CN102153511A - Industrial synthetic method for rubber antioxidant (RD) - Google Patents
Industrial synthetic method for rubber antioxidant (RD) Download PDFInfo
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- CN102153511A CN102153511A CN 201010110589 CN201010110589A CN102153511A CN 102153511 A CN102153511 A CN 102153511A CN 201010110589 CN201010110589 CN 201010110589 CN 201010110589 A CN201010110589 A CN 201010110589A CN 102153511 A CN102153511 A CN 102153511A
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Abstract
The invention discloses a method for preparing a rubber antioxidant (RD). The method is characterized in that aniline and acetone which serve as raw materials are introduced into a reaction tower with a solid acid catalyst continuously to ensure that a reactant is subjected to a condensation reaction under the catalysis of the solid acid catalyst. The method is easy and convenient to operate, and aftertreatment burden and environmental burden are relieved.
Description
Technical field
The present invention relates to a kind of industrial process of chemical.Relate more specifically to the production method of rubber antioxidant.
Background technology
Rubber antiager RD is 2,2,4-trimethylammonium-1, the oligopolymer of 2-dihydroquinoline, the polymerization degree is 2～4, is a kind of ketoamine class anti-aging agent, to amber powder or thin slice, as rubber antioxidant, is one of rubber antioxidant product that has the call on the domestic and international market for faint yellow mainly.
Anti-aging agent RD is to be catalyzer with acid, and aniline and acetone are changed into 2,2 by condensation, 4-trimethylammonium-1, and 2-dihydroquinoline monomer will make the gained monomer polymerization reactions become dimer or polymer then.The synthetic method of anti-aging agent RD can be divided into single stage method and two-step approach.Two-step approach is that at first condensation makes 2,2,4-trimethylammonium-1,2-dihydroquinoline monomer, remove excess reactant and other low-boiling-point substance after, under acidic conditions, carry out monomeric polymerization again; And single stage method is that monomer preparation and polyreaction are finished simultaneously, and then separates unnecessary reactant and other low-boiling-point substance.The two-step process process is long, consumes greatly, but the working substance content height in the products obtained therefrom; And the single stage method process is simple, consumes for a short time, but working substance content is low.
In the industrial preparative method of existing anti-aging agent RD, no matter be single stage method or two-step approach, all adopt still reaction method intermittently, that is, raw material and catalyzer are thrown in the reactor quantitatively, do corresponding aftertreatment again after reaction for some time.Because the per pass conversion of raw material aniline is very low during synthon, generally between 30～50%, complex operation, production cost height, problem such as environment is poor, and production efficiency is low.
Summary of the invention
The object of the present invention is to provide a kind of new industrial method that is used for synthetic anti-aging agent RD, with the low problem of production efficiency that prior art is provided.
Method of the present invention is that aniline and acetone as raw material are fed the reaction tower that solid acid catalyst is housed continuously, makes it to react in fixed bed under the catalysis of solid acid catalyst.
In the method for the invention, the throughput ratio of described aniline and acetone is preferably 1 by weight: 2-5 is preferably 1: 2-3.
In a kind of embodiment, the condensation reaction of aniline and acetone and generate and monomericly further be aggregated in the reaction tower step and finish.In this case, the temperature maintenance of reaction bed is at 80-150 ℃ in the tower, and preferably at 100-135 ℃, the residence time of material in tower is 8-25 hour, is preferably 15-20 hour.
In another embodiment, described polymerization is to carry out separately outside reaction tower.In this case, the temperature maintenance of reaction bed is at 80-150 ℃ in the tower, and preferably at 100-135 ℃, the residence time of material in tower is 0.5-hour, is preferably 2-7 hour.
Method of the present invention has compared with prior art been saved the separating step of producing the catalyzer in the rubber antiager RD process, has also therefore saved the loss when applying mechanically catalyzer, has saved the treatment time simultaneously.In addition,, alleviated the burden of aftertreatment greatly, also alleviated environmental pressure owing to do not re-use liquid acid catalyst.
Description of drawings
Fig. 1 is the synoptic diagram that is used for the reaction unit of one embodiment of the invention.
Fig. 2 is the operational flowchart of one embodiment of the invention.
Embodiment
Be described in further detail below in conjunction with the industrial preparative method of the drawings and specific embodiments rubber antiager RD of the present invention:
In continuous tower reaction of the present invention, utilize fixed bed or trickle-bed reactor, and in reactor the filling solid acid catalyst.Particularly, solid acid catalyst is seated in the reaction tower, aniline is from the cat head continuously feeding, and acetone from the continuously feeding of tower spirit phase, carries out successive reaction under the catalysis of the solid acid catalyst of two kinds of raw materials in being in fixed bed after vaporization.
Fig. 1 is the synoptic diagram that is used for the reaction unit of one embodiment of the invention.As shown in Figure 1, this reaction unit comprises reaction feed liquid receiver 1, and acetone vaporization back opening for feed 2 is equipped with the reaction tower 3 of catalyzer, aniline opening for feed 4, reaction back acetone and steam outlet 5.
Being used for solid acid catalyst of the present invention is storng-acid cation exchange resin, vinylbenzene-divinyl benzene series storng-acid cation exchange resin normally, operable example comprises 732 types, 734 types, DH type, D001 type, D002 type, D061 type, D072 type, JK008 type etc., or their composition, most preferably being D002 is storng-acid cation exchange resin.
The matrix of storng-acid cation exchange resin is except can being made by other organic monomer polymerizations by vinylbenzene or vinylformic acid (ester) polymerization.As phenolic aldehyde system (FP), epoxy system (EPA), vinylpyridine system (VP), urea aldehyde system (UA) etc.Strong acid group in the resin is sulfonic group normally.Except that sulfonic group, can also hang other acidic-group in the resin matrix in addition, for example-COOH.
As preferably, solid acid catalyst of the present invention is to be that material is composited by above-mentioned storng-acid cation exchange resin and extra aromatic sulphonic acid.About the detailed content of this composite catalyst, be disclosed in the applicant's the Chinese patent application 200910215840.9, the detailed content of its disclosure is incorporated this paper into the form of quoting.
Above-mentioned catalyzer needs reactivate behind life-time service.At this moment, only needing that above-mentioned catalyzer is stirred the time that suits in dilute hydrochloric acid gets final product.
Successive reaction pattern of the present invention can be used for single stage method and two-step approach.So-called single stage method is meant: by the control reaction conditions, carry out polyreaction in condensation reaction, but reaction mixture need not to obtain product through special processing straight run distillation.In two-step approach, the mixture after the condensation is handled, obtain the monomer of higher degree, make monomer polymerization again.
In single stage method, composite solid-acid catalyst is disposable to be seated in the tower, aniline is from the cat head continuously feeding, acetone is after vaporization, from the charging of tower spirit phase, in tower, carry out successive reaction, reaction pressure is a normal pressure, the temperature of reaction bed is 80-150 ℃ in the tower, more excellent is 100-135 ℃, and optimum is 120-130 ℃, by regulating the residence time of material in tower, realize the disposable purpose that reaches condensation polymerization, be generally 8-25 hour, more excellent is 15-20 hour, and optimum is 16-18 hour, regulate the inlet amount of acetone simultaneously, general aniline and acetone weight ratio are 1: 2-5, and more excellent is 1: 2-3, optimum are 1: 2-2.5, the water that excessive acetone and reaction produce reclaims simultaneously by the distillation tower of ligation cat head, the anti-aging agent RD feed liquid that reaction generates continuously flows into Receiving bin at the bottom of the tower, after directly under-0.098Mpa vacuum reclaim unreacted aniline, distillation temperature is controlled at 240-280 ℃, optimum is 260-270 ℃, to reclaim unreacted aniline and monomer.Still material cooling back granulation makes the anti-aging agent RD finished product.The anti-aging agent RD product that makes, dimer content 25-35%, two, three, tetramer content 50-60%.
Compare with the single stage method that adopts step still reaction method, successive reaction pattern of the present invention, disposable composite solid-acid catalyst is seated in the tower, aniline is from the cat head continuously feeding, and acetone is after vaporization, from the continuously feeding of tower spirit phase, continual continuous production, shorten the production time, improved production rate, formed the suitability for industrialized production scale, simultaneously, the successive reaction pattern in the process of reaction, can reclaim raw material excessive in the reaction simultaneously and remove waste material in reaction, the raw material that reclaims can reuse, reduced the waste of raw material, saved cost, and the working substance content of the anti-aging agent RD product that generates through this reaction obviously raises.
In two-step approach, the monomeric feed liquid of RD that contains that condensation can be made is directly carried out next step polymerization.Specifically, aniline and acetone were stopped 0.5-10 hour in tower under normal pressure, more excellent is 1-8 hour, optimum is 2-6 hour, the reaction bed temperature is 80-150 ℃ in the tower, more excellent is 100-135 ℃, and optimum is 120-130 ℃, and the water that excessive acetone and reaction produce reclaims continuously by the distillation tower that is connected cat head.The condensated liquid that obtains (wherein containing anti-aging agent RD monomer, aniline and a spot of RD dimer and tripolymer etc.) continuously flows into Receiving bin at the bottom of the tower, through the excessive aniline of reclaim under reduced pressure, the still material changes in the polymeric kettle, and after regulating acidity, carries out polyreaction under the normal pressure, polymeric reaction temperature is 70-130 ℃, more excellent is 80-110 ℃, and optimum is 95-105 ℃, and the reaction times is 4-10 hour, more excellent is 5-8 hour, and optimum is 6-7 hour.
In aftertreatment, need remove the acidic substance in the mixture, for example the hydrochloric acid of Yin Ruing also needs to reclaim unreacted aniline.In order to remove acidic substance, can neutralize acid with a spot of alkaline solution.Preferably, in and the time can also introduce organic solvent, to reduce monomer or the polymkeric substance meltage in the aqueous solution.In a kind of embodiment,, add diluted alkaline again and neutralize with dilution with toluene reaction back feed liquid, branch vibration layer, oil reservoir reclaims toluene by normal pressure, and distillation is reclaimed under-0.098MPa vacuum does not have complete polymeric monomer, residuum is controlled at 240-280 ℃, and optimum is 260-270 ℃.Still material cooling back granulation makes the anti-aging agent RD finished product.Dimer content is generally 50-60%, and two, three, the tetramer is 70-80%.
As the another kind of embodiment of two-step approach, the monomer that condensation can be made steams from mixture, makes highly purified monomer polymerization become dimer or polymer then.Particularly, condensated liquid to Receiving bin at the bottom of the inflow tower after the condensation reaction carries out underpressure distillation, to reclaim unreacted aniline, continues then to reclaim 2,2,4-trimethylammonium-1,2-dihyaroquinoline monomer, the control monomer content is 〉=85%, be preferably 〉=90%, best 〉=94%, after the monomer that reclaims is directly added after hydrochloric acid regulates feed acidity, carry out polyreaction under the normal pressure.
Compare with the two step method that adopts step still reaction method, successive reaction pattern two step method of the present invention has been heightened the working substance content of anti-aging agent RD product effectively on the basis that comprises the single stage method advantage.
Embodiment 1
The D002 storng-acid cation exchange resin of 100g is added in the there-necked flask of band stirring, thermometer, tail gas condensation absorption system of 500ml, add p-methyl benzenesulfonic acid 7.5g then, the hydrochloric acid that adds 250g 5% again, normal temperature and pressure stirred 30 minutes down, static 2 hours, repeat 1-2 time after, filter, dry, used oven heat dry 2-4 hour, the cooling back is standby.
Embodiment 2 (reference examples)
During employing still reaction at intermittence, the agitator that has with the disposable input 1000ml of composite solid-acid catalyst 50g of the aniline of 250g and embodiment 1, thermometer and discharging pipeline (are connected to a distillation tower, make acetone and the water that reaction produces enter distillation tower) four-hole boiling flask in, acetone 1750g adopts the mode charging of volume pump continuous charging, the charging reaction time is 8 hours, reaction pressure is a normal pressure, temperature of reaction is for being 135-140 ℃, water that produces during reaction and excessive acetone reclaim the water of acetone and separating reaction generation simultaneously by distillation tower, the aniline per pass conversion 78% of condensation reaction, anti-aging agent RD condensation feed liquid, after reclaiming aniline under the process-0.098MPa vacuum, directly add hydrochloric acid (30%) 17.5g and regulate feed acidity, carry out polyreaction under the normal pressure, temperature of reaction is 95-100 ℃, reaction times is 6 hours, after add toluene 50g dilution feed liquid, the alkali lye of adding 30% neutralizes, branch vibration layer after the static layering, oil reservoir reclaims toluene by normal pressure, distillation is reclaimed under-0.098MPa vacuum does not have complete polymeric monomer to apply mechanically, monomeric one way polymerisation conversion 70%, warm 260-280 ℃ in control material, still material cooling back granulation makes the anti-aging agent RD finished product.The anti-aging agent RD product 135g that makes, one way yield 54%, aniline and monomer cover are used for the effective yield 98% of the product RD after condensation and the polyreaction, dimer content 52%, two, three, tetramer content 74% in the analysed preparation anti-aging agent RD.
As embodiment 1 preparation solid acid catalyst, but adopt continuous tower reaction pattern, be seated in the tower the 50g composite solid-acid catalyst is disposable, control aniline is 1: 5 with the feed weight ratio of acetone.Aniline is from the cat head continuously feeding, and acetone from the charging of tower spirit phase, carries out successive reaction in tower after vaporization, and reaction pressure is a normal pressure, and temperature of reaction is 120-130 ℃.Regulating material residence time in tower is 2 hours, reclaims the water of excessive acetone and separating reaction generation simultaneously by the distillation tower that is connected the reaction cat head.The feed liquid of the anti-aging agent RD that reaction generates continuously flows into Receiving bin at the bottom of the tower.The schema of present embodiment as shown in Figure 2.The transformation efficiency 82% of analysis and investigation aniline.Anti-aging agent RD condensation feed liquid 175g, after reclaiming aniline under the process-0.098MPa vacuum, directly add hydrochloric acid (30%) 17.5g and regulate feed acidity, carry out polyreaction under the normal pressure, temperature of reaction is 95-100 ℃, reaction times is 6 hours, after add toluene 50g dilution feed liquid, the alkali lye of adding 30% neutralizes, branch vibration layer after the static layering, and oil reservoir reclaims toluene by normal pressure, distillation is reclaimed under-0.098MPa vacuum does not have complete polymeric monomer to apply mechanically, monomeric one way polymerisation conversion 73%, warm 260-280 ℃ in control material, still material cooling back granulation makes the anti-aging agent RD finished product.The anti-aging agent RD product 140g that makes, one way yield 61%, aniline and monomer cover are used for the effective yield 99% of the product RD after condensation and the polyreaction, dimer content 54%, two, three, tetramer content 76% in the analysed preparation anti-aging agent RD.
By the reaction process of embodiment 2 and embodiment 3 as can be known, example 2 adopts intermittent type, and example 3 adopts continous way, and its effect is better than embodiment 2, simultaneously, embodiment 3 continuous processes: saved filtration, the catalyzer cover time spent adds and loss, has also saved the treatment time, the corresponding throughput that increased, improved production environment simultaneously, it has obviously improved production efficiency, with being applicable to suitability for industrialized production.
It is evident that method of the present invention is not limited to above-mentioned concrete aniline and acetone raw material, also can be anils and/or acetone derivatives.For example, as acetone derivatives, can be diacetone alcohol (diacetone alcohol) and mesityl oxide (mesityloxide).When employing is different from the raw material of acetone and aniline, may need suitably to regulate the processing condition of condensation reaction or polyreaction.These raw materials change belong to and are equal to replacement to of the present invention.
Although the present invention is illustrated with reference to accompanying drawing and preferred embodiment, obviously, for a person skilled in the art, under the prerequisite that does not deviate from the spirit and scope of the present invention, can make various changes and variation to the present invention.Therefore, various change of the present invention, the content that changes by appending claims and equivalent thereof contain.
Claims (10)
1. method of producing rubber antiager RD, it is characterized in that, raw material is fed the reaction tower that solid acid catalyst is housed continuously, make reactant under the catalysis of solid acid catalyst, carry out condensation reaction, wherein, described raw material is aniline and acetone or their derivative.
2. method according to claim 1, described raw material are aniline and acetone.
3. method according to claim 1 and 2 is characterized in that, carries out following reaction in described reaction tower simultaneously:
The condensation reaction of aniline and acetone generates anti-aging agent RD monomer 2,2,4-trimethylammonium-1,2-dihydroquinoline; With
The monomeric polymerization of described anti-aging agent RD generates anti-aging agent RD.
4. method according to claim 3 is characterized in that, the temperature maintenance of reaction bed is at 80-150 ℃ in the described tower, and the residence time of material in tower is 8-25 hour.
5. method according to claim 4 is characterized in that, the temperature maintenance of reaction bed is at 100-135 ℃ in the described tower, and the residence time of material in tower is 15-20 hour.
6. method according to claim 2, it is characterized in that, in described reaction tower, carry out condensation reaction, to generate the anti-aging agent monomer, wherein, the reaction bed temperature is 80-150 ℃, and aniline and acetone stopped 0.5-8 hour in tower under normal pressure, outside described reaction tower, carry out polyreaction, to obtain described anti-aging agent RD.
7. method according to claim 6 is characterized in that, carries out condensation reaction in described reaction tower, and to generate the anti-aging agent monomer, wherein, the reaction bed temperature is 100-135 ℃, and aniline and acetone stopped 2-7 hour in tower under normal pressure.
8. according to claim 5 or 6 described methods, it is characterized in that, the feed liquid after the polymerization is kept 260-270 ℃ temperature and decompression state.
9. according to claim 6 or 7 described methods, it is characterized in that the monomer that condensation is made steams from mixture, make highly purified monomer polymerization become dimer or polymer then.
10. according to each described method of claim 1-9, wherein, feed aniline, feed acetone at the bottom of the tower through vaporization from cat head, excessive acetone reclaims by the distillation tower that is connected the reaction cat head with the water that reacts generation, receiving trap at the bottom of the feed liquid inflow tower of condensation or polymerization generation.
Priority Applications (14)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010110589 CN102153511B (en) | 2010-02-12 | 2010-02-12 | Industrial synthetic method for rubber antioxidant (RD) |
| US12/943,930 US8293137B2 (en) | 2009-12-30 | 2010-11-10 | Solid acid catalyst and method for preparing and using the same |
| MYPI2010005471A MY158181A (en) | 2009-12-30 | 2010-11-19 | Solid acid catalyst and method for preparing and using the same |
| JP2010262798A JP5739140B2 (en) | 2009-12-30 | 2010-11-25 | Solid acid catalyst, method for producing the same, and method for synthesizing rubber anti-aging agent RD |
| EP10193059.2A EP2354127A3 (en) | 2009-12-30 | 2010-11-30 | Solid acid catalyst and method for preparing and using the same |
| KR1020100122542A KR101257832B1 (en) | 2009-12-30 | 2010-12-03 | Solid acid catalyst and method for preparing and using the same |
| CA2724338A CA2724338C (en) | 2009-12-30 | 2010-12-07 | Solid acid catalyst and method for preparing and using the same |
| TR2010/10211A TR201010211A2 (en) | 2009-12-30 | 2010-12-08 | Solid acid catalyst and method of preparation and use. |
| EA201001800A EA018157B1 (en) | 2009-12-30 | 2010-12-15 | Solid acid catalyst and method for preparing and using the same |
| BRPI1005271-2A BRPI1005271B1 (en) | 2009-12-30 | 2010-12-16 | SOLID ACID CATALYST AND METHOD FOR PREPARATION AND USE |
| MX2010014004A MX2010014004A (en) | 2009-12-30 | 2010-12-16 | Solid acid catalyst and method for preparing and using the same. |
| MX2013004397A MX367411B (en) | 2009-12-30 | 2010-12-16 | Solid acid catalyst and method for preparing and using the same. |
| ARP100104715A AR082362A1 (en) | 2009-12-30 | 2010-12-17 | SOLID ACID CATALYST; PROCESS FOR PREPARATION; METHOD FOR USE; PROCESS FOR PREPARING RUBBER ANTIOXIDANT RD |
| US13/623,037 US9186660B2 (en) | 2009-12-30 | 2012-09-19 | Solid acid catalyst and method for preparing and using the same |
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| CN 201010110589 CN102153511B (en) | 2010-02-12 | 2010-02-12 | Industrial synthetic method for rubber antioxidant (RD) |
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| CN102153511A true CN102153511A (en) | 2011-08-17 |
| CN102153511B CN102153511B (en) | 2013-05-15 |
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| CN 201010110589 Active CN102153511B (en) | 2009-12-30 | 2010-02-12 | Industrial synthetic method for rubber antioxidant (RD) |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| CN103613537A (en) * | 2013-11-11 | 2014-03-05 | 河南省开仑化工有限责任公司 | Clean high-efficiency synthetic method of high-content anti-aging agent RD |
| CN103694169A (en) * | 2012-09-28 | 2014-04-02 | 中国石油化工股份有限公司 | Method for synthesis of 2,2,4-trimethyl-1,2-dihydroquinoline and polymer thereof by utilizing microchannel reactors |
| CN105017144A (en) * | 2014-04-25 | 2015-11-04 | 江苏圣奥化学科技有限公司 | Rubber aging inhibitor RD and preparation method for same |
| CN107416911A (en) * | 2017-09-01 | 2017-12-01 | 河北正润环境科技有限公司 | The device and method of polymerized ferric-aluminum chloride is prepared using steel finishing pickle liquor |
| CN109438341A (en) * | 2018-10-24 | 2019-03-08 | 科迈化工股份有限公司 | Anti-aging agent TMQ and preparation method thereof |
| 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 |
| CN113402457A (en) * | 2021-07-13 | 2021-09-17 | 宁波海利化工有限公司 | Preparation method of efficient antioxidant RD |
| 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 |
| CN114773265A (en) * | 2022-06-21 | 2022-07-22 | 科迈(天津)建设工程股份有限公司 | Synthesis process of rubber antioxidant RD |
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| 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 |
| 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 |
| CN103694169B (en) * | 2012-09-28 | 2016-04-06 | 中国石油化工股份有限公司 | Micro passage reaction is utilized to synthesize the method for 2,2,4-trimethylammonium-1,2-dihydroquinoline and polymkeric substance thereof |
| CN103694169A (en) * | 2012-09-28 | 2014-04-02 | 中国石油化工股份有限公司 | Method for synthesis of 2,2,4-trimethyl-1,2-dihydroquinoline and polymer thereof by utilizing microchannel reactors |
| CN103613537A (en) * | 2013-11-11 | 2014-03-05 | 河南省开仑化工有限责任公司 | Clean high-efficiency synthetic method of high-content anti-aging agent RD |
| CN105017144B (en) * | 2014-04-25 | 2019-05-28 | 圣奥化学科技有限公司 | A kind of rubber antiager RD and preparation method thereof |
| CN105017144A (en) * | 2014-04-25 | 2015-11-04 | 江苏圣奥化学科技有限公司 | Rubber aging inhibitor RD and preparation method for same |
| CN107416911A (en) * | 2017-09-01 | 2017-12-01 | 河北正润环境科技有限公司 | The device and method of polymerized ferric-aluminum chloride is prepared using steel finishing pickle liquor |
| CN107416911B (en) * | 2017-09-01 | 2023-06-23 | 河北正润环境科技有限公司 | Device and method for preparing polyaluminium ferric chloride by utilizing steel finishing pickling waste liquid |
| CN109438341A (en) * | 2018-10-24 | 2019-03-08 | 科迈化工股份有限公司 | Anti-aging agent TMQ and preparation method thereof |
| CN109438341B (en) * | 2018-10-24 | 2022-04-08 | 科迈化工股份有限公司 | Anti-aging agent TMQ and preparation method thereof |
| 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 |
| 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 |
| 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 |
| CN114773265A (en) * | 2022-06-21 | 2022-07-22 | 科迈(天津)建设工程股份有限公司 | Synthesis process of rubber antioxidant RD |
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