending CN108003095A (en)

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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
CN110963965A (en) * 2018-09-30 2020-04-07 中国石油化工股份有限公司 Recycling method of waste residue in antioxidant AW production
CN111039863A (en) * 2018-10-12 2020-04-21 中国石油化工股份有限公司 Preparation method of rubber antioxidant TMQ
CN112142657A (en) * 2019-06-26 2020-12-29 中石化南京化工研究院有限公司 Preparation method of anti-aging agent TMQ
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CN113735766A (en) * 2020-05-27 2021-12-03 中石化南京化工研究院有限公司 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

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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
CN110963965A (en) * 2018-09-30 2020-04-07 中国石油化工股份有限公司 Recycling method of waste residue in antioxidant AW production
CN110963965B (en) * 2018-09-30 2022-10-18 中国石油化工股份有限公司 Recycling method of waste residue in antioxidant AW production
CN111039863A (en) * 2018-10-12 2020-04-21 中国石油化工股份有限公司 Preparation method of rubber antioxidant TMQ
CN111039863B (en) * 2018-10-12 2022-11-11 中国石油化工股份有限公司 Preparation method of rubber antioxidant TMQ
CN112142657A (en) * 2019-06-26 2020-12-29 中石化南京化工研究院有限公司 Preparation method of anti-aging agent TMQ
CN112142658A (en) * 2019-06-26 2020-12-29 中石化南京化工研究院有限公司 Preparation method of low primary amine antioxidant 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
CN113735766A (en) * 2020-05-27 2021-12-03 中石化南京化工研究院有限公司 Preparation method of anti-aging agent
CN113735766B (en) * 2020-05-27 2023-08-29 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
CN113402457A (en) * 2021-07-13 2021-09-17 宁波海利化工有限公司 Preparation method of efficient antioxidant RD
CN113402457B (en) * 2021-07-13 2022-05-27 宁波海利化工有限公司 Preparation method of efficient antioxidant RD

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